Kyushu University [Atsushi Takahara (Post-doctoral Fellow) Research Center for Negative Emissions Technologies, CO2 Capture Research Division]

Atsushi Takahara

Last modified date：2021.09.24

Post-doctoral Fellow / CO2 Capture Research Division / Research Center for Negative Emissions Technologies

Papers

1.	Ken Kojio, Shuhei Nozaki, Atsushi Takahara, Satoshi Yamasaki, Influence of chemical structure of hard segments on physical properties of polyurethane elastomers a review, Journal of Polymer Research, 10.1007/s10965-020-02090-9, 27, 6, 2020.06, Hard segments of polyurethanes (PUs) are generally formed from diisocyanate and diol. Diol can be replaced with triol and thiol. These chemical structures of hard segments strongly affect not only a microphase separated structure but mechanical properties of resultant PUs. In this review, we focus on the relationship between chemical structure like symmetry and bulkiness of diisocyanate and mechanical properties of PU. Then, influence of hard segment content, incorporation of 1,1,1-trimethylol propane with trifunctional groups, and alkyldithiol was reviewed mainly on trans-1,4-bis(isocyanatomethyl) cyclohexane-poly(oxytetramethylene) glycol-based PU..
2.	Manus Sriring, Adun Nimpaiboon, Sirirat Kumarn, Keiko Higaki, Yuji Higaki, Ken Kojio, Atsushi Takahara, Chee Cheong Ho, Jitladda Sakdapipanich, Film formation process of natural rubber latex particles roles of the particle size and distribution of non-rubber species on film microstructure, Colloids and Surfaces A: Physicochemical and Engineering Aspects, 10.1016/j.colsurfa.2020.124571, 592, 2020.05, Natural rubber (NR) films from various mixing ratios of large- (LRP) and small rubber particles (SRP) were prepared through latex and solution casting methods. Film-forming behaviours of the resulting films were investigated by monitoring their surface characteristics using atomic force microscopy (AFM). When the SRP portion was higher, the surface of the latex-cast films was found to be smoother as smaller particles protruded out of the surface less than larger ones did. AFM phase micrographs revealed a hexagonal shape of packed rubber particles (RPs) of the LRP film, while the RPs in the other samples were sphere-like. After aging under ambient conditions, the packed RPs were flattened while retaining their RP boundaries, creating a supporting framework within the rubber matrix. On the contrary, when the rubber film was cast from a toluene solution, the characteristic of RP boundaries disappeared and became aggregates of the membrane components on the film surface. The latex-cast films performed much better in mechanical strength than the solution-cast films did due to the destruction of the supporting framework arisen from the non-rubber components at the RP boundaries of the solution-cast film. An inhomogeneous density distribution produced by the non-rubber aggregates in the latex-cast films was observed in small angle X-ray scattering measurements..
3.	Wei Ma, Bruno Ameduri, Atsushi Takahara, Molecular Aggregation Structure and Surface Properties of Biomimetic Catechol-Bearing Poly[2-(perfluorooctyl)ethyl acrylate] and Its Application to Superamphiphobic Coatings, ACS Omega, 10.1021/acsomega.0c00439, 5, 14, 8169-8180, 2020.04, The molecular aggregation structure and surface properties of a catechol-bearing fluoropolymer, P(FAC₈-co-DOPAm), which was synthesized by conventional radical copolymerization of 2-(perfluorooctyl)ethyl acrylate (FAC₈) and N-(3,4-dihydroxyphenethyl)acrylamide (DOPAm), and its application to the superamphiphobic surfaces are presented. The crystallinity of P(FAC₈-co-DOPAm) was lower than that of poly[2-(perfluorooctyl)ethyl acrylate] (PFAC₈). The perfluoroalkyl (R_f) groups were ordered on the surface with CF₃ terminals exposed to air, and the R_f ordering was influenced by thermal history: the thermally annealed film exhibited higher R_f ordering than the unannealed one. The surface free energy was estimated to be γ= 7.32 mJ m^-2 for both the unannealed and annealed films. Based on contact angle measurement, various interfacial structures of water and oils in accordance with the surface aggregation structure of R_f groups were proposed. Dewetting of the PFAC₈ film at elevated temperature was suppressed by the introduction of catechol groups in the backbone. The degradation temperature of PFAC₈ was improved significantly, and the evaporation of the low molar mass-polymer was inhibited by the introduction of catechol groups under both nitrogen and air atmospheres. The hydrophobicity of the copolymer films could be healed after the surface was damaged by vacuum ultraviolet (VUV) irradiation. This copolymer was used to create superamphiphobic fabrics and halloysite nanotube (HNT)-based organic/inorganic hybrid coatings successfully. Wetting behaviors of the superamphiphobic fabrics and coatings both follow the Cassie-Baxter wetting model..
4.	Masaru Mukai, Chao Hung Cheng, Wei Ma, Mi Chin, Chia Hsin Lin, Shyh Chyang Luo, Atsushi Takahara, Synthesis of a conductive polymer thin film having a choline phosphate side group and its bioadhesive properties, Chemical Communications, 10.1039/c9cc09949b, 56, 18, 2691-2694, 2020.03, A conductive polymer thin film having choline phosphate as the side group was prepared. Quartz crystal microbalance (QCM) was employed to evaluate the adsorption of the model protein, bovine serum albumin (BSA), on the films deposited on indium tin oxide (ITO) electrodes. Cell adsorption on the film was evaluated by a fibroblast NIH3T3..
5.	Wei Ma, Gérald Lopez, Bruno Ameduri, Atsushi Takahara, Fluoropolymer Nanoparticles Prepared Using Trifluoropropene Telomer Based Fluorosurfactants, Langmuir, 10.1021/acs.langmuir.9b03914, 36, 7, 1754-1760, 2020.02, A fluorosurfactant based on 3,3,3-trifluoropropene (TFP) telomer was synthesized as an environmentally friendly alternative to perfluorooctanoic acid (PFOA) using TFP and 2-iodoperfluoropropane ((CF₃)₂CF-I) as starting materials. TFP telomerization was initiated by addition of di-tert-butylperoxide in the presence of (CF₃)₂CF-I as a chain transfer agent. The surfactant was obtained by modification of the iodine end-group on the TFP telomer to form an allylic functionality followed by the addition of thioglycolic acid via a thiol-ene reaction. The resulting fluorosurfactant exhibited a lower critical micellar concentration (CMC = 0.87 g·L^-1) than that of PFOA (CMC = 3.0 g·L^-1). This surfactant was used to prepare fluoropolymer nanoparticles by solvent evaporation from a solution composed of the surfacant and poly[2-(perfluorobutyl)ethyl methacrylate]. The oil-in-water emulsion was initially formed due to the adsorption of the surfactant molecules at the oil/water interface and subsequently converted into a nanoparticle suspension after solvent evaporation. Because of the strong hydrophobic interactions between the fluorinated surfactant tail and fluoropolymer, the obtained nanoparticle suspension was quite stable against water dialysis..
6.	Yuma Morimitsu, Hisao Matsuno, Noboru Ohta, Hiroshi Sekiguchi, Atsushi Takahara, Keiji Tanaka, Mechanical Stabilization of Deoxyribonucleic Acid Solid Films Based on Hydrated Ionic Liquid, Biomacromolecules, 10.1021/acs.biomac.9b01207, 21, 2, 464-471, 2020.02, Solid films of deoxyribonucleic acid (DNA) containing a hydrated ionic liquid, choline dihydrogen phosphate (CDP), were prepared by a solvent-casting method. Thermal properties, aggregation structure, thermal molecular motion, and tensile properties of CDP-containing DNA films were examined by thermogravimetry (TG), wide-angle X-ray diffraction (WAXD) measurement, dynamic mechanical analysis (DMA), and tensile tests, respectively. The water retentivity of the films at room temperature was much improved with CDP. The packing density of DNA helical chains clearly depended on the amount of CDP in the film. A small amount of CDP contributed to the suppression of the B_I → B_II conformational transition and the cooperative motion of the DNA duplex in the film. The tensile properties of the film drastically changed in the presence of CDP. When the amount of hydrated CDP in the film increased, the mechanical response of the film changed from glassy-like to rubbery-like via a semicrystalline-like state. The above results make it clear that CDP plays two major roles as a water absorber and plasticizer in the DNA film. Thus, it can be concluded that the use of an ionic liquid as an additive significantly increases the possibility of using a DNA solid film as a structural material..
7.	Linlin Li, Akihiko Takada, Wei Ma, Shigenori Fujikawa, Miho Ariyoshi, Kosuke Igata, Maiko Okajima, Tatsuo Kaneko, Atsushi Takahara, Structure and Properties of Hybrid Film Fabricated by Spin-Assisted Layer-by-Layer Assembly of Sacran and Imogolite Nanotubes, Langmuir, 10.1021/acs.langmuir.9b03626, 36, 7, 1718-1726, 2020.02, A free-standing (biomacomolecule/synthetic inorganic nanotubes) hybrid film was fabricated through an alternative layer-by-layer (LBL) assembly of sacran and imogolite nanotubes. Sacran is a natural polysaccharide extracted from the cyanobacterium Aphanothece sacrum, while imogolite is a natural tubular aluminosilicate clay found in volcano ash. The hybrid film thickness increased linearly with the number of the bilayers, because of the interaction between the negatively charged surface of sacran and the positively charged surface of imogolite. UV-vis spectroscopy indicated that the LBL film exhibited good transparency. The surface morphology of the LBL film was smooth in the micrometer scale; many imogolite nanotubes were adsorbed onto the sacran layer, while no imogolite clusters were observed. Furthermore, the structure, stability, gas permeability, and mechanical properties of the LBL films were investigated..
8.	Manus Sriring, Adun Nimpaiboon, Sirirat Kumarn, Atsushi Takahara, Jitladda Sakdapipanich, Enhancing viscoelastic and mechanical performances of natural rubber through variation of large and small rubber particle combinations, Polymer Testing, 10.1016/j.polymertesting.2019.106225, 81, 2020.01, There have been several reports investigating independent properties of large- (LRP) and small rubber particles (SRP). This work envisaged that, when co-existing, they could offer exceptional viscoelastic and mechanical properties from both components. Latex samples of various mixing ratios were prepared and properties of their rubber films were investigated against those of pure LRP and SRP to find that those containing 10–30% SRP were the best in mechanical strength and elasticity. This could be due to the combination of stronger phospholipid linkages in the LRP and void-filling ability of the SRP. The presence of SRP was shown to enhance curability in the vulcanised samples resulting in better mechanical performance of the vulcanisates. The 70/30 (LRP/SRP) blend showed the best thermal aging resistance among the vulcanisates. This suggested that the mixing ratios of the LRP and SRP contents were tunable to improve desirable properties of rubber products of interest, both green and cured..
9.	Ya Ting Hsieh, Shuhei Nozaki, Makoto Kido, Kazutaka Kamitani, Ken Kojio, Atsushi Takahara, Crystal polymorphism of polylactide and its composites by X-ray diffraction study, Polymer Journal, 10.1038/s41428-020-0343-8, 2020.01, Polylactide (PLA) exhibits various types of crystal modifications depending on the preparation conditions, including the components. To solve the open question, a reliable calculation method for crystallinity, crystal forms, and composition in neat PLA and PLA composites was developed on the basis of temperature-dependent synchrotron wide-angle X-ray diffraction results. The relative composition of amorphous, α-form, and α’-form phases of PLA and its composites filled with halloysite nanotubes during heating was successfully obtained. It was found that only 47–56% of α’-form crystals transform into α-form crystals during a 2 °C/min heating process for PLA with a molecular weight of 54,300 g/mol. The loading of halloysite nanotubes decreases the cold crystallization and starting transition (α’ crystals transform into α-form crystals) temperatures of PLA. The crystallinity and the main diffraction peak intensity as a function of temperature were also analyzed. These results suggest that the α’-to-α form transition is a solid-solid phase transition..
10.	Yucheng Zhang, Chien Wei Chu, Wei Ma, Atsushi Takahara, Functionalization of Metal Surface via Thiol-Ene Click Chemistry Synthesis, Adsorption Behavior, and Postfunctionalization of a Catechol- And Allyl-Containing Copolymer, ACS Omega, 10.1021/acsomega.0c00259, 2020.01, Surface functionalization tailors the interfacial properties without impacts on the mechanical strength, which is beneficial for industry and daily applications of various metallic materials. Herein, a two-step surface functionalization strategy, (1) catechol-mediated immobilization of clickable agent and (2) postfunctionalization based on thiol-ene click reaction, is achieved using a copolymer, namely poly[2-(methacryloyloxy)ethylundec-10-enoate]-co-(N-(3,4-dihydroxyphenethyl) methacrylamide) [P(MEUE-co-DPMAm)]. To reduce the potential side reactions of allylic double bonds in allyl methacrylate during the polymerization, the MEUE are designed and synthesized with better control over the polymer chain growth. The surface functionalization via the two-step method is demonstrated using various thiols, e.g., hydrophobic, hydrophilic, and polymeric thiols under room conditions. Additionally, the hydrophobic-thiol-functionalized anodic aluminum oxide is found to be a candidate for the oil/water separation with a separation efficiency of ∼99.2%. This surface modifier provides practical insights into the further design of functional materials..
11.	Ryosuke Matsuno, Yota Kokubo, Shinji Kumagai, Shigeaki Takamatsu, Kazunobu Hashimoto, Atsushi Takahara, Molecular Design and Characterization of Ionic Monomers with Varying Ion Pair Interaction Energies, Macromolecules, 10.1021/acs.macromol.9b02731, 2020.01, Ionic liquid monomers with ion pair interaction energies ranging from 73.0 to 101.4 kcal/mol were designed by using the calculated electrostatic potential (ESP) values of the component ions. The ionic liquid monomers were classified as cationic monomers with an anionic counterion and anionic monomers with a cationic counterion. We evaluated the calculated ion pair interaction energy using counterion mobility as an indicator. One component of the ion pair was fixed onto a dielectric elastomer by using alkoxysilane coupling agents, while the counterion remained free to move under the applied voltage. We then measured the relative dielectric constant at 0.01 Hz, which is an indicator of the mobility of the counterion. The results showed a good correlation between the calculated ion pair interaction energy and the relative dielectric constant. The lower the ion pair interaction energy is, the easier the dissociation of the ion pair. From this result, we were able to prove the correlation between the calculated ion pair interaction energy and the mobility of the counterion. Furthermore, classification of other ion pair compounds and polyelectrolyte polymer brushes that follow the anion Hofmeister series based on ion pair interaction energies revealed the correlation between physical properties and the ionic structure. Various ionic compounds with desired physical properties can be designed by using the calculated ion pair interaction energies..
12.	Yi Liu, Yuji Higaki, Masaru Mukai, Atsushi Takahara, Molecular aggregation structure and water repellency of Poly(perfluorohexyl acrylate) with a carbamate linkage, polymer, 10.1016/j.polymer.2019.121846, 182, 2019.11, Liquid repellency of comb-shaped polyacrylates with perfluoroalkyl side-chains associates with the ordered structure of the side-chains at the surface. The molecular aggregation structure and surface properties of poly{2-[(perfluorohexylethyl)carbamate]ethyl}acrylate (PFAUr-C₆) were studied using differential scanning calorimetry (DSC), polarized optical microscopy (POM), powder wide-angle X-ray diffraction (WAXD), grazing incidence wide-angle X-ray diffraction (GI-WAXD), temperature-controlled Fourier transform infrared spectroscopy (FTIR), contact angle measurements, and X-ray photoelectron spectroscopy (XPS). Poly[2-(perfluorohexyl)ethyl]acrylate (PFA-C₆) was compared with PFAUr-C₆ to verify the effect of carbamate linkage on the aggregation structure and surface properties. The perfluorohexyl groups in PFAUr-C₆ produced a double-layered smectic structure, whereas the perfluorohexyl groups in PFA-C₆ showed no ordered structure. The double-layered smectic structure in PFAUr-C₆ was induced by the hydrogen bonding interaction in the carbamate linkers. PFAUr-C₆ showed poor water repellency similar to PFA-C₆ because of the rapid surface rearrangement. Although the perfluorohexyl groups produced smectic order structure at the film surface, the lack of positional order in the smectic layers and the low ordered structure content allowed the surface rearrangement..
13.	Ken Kojio, Tomoko Kajiwara, Saburo Yamamoto, Aya Fujimoto, Kento Fukada, Chigusa Nagano, Shiori Masuda, Chao Hung Cheng, Shuhei Nozaki, Kazutaka Kamitani, Atsushi Takahara, Direct visualization of the molecular orientation and microstructure of glassy transparent polymers after the scratch test based on optical microscopy and X-ray scattering, polymer, 10.1016/j.polymer.2019.121773, 181, 2019.10, The scratch test was conducted for polycarbonate (PC) and poly(methyl methacrylate) (PMMA) with a load-progressive mode. Changes in the molecular aggregation structure of PC and PMMA induced by the scratch test were investigated based on polarized optical microscopic observation and small-angle X-ray scattering (SAXS) measurement. The scratching coefficient of friction (SCOF), the ratio of tangential load to normal load, of PC was much larger than that of PMMA. The width and depth of the damage on the scratch path was increased monotonically with the increase in the normal load. Hardness obtained by nanoindentation and microindentation tests were similar to those with SCOF, indicating that compression resistance mainly governs the scratch properties. The polarized optical microscopic images revealed that molecules were oriented from the edge to the center of the scratch path at a certain acute angle for both PC and PMMA. SAXS measurement revealed that microfibrils were formed along the direction of stress for PC..
14.	Yasuhiro Matsuda, Takahiro Fukui, Shun ich Ishima, Atsushi Takahara, Shigeru Tasaka, Elevation of the flow temperature of gels formed by nano fibers of Poly(L-lactic acid) by surface crystallization induced by block copolymers, polymer, 10.1016/j.polymer.2019.121768, 181, 2019.10, Block copolymers of poly (L-lactic acid) (PLLA) and polystyrene with different lengths of PLLA blocks entered into the network structures of PLLA gels formed with complex crystals with solvent molecules. The induced changes of the structure and the flow temperature of the gels were investigated to elucidate the mechanism of the block copolymers to elevate the flow temperature. The block copolymer with shorter PLLA blocks elevated the flow temperature of the PLLA gels from 40 °C to 70 °C by immersing in the block copolymer solution with a lower concentration (0.5 wt%). For the block copolymers with longer PLLA blocks, higher concentrations (2.0 wt%) were necessary to elevate the flow temperature to 70 °C, and the flow temperature was elevated to 80 °C by immersing more concentrated solutions (3.0 wt%). This behavior can be explained by assuming that the surface crystallization of PLLA fibers induced by the block copolymers elevated the flow temperature to 70 °C, and the reinforcement of the fibers by spherical structure of the block copolymers elevated the flow temperature to 80 °C, was proposed based on the experimental results..
15.	Ken Kojio, Aya Fujimoto, Tomoko Kajiwara, Chigusa Nagano, Shiori Masuda, Chao Hung Cheng, Shuhei Nozaki, Kazutaka Kamitani, Hirohmi Watanabe, Atsushi Takahara, Advantages of bulge testing and rupture mechanism of glassy polymer films, polymer, 10.1016/j.polymer.2019.121632, 179, 2019.09, The advantages of bulge testing as a method of mechanical property analysis for polymer films was described. Deformation and rupture mechanisms of glassy polymer films during bulge testing were investigated by in situ molecular aggregation structure analyses. Heat-pressed polycarbonate (PC, weight-average molecular weight (M_w) = 38k) and poly(methyl methacrylate) (PMMA, M_w = 70k and 1.2 M (PMMA-70k and PMMA-1.2 M)) films were employed as transparent glassy polymers. Evaluations of molecular aggregation structures during bulge testing were conducted by polarized high-speed camera observation and wide-angle X-ray diffraction (WAXD) measurements. PC and PMMA-1.2 M films showed a yield point in their stress-strain curves, indicating ductility, while PMMA-70k film showed brittleness. WAXD measurements revealed that the distances between the main chains slightly increased with increasing strain. With increasing film strain above the yield point, a craze-like morphology with thinning of the film was seen for the PC film, likely due to the flexible PC molecules. Although it is difficult for PMMA molecules to orient along applied stress, a transition to the thinner state with the formation of wrinkled structures occurred for the PMMA-1.2 M film above the yield point. The transition to the thinner state, which corresponds to a discontinuous decrement of the cross-section area by deformation, might be categorized as two-dimensional crazing and/or shear deformation. PMMA-70k did not show such behavior because of the small number of entanglements. The use of a small amount of films in terms of thickness and size and the capability of observation of the entire film were given as advantages of the bulge test..
16.	Rahmawati Rahmawati, Shiori Masuda, Chao Hung Cheng, Chigusa Nagano, Shuhei Nozaki, Kazutaka Kamitani, Ken Kojio, Atsushi Takahara, Naoki Shinohara, Kazuki Mita, Kiminori Uchida, Satoshi Yamasaki, Investigation of Deformation Behavior of Thiourethane Elastomers Using in Situ X-ray Scattering, Diffraction, and Absorption Methods, Macromolecules, 10.1021/acs.macromol.9b00982, 52, 18, 6825-6833, 2019.09, The deformation behavior of polythiourethane (PTU) elastomers was investigated using in situ small-angle X-ray scattering (SAXS), wide-angle X-ray diffraction (WAXD), and X-ray absorption fine structure (XAFS) methods. Two PTUs were prepared from poly(oxytetramethylene) glycol, 1,4-bis(isocyanatomethyl) cyclohexane, and 1,4-butanedithiol (PTU-B) or 1,5-pentanedithiol (PTU-P). The effect of methylene length of the chain extender on molecular aggregation structure of PTU during the elongation process was evaluated. SAXS measurement revealed that the spacing of hard segment domains of PTUs increased and decreased in the directions parallel and perpendicular to the elongation direction and showed a constant value of strain above 2. The strain calculated from the spacing of the hard segment domains for PTU-B was larger than that for PTU-P, suggesting that well-developed hard segment domains were formed for PTU-B. WAXD measurement showed that strain-induced crystallization of the soft segment occurred at around the strain of 2. XAFS measurement showed that at the strain of 2 or 3, atoms in the vicinity of sulfur became more ordered, which is confirmed by the decrement of the extended XAFS Debye-Waller factor. It seems reasonable from these SAXS, WAXD, and XAFS results that the hard segment domains orientation occurred for both PTUs during the deformation process, followed by strain-induced crystallization of the soft segment. In addition, PTU-B exhibits more ordered hard segment domains that maintain their aggregation structure upon uniaxial deformation in comparison with PTU-P..
17.	Linlin Li, Wei Ma, Akihiko Takada, Nobuhisa Takayama, Atsushi Takahara, Organic-Inorganic Hybrid Films Fabricated from Cellulose Fibers and Imogolite Nanotubes, Biomacromolecules, 10.1021/acs.biomac.9b00881, 20, 9, 3566-3574, 2019.09, Owing to the increasing environmental awareness, nanocellulose/natural clay composites with improved mechanical performance have attracted growing interest due to their eco-friendly properties. In this study, hybrid films composed of cellulose fibers (CFs) and imogolite nanotubes (natural aluminosilicate nanotubes) were fabricated. We mainly studied the structure, density, and properties of the hybrid materials. Specifically, the hybrid materials were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), a rheological test, and wide-angle X-ray diffraction (WAXD). The mechanical properties of the hybrid materials were measured by a tensile test, which demonstrated that the mechanical properties of the hybrid films were considerably improved by the addition of imogolite up to 1 wt %; meanwhile, the thermal-mechanical properties of the hybrid film were also enhanced..
18.	Manus Sriring, Adun Nimpaiboon, Nattanee Dechnarong, Sirirat Kumarn, Yuji Higaki, Ken Kojio, Atsushi Takahara, Chee Cheong Ho, Jitladda Sakdapipanich, Pre-Vulcanization of Large and Small Natural Rubber Latex Particles Film-Forming Behavior and Mechanical Properties, Macromolecular Materials and Engineering, 10.1002/mame.201900283, 304, 9, 2019.09, The pre-vulcanized large rubber particle (LRP) and small rubber particle (SRP) latices are independently prepared to investigate their film-forming process and mechanical properties after being cast into films. The surface morphologies and roughness of both LRP and SRP films are found to be dependent on crosslink densities. The networks inside each rubber particle (RP) restrict particle deformation resulting in residual contour of RP within the film surface. For highly crosslinked RP, the collapse of the top surface of the RPs in the LRP films appears to create many “crater-like” structures within the film surfaces, while they present only protruding particles within the SRP and blend films. This seems to indicate that LRPs are easier to coalesce and form film than SRPs. Additionally, dynamic and mechanical properties and strain-induced crystallization (SIC) behaviors of the latex films, are effectively enhanced after pre-vulcanization. The pre-vulcanized LRP films perform better tensile properties and SIC than the SRP can..
19.	Masaru Mukai, Wei Ma, Keiko Ideta, Atsushi Takahara, Preparation and characterization of boronic acid- functionalized halloysite nanotube/poly(vinyl alcohol) nanocomposites, polymer, 10.1016/j.polymer.2019.121581, 178, 2019.09, Organic-inorganic nanocomposite films consisting of surface functionalized halloysite nanotube (HNT) and poly (vinyl alcohol) (PVA) with improved mechanical and thermal properties were prepared. The surface of HNT was modified with boronic acid by two different methods. In the first method, a boronic acid group bearing a triethoxysilane was synthesized and used to modify HNT directly. In the second method, HNT was modified by 3-aminopropyltriethoxysilane (APTES) and 4-formylphenylboronic acid sequentially. The surface-modified HNT was characterized by ζ-potential, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis. The nanocomposite films were prepared by solvent casting, followed by compression molding. The molecular aggregation structure and physicochemical properties were investigated by UV–Vis spectrophotometry, differential scanning calorimetry, wide-angle X-ray diffraction, tensile test, and dynamic mechanical analysis..
20.	Hitoshi Shimamoto, Chao Hung Cheng, Kazutaka Kamitani, Ken Kojio, Yuji Higaki, Atsushi Takahara, Nanocomposite elastomers composed of silica nanoparticles grafted with a comb-shaped copolymer Brush, Macromolecules, 10.1021/acs.macromol.9b00927, 52, 15, 5963-5970, 2019.08, Nanocomposites composed of monodisperse silica nanoparticles (SiNPs) modified with an elastic comb-shaped block copolymer brush were produced for the first time. Comb-shaped polymer brushes consisting of glassy poly(methyl methacrylate) branches and a rubbery poly(butyl acrylate) backbone were grafted from 100 nm diameter SiNPs by surface-initiated atom transfer radical polymerization. The comb-shaped polymer brush-grafted SiNPs produced self-standing films with a face-centered cubic ordered lattice structure via solvent-casting. The composite films showed rubber elasticity because of the interparticle rubbery polymer brush boundary phase. The ordered lattice exhibited significant alignment and distortion in response to the macroscopic film strain, and then reproduced the initial ordered lattice after unloading. ©.
21.	Motomu Tanaka, Francoise Brochard-Wyart, Francoise M. Winnik, Atsushi Takahara, Preface to the Interfaces and Biology 1 Mechanobiology Special Issue, Langmuir, 10.1021/acs.langmuir.9b01206, 35, 23, 7333-7334, 2019.06.
22.	Françoise M. Winnik, Walter Richtering, Atsushi Takahara, Zhan Chen, Preface to the 15th Pacific Polymer Conference (PPC-15) Virtual Issue, Langmuir, 10.1021/acs.langmuir.9b00560, 35, 13, 4413-4414, 2019.04.
23.	Takeshi Higuchi, Yuji Konyuba, Hidetoshi Nishiyama, Mitsuo Suga, Atsushi Takahara, Hiroshi Jinnai, Direct observation of polyelectrolyte brushes under wet and dry conditions by atmospheric scanning electron microscopy, Microscopy, 10.1093/jmicro/dfv357, 65, 2, 139-144, 2019.04, Polyelectrolyte brushes are polyelectrolyte polymers with one end fixed to a substrate. In this study, direct nano-scale visualization of polyelectrolyte brushes was carried out under 'aqueous conditions' by atmospheric scanning electron microscopy. The thickness of the polyelectrolyte brush layer was measured under both dry and aqueous conditions, experimentally confirming the swollen state of the brushes. These experimental findings qualitatively agreed with the results from previous neutron reflectivity experiments using similar polyelectrolyte brushes. Such direct visualization of polymer brushes in real space opens up a new route for better understanding their surface properties, such as friction, adhesion and wettability..
24.	Sorapat Niyomsin, Tomoyasu Hirai, Atsushi Takahara, Suwabun Chirachanchai, Incorporation of Benzoxazine Pendants in Polymer Chains A Simple Approach to Add-Up Multi-Responsive Functions, Macromolecular Chemistry and Physics, 10.1002/macp.201800526, 220, 5, 2019.03, External stimuli responsive polymers can be derived from the functional side group in copolymers. Benzoxazine dimer is a good candidate for expressing multi-responsive properties based on the type of phenol in combination with its metal complexation. The present work proposes a vinyl monomer containing a benzoxazine pendant, which contains an azo group as the functional monomer. The copolymerization with methylmethacrylate (MMA) via atom transfer radical polymerization leads to a block copolymer, specifically, PA-Azo-C3-b-PMMA, which forms uniform nanoparticles. The ring opening of benzoxazine monomer results in dimer pendants. The copolymer obtained, PA-Azo-C3-b-PMMA, shows multi-responsive functions in terms of metal ion complexation, and UV responsiveness through the dimer pendants and azobenzene groups. The UV exposure results in loss of uniformity of the nanoparticles as well as a decrease in size. This work demonstrates the role of benzoxazine pendants in developing PMMA copolymer showing external stimuli responsive functions..
25.	Shuhei Nozaki, Shiori Masuda, Chao Hung Cheng, Chigusa Nagano, Kazutoshi Yokomachi, Kazutaka Kamitani, Kohki Aoyama, Hiroyasu Masunaga, Ken Kojio, Atsushi Takahara, Direct Evaluation of Local Dynamic Viscoelastic Properties of Isotactic Polypropylene Films Based on a Dynamic μ-Beam X-ray Diffraction Method, ACS Macro Letters, 10.1021/acsmacrolett.8b00994, 8, 2, 218-222, 2019.02, The local mechanical properties of crystalline polymer were evaluated using synchrotron radiation X-ray diffraction with 10 μm lateral resolution. A nonoriented isotactic polypropylene (iPP) film with isolated spherulites in a crystallized matrix was used as a model sample. In situ wide-angle X-ray diffraction (WAXD) measurement was performed on the iPP film using a microbeam synchrotron radiation X-ray under sinusoidal strain. The lattice spacing of the crystal planes increased and decreased in response to the applied sinusoidal strain. Local dynamic viscoelastic functions (dynamic storage and loss moduli (E′ and E″)) were calculated at room temperature from the relationship between the calculated applied stress and the response strain obtained by dynamic μ-beam WAXD measurement inside and outside of the spherulites. The E′ values inside and outside of spherulite obtained from the change in spacing of the (110) plane were 1.8 and 1.1 GPa, respectively. Furthermore, the E′ value inside of spherulite obtained from the change in spacing of the (113) plane was 6.0 GPa. These values can be explained by the deformation of crystallite, which depends on the direction of crystal planes. The results obtained here revealed that synchrotron radiation X-ray diffraction measurement gives not only structural information but also the local mechanical properties of the materials E′..
26.	Biao Shen, Takeshi Hamazaki, Wei Ma, Naoki Iwata, Sumitomo Hidaka, Atsushi Takahara, Koji Takahashi, Yasuyuki Takata, Enhanced pool boiling of ethanol on wettability-patterned surfaces, Applied Thermal Engineering, 10.1016/j.applthermaleng.2018.12.049, 325-331, 2019.02, Due to the considerably reduced boiling point, organic fluids such as ethanol provide an attractive alternative to water as the working fluid in two-phase thermal management systems for high-heat-flux applications. The state-of-the-art enhancement methods for ethanol boiling normally involve surface structure engineering. Here we report, for the first time, enhancement of nucleate boiling of ethanol using wettability-patterned surfaces. By depositing onto a polished copper surface an array of circular spots of superamphiphobic coating of modified halloysite nanotubes (HNT) with fluoropolymer, which was shown to repel low-surface-tension fluids, we managed to create a meaningful biphilic pattern of alternating hydrophobicity (with ethanol contact angle exceeding 100°) and hydrophilicity (with contact angle close to 0°) on the surface. Boiling heat transfer was found to be improved dramatically on the coated surface. Specifically, the onset of nucleate boiling was found to drop by more than 35%. Moreover, at 20 K surface superheat (above the boiling point), a maximum heat transfer enhancement over 300% compared with a plain copper surface occurred on the surface with a pitch-to-spot ratio close to 2.5. The significantly increased heat transfer rate of the biphilic surfaces could be attributed to facilitated bubble nucleation and stronger agitation effect..
27.	Tatsunori Sakamaki, Yoshihiro Inutsuka, Kosuke Igata, Keiko Higaki, Norifumi L. Yamada, Yuji Higaki, Atsushi Takahara, Ion-Specific Hydration States of Zwitterionic Poly(sulfobetaine methacrylate) Brushes in Aqueous Solutions, Langmuir, 10.1021/acs.langmuir.8b03104, 35, 5, 1583-1589, 2019.02, The ion-specific hydration states of zwitterionic poly(3-(N-2-methacryloyloxyethyl-N,N-dimethyl)ammonatopropanesulfonate) (PMAPS) brushes in various aqueous solutions were investigated by neutron reflectivity (NR) and atomic force microscopy (AFM). The asymmetric hydration state of the PMAPS brushes was verified from the NR scattering-length density profiles, while the variation in their swollen thickness was complementary as determined from AFM topographic images. PMAPS brushes got thicker in any salt solutions, while the extent of swelling and the dimensions of swollen chain structure were dependent on the ion species and salt concentration in the solutions. Anion specificity was clearly observed, whereas cations exhibited weaker modulation in ion-specific hydration states. The anion specificity could be ascribed to ion-specific interactions between the quaternary ammonium cation in sulfobetaine and the anions. The weak cation specificity was attributed to the intrinsically weak cohesive interactions between the weakly hydrated sulfonate anion in sulfobetaine and the strongly hydrated cations. The ion-specific hydration of PMAPS brushes was largely consistent with the ion-specific aggregation state of the PMAPS chains in aqueous solutions..
28.	Kiminori Uchida, Kazuki Mita, Yuji Higaki, Ken Kojio, Atsushi Takahara, Lamellar orientation in isotactic polypropylene thin films a complement study via grazing incidence X-ray diffraction and surface/cross-sectional imaging, Polymer Journal, 10.1038/s41428-018-0138-3, 51, 2, 183-188, 2019.02, The crystalline structures of isotactic polypropylene (iPP) thin films were investigated using grazing incident wide-angle X-ray diffraction (GIWAXD), atomic force microscopy (AFM), and transmission electron microscopy (TEM). The out-of-plane (110) reflection split with 99° inclination in the GIWAXD pattern. The film surface was covered with flat-on mother lamellae with orthogonal daughter lamellae. The cross-sectional TEM image and the fast Fourier transform-processed image showed vertically aligned daughter lamellae and cross-hatched lateral mother lamellae. Flat-on lamellae may be preferentially produced at the substrate interface, after which the mother lamellae may yield daughter lamellae from the ac plane to give vertically aligned lamellae. The daughter lamellae yield in-plane lamellae with flat-on alignment from the ac plane, resulting in the global growth of a cross-hatched lamellar structure..
29.	Rahmawati Rahmawati, Shuhei Nozaki, Ken Kojio, Atsushi Takahara, Naoki Shinohara, Satoshi Yamasaki, Microphase-separated structure and mechanical properties of cycloaliphatic diisocyanate-based thiourethane elastomers, Polymer Journal, 10.1038/s41428-018-0148-1, 51, 2, 265-273, 2019.02, Abstract: Polythiourethane (PTU) and polyurethane (PU) elastomers were prepared from poly(oxytetramethylene) glycol, 1,4-bis(isocyanatomethyl) cyclohexane and a dithiol or diol chain extender with two methylene numbers (tetramethylene (C4) and pentamethylene (C5)). The effect of dithiol and diol and the methylene length of the chain extenders on the microphase-separated structure and mechanical properties of PTU and PU were evaluated. Differential scanning calorimetry (DSC) and wide-angle X-ray diffraction measurements revealed that the degree of ordering of hard segment chains in PTUs is lower than that for PU elastomers. However, it was revealed from the DSC, small-angle X-ray scattering and temperature dependent dynamic viscoelasticity measurements that the degree of microphase separation in the PTUs became stronger than that for the PUs. As a result, the mechanical property of PTUs is comparable with PUs. Furthermore, the glass transition temperature for the soft segment of PTU became lower than that for PU. PTU and PU exhibited a larger degree of microphase separation and mechanical property when the chain extender was composed of a tetramethylene (C4) chain compared to a pentamethylene (C5) chain..
30.	Yi Liu, Yuji Higaki, Masaru Mukai, Noboru Ohta, Taizo Kabe, Atsushi Takahara, Smectic ordered structure and water repellency of a poly(fluoroalkyl acrylate) with a carbamate linker, Polymer Journal, 10.1038/s41428-018-0139-2, 51, 2, 189-198, 2019.02, Thermal behavior, molecular aggregation structure, and water repellency for poly{2-[(perfluorooctylethyl)carbamate]ethyl}acrylate (PFAUr-C₈) were studied by differential scanning calorimetry (DSC), polarized optical microscopy (POM), wide-angle X-ray diffraction (WAXD), grazing-incidence wide-angle X-ray diffraction (GI-WAXD), contact angle measurements, and X-ray photoelectron spectroscopy (XPS). The impact of the carbamate linker was verified by comparison with poly[2-(perfluorooctyl)ethyl]acrylate (PFA-C₈). PFAUr-C₈ exhibited two phase transitions at 357 K and 416 K, whereas PFA-C₈ showed a single-phase transition at 347 K. Both PFAUr-C₈ and PFA-C₈ formed a bilayered hexatic smectic-B phase at room temperature. Although the lamellar structure for the fluoroalkyl (R_f) groups was immediately lost in PFA-C₈ after disordering of the lateral translational order, PFAUr-C₈ maintained a stacked lamellar structure without lateral translational order. PFAUr-C₈ exhibited excellent water repellency at room temperature similar to PFA-C₈. The outstanding thermal stability of the lamellar structure in PFAUr-C₈ is attributed to the cohesive interaction of the carbamate linkage..
31.	Ken Kojio, Yudai Kiyoshima, Tomoko Kajiwara, Yuji Higaki, Hung Jue Sue, Atsushi Takahara, Effect of Blend Composition on Scratch Behavior of Polystyrene/Poly(2,6-dimethyl-1,4-phenyleneoxide) Blends, Macromolecular Chemistry and Physics, 10.1002/macp.201800371, 220, 1, 2019.01, The relationship between the scratch behavior and molecular aggregation states of polystyrene (PS), poly(2,6-dimethyl-1,4-phenyleneoxide) (PPO), and their blends, is investigated based on differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), polarized optical microscopy (POM), and indentation and scratch tests. DSC reveals that all the PS/PPO blends show the single glass transition temperature (T_g) and the T_g monotonically increase and T_g breadth exhibits a maximum, with an increase in PPO content. Furthermore, density and intermolecular chain distance obtained by WAXD exhibits maximum and minimum values at near 50 wt% of PPO, respectively. It is evident that densification occurs by blending PS and PPO. The scratch coefficient of friction (SCOF) value of PS is the largest and PS exhibits a fish-scale pattern after scratch testing, while the SCOF value of PPO is much smaller than PS and PPO exhibits smooth groove formation. The PS50/PPO50 and PS20/PPO80 blends exhibit superior scratch and indentation resistance than PS and PPO. Damage morphology observation by POM and indentation tests reveals that molecular orientation is more restricted, and resistance against indentation increases for blends. This is due mainly to densification of the blend system..
32.	Haobing Wang, Yang Yang, Masayoshi Nishiura, Yuji Higaki, Atsushi Takahara, Zhaomin Hou, Synthesis of Self-Healing Polymers by Scandium-Catalyzed Copolymerization of Ethylene and Anisylpropylenes, Journal of the American Chemical Society, 10.1021/jacs.8b13316, 2019.01, Self-healing materials are of fundamental interest and practical importance. Herein we report the synthesis of a new class of self-healing materials, formed by the copolymerization of ethylene and anisyl-substituted propylenes using a sterically demanding half-sandwich scandium catalyst. The copolymerization proceeded in a controlled fashion, affording unique multi-block copolymers composed of relatively long alternating ethylene-alt-anisylpropylene sequences and short ethylene-ethylene units. By controlling the molecular weight and varying the anisyl substituents, a series of copolymers that show a wide range of glass-transition temperatures (T _g ) and mechanical properties have been obtained. The copolymers with T _g below room temperature showed high elastic modulus, high toughness, and remarkable self-healability, being able to autonomously self-heal upon mechanical damage not only in a dry environment but also in water and aqueous acid and alkaline solutions, while those with T _g around or above room temperature exhibited excellent shape-memory property. The unique mechanical properties may be ascribed to the phase separation of the crystalline ethylene-ethylene nanodomains from the ethylene-alt-anisylpropylene matrix..
33.	Xinxing Lin, Wei Ma, Lihui Chen, Liulian Huang, Hui Wu, Atsushi Takahara, Influence of water evaporation/absorption on the stability of glycerol-water marbles, RSC Advances, 10.1039/c9ra05728e, 9, 59, 34465-34471, 2019.01, The porous shell structure of liquid marbles allows liquid vapor to enter in/out of the liquid marbles, leading to the deformation/collapse of liquid marbles, which limits their application as miniature reactors for long-term chemical reactions. In this study, to prevent volatilization and maintain long-term stability, stable liquid marbles were fabricated by encapsulating glycerol/water droplets using superhydrophobic cellulose nanocrystals. The influence of water evaporation and absorption on the stability of aqueous glycerol marbles at different relative humidities (RHs) was investigated. At the same RH, the evaporation/absorption rates of the liquid marbles decreased on increasing the glycerol concentration. For the liquid marbles with the same glycerol volume concentration, the evaporation rates decreased with the increase in RH. The liquid marbles exhibited higher evaporation/absorption resistance compared with pure naked liquid droplets..
34.	Linlin Li, Wei Ma, Yuji Higaki, Kazutaka Kamitani, Atsushi Takahara, Organic-Inorganic Hybrid Thin Films Fabricated by Layer-by-Layer Assembly of the Phosphorylated Cellulose Nanocrystal and Imogolite Nanotubes, Langmuir, 10.1021/acs.langmuir.8b03107, 34, 44, 13361-13367, 2018.11, Phosphorylated cellulose nanocrystal (P-CNC)/imogolite nanotube (natural aluminosilicate nanotube) hybrid thin films were fabricated by spin-assisted layer-by-layer assembly. Phosphorylation of CNC with diammonium hydrogen phosphate ((NH ₄ ) ₂ HPO ₄ ) was carried out to introduce phosphate groups on the CNC surface for enhanced interaction with imogolite. Structure of the P-CNC/imogolite thin film was characterized by atomic force microscopy, scanning electron microscopy, X-ray diffraction (XRD), and grazing incidence wide-angle XRD. The film thickness increased linearly with the increment of the P-CNC/imogolite bilayer. Benefitting from the strong affinity between the phosphate group of the P-CNC and the Al-OH group of imogolite, the P-CNC/imogolite thin films were quite stable in water within a wide range of pH values, compared with the deterioration of the CNC/imogolite film under same soaking conditions..
35.	Sirirat Kumarn, Nut Churinthorn, Adun Nimpaiboon, Manus Sriring, Chee Cheong Ho, Atsushi Takahara, Jitladda Sakdapipanich, Investigating the Mechanistic and Structural Role of Lipid Hydrolysis in the Stabilization of Ammonia-Preserved Hevea Rubber Latex, Langmuir, 10.1021/acs.langmuir.8b02321, 34, 43, 12730-12738, 2018.10, The stabilization mechanism of natural rubber (NR) latex from Hevea brasiliensis was studied to investigate the components involved in base-catalyzed ester hydrolysis, namely, hydrolyzable lipids, ammonia, and the products responsible for the desired phenomenon observed in ammonia-preserved NR latex. Latex stability is generally thought to come from a rubber particle (RP) dispersion in the serum, which is encouraged by negatively charged species distributed on the RP surface. The mechanical stability time (MST) and zeta potential were measured to monitor field latices preserved in high (FNR-HA) and low ammonia (FNR-LA) contents as well as that with the ester-containing components removed (saponified NR) at different storage times. Amounts of carboxylates of free fatty acids (FFAs), which were released by the transformation and also hypothesized to be responsible for the like-charge repulsion of RPs, were measured as the higher fatty acid (HFA) number and corroborated by confocal laser scanning microscopy (CLSM) both qualitatively and quantitatively. The lipids and their FFA products interact differently with Nile red, which is a lipid-selective and polarity-sensitive fluorophore, and consequently re-emit characteristically. The results were confirmed by conventional ester content determination utilizing different solvent extraction systems to reveal that the lipids hydrolyzed to provide negatively charged fatty acid species were mainly the polar lipids (glycolipids and phospholipids) at the RP membrane but not those directly linked to the rubber molecule and, to a certain extent, those suspended in the serum. From new findings disclosed herein together with those already reported, a new model for the Hevea rubber particle in the latex form is proposed..
36.	Tomoyasu Hirai, Masanao Sato, Tomoki Kato, Hitoshi Shimamoto, Kiyu Uno, Nobuyuki Otozawa, Atsushi Takahara, Preparation of polymer brushes with well-controlled stereoregularity and evaluation of their functional properties, Polymer Journal, 10.1038/s41428-018-0078-y, 50, 10, 931-939, 2018.10, Polymer brushes in which one polymer chain end is tethered to a substrate show permanent properties related to the chemical structure of the polymer. However, they cannot accommodate functional molecules in the desired space because of the steric hindrance between neighboring polymer chains. To overcome this problem, the preparation of polymer brushes with ordered nanopores is strongly desired. High-density poly(methyl methacrylate) brushes with well-controlled stereoregularity were prepared using a surface-initiated living anionic polymerization method in the presence of a Lewis acid. A molecular weight range from 6 to 400 K with a narrow polydispersity index was obtained. Grazing incidence wide-angle X-ray diffraction measurements indicated that the polymer brushes formed a helical structure approximately 1 nm in diameter and consisting of encapsulated functional molecules or polymers, leading to the formation of inclusion complexes or stereocomplexes..
37.	Youngwook P. Seo, Sangsok Han, Junsok Choi, Atsushi Takahara, Hyoung Jin Choi, Yongsok Seo, Searching for a Stable High-Performance Magnetorheological Suspension, Advanced Materials, 10.1002/adma.201704769, 30, 42, 2018.10, Magnetorheological (MR) fluids are a type of smart material with rheological properties that may be controlled through mesostructural transformations. MR fluids form solid-like fibril structures along the magnetic field direction upon application of a magnetic field due to magnetopolarization of soft-magnetic particles when suspended in an inert medium. A reverse structural transition occurs upon removal of the applied field. The structural changes are very fast on the order of milliseconds. The rheological properties of MR fluids vary with the application of a magnetic field, resulting in non-Newtonian viscoplastic flow behaviors. Recent applications have increased the demand for MR materials with better performance and good long-term stability. A variety of industrial MR materials have been developed and tested in numerous experimental and theoretical studies. Because modeling and analysis are essential to optimize material design, a new macroscale structural model has been developed to distinguish between static yield stress and dynamic yield stress and describe the flow behavior over a wide range of shear rates. Herein, this recent progress in the search for advanced MR fluid materials with good stability is described, along with new approaches to MR flow behavior analysis. Several ways to improve the stability and efficiency of the MR fluids are also summarized..
38.	Kazutaka Kamitani, Ayumi Hamada, Kazutoshi Yokomachi, Kakeru Ninomiya, Kiyu Uno, Masaru Mukai, Yuko Konishi, Noboru Ohta, Maiko Nishibori, Tomoyasu Hirai, Atsushi Takahara, Depth-Resolved Characterization of Perylenediimide Side-Chain Polymer Thin Film Structure Using Grazing-Incidence Wide-Angle X-ray Diffraction with Tender X-rays, Langmuir, 10.1021/acs.langmuir.8b01566, 34, 29, 8516-8521, 2018.07, Polymers with a perylenediimide (PDI) side chain (PAc12PDI) consist of two kinds of crystalline structures with various types of orientations in a thin film. Understanding the population of the microcrystalline structure and its orientation along the thickness is strongly desired. Grazing-incidence wide-angle X-ray diffraction (GIWAXD) measurements with hard X-rays, which are generally chosen as λ = 0.1 nm, are a powerful tool to evaluate the molecular aggregation structure in thin films. A depth-resolved analysis for the outermost surface of the polymeric materials using conventional GIWAXD measurements, however, has limitations on depth resolution because the X-ray penetration depth dramatically increases above the critical angle. Meanwhile, tender X-rays (λ = 0.5 nm) have the potential advantage that the penetration depth gradually increases above the critical angle, leading to precise characterization for the population of crystallite distribution along the thickness. The population of the microcrystalline states in the PAc12PDI thin film was precisely characterized utilizing GIWAXD measurements using tender X-rays. The outermost surface of the PAc12PDI thin film is occupied by a monoclinic lattice with a = 2.38 nm, b = 0.74 nm, c = 5.98 nm, and β = 108.13°, while maintaining the c-axis perpendicular to the substrate surface. Additionally, the presence of solid substrate controls the formation of the crystallite with unidirectional orientation..
39.	Wei Ma, Hui Wu, Yuji Higaki, Atsushi Takahara, Halloysite Nanotubes Green Nanomaterial for Functional Organic-Inorganic Nanohybrids, Chemical Record, 10.1002/tcr.201700093, 18, 7, 986-999, 2018.07, The unique one-dimensional nanoporous structure and the reactive external and internal surfaces make halloysite nanotube (HNT) an interesting nanomaterial for various applications. HNT is a green nanomaterial because it is easily available from abundant deposits in nature and is biocompatible with low cytotoxicity. After a brief introduction on the structure of HNT, recent advances in surface modification of HNT and its functional organic-inorganic nanohybrids including hybrid nanocontainers, flame retardant nanocomposites, dye removal adsorbents, liquid marbles, and superamphiphobic coatings are introduced..
40.	Tomoko Honda, Aiko Nakao, Kazuhiko Ishihara, Yuji Higaki, Keiko Higaki, Atsushi Takahara, Yasuhiko Iwasaki, Shin Ichi Yusa, Polymer coating glass to improve the protein antifouling effect, Polymer Journal, 10.1038/s41428-018-0026-x, 50, 5, 381-388, 2018.05, Random copolymers (P(M_100-m/T _m )) composed of 2-methacryloyloxyethyl phosphorylcholine (MPC), which suppresses protein adsorption, and 3-(triethoxysilyl)propyl methacrylate (MTEOS), which can be covalently fixed on a glass surface, were prepared via photoinitiated radical polymerization. When P(M_100-m/T _m ) was coated on a glass surface, a protein antifouling effect could be observed because of the presence of MPC units on the glass surface. To confirm the coating of the glass surface with P(M_100-m/T _m ) by fluorescence microscopy, pyrene-labeled P(M_100-m/T _m ) was also prepared. An ethanol solution of P(M_100-m/T _m ) was spin-coated on the glass, which was exposed to NH₃ vapor to promote the reaction of the pendant triethoxysilyl groups in P(M_100-m/T _m ) with silanol groups on the glass. The coating of the glass with MPC was confirmed by fluorescence microscopy. The protein antifouling effects of the P(M_100-m/T _m )-coated glass were confirmed using fluorescence-labeled proteins. It is expected that P(M_100-m/T _m ) can be applied as a surface-coating agent on glass containers for protein formulations..
41.	Yuji Higaki, Yoshihiro Inutsuka, Hitomi Ono, Norifumi L. Yamada, Yuka Ikemoto, Atsushi Takahara, Counteranion-Specific Hydration States of Cationic Polyelectrolyte Brushes, Industrial and Engineering Chemistry Research, 10.1021/acs.iecr.8b00210, 57, 15, 5268-5275, 2018.04, While polyelectrolyte brushes have received extensive attention due to their particular surface properties, the ion-specific hydration states remain largely unknown. Here, we report the counteranion-specific hydration states of cationic poly[2-(methacryloyloxy)ethyltrimethylammonium] (PMTA) brushes in salt-free water. The water droplet contact angle on the PMTA brushes depends on the counteranion species, and the order is consistent with the Hofmeister series. Weakly hydrated chaotropic counteranions are strongly bound to weakly hydrated quaternary ammonium (QA⁺) cations in the PMTA brush chains, which induces a reduction in the ζ-potential, dehydration, and collapse of the PMTA brushes. The PMTA brushes with strongly hydrated chloride counteranions produce a more diffuse tail and less swollen bound layer under salt-free deuterium oxide than brushes with weakly hydrated thiocyanate counteranions. Ion pairing disturbs the ordering of hydrated water in the PMTA brushes. Our work enhances the understanding of the ion specificity in the hydration states of polyelectrolyte brushes and encourages the rational design of charged polymer materials..
42.	Yuji Higaki, Motoyasu Kobayashi, Atsushi Takahara, Friction behavior of polymer brush immobilized surfaces in good solvents, Handbook of Polymer Tribology, 10.1142/9789813227798_0015, 507-528, 2018.03.
43.	Tomoki Kato, Masanao Sato, Hitoshi Shimamoto, Kiyu Uno, Kazutoshi Yokomachi, Yuko Konishi, Kazutaka Kamitani, Maiko Nishibori, Noboru Ohta, Ryohei Ishige, Kevin L. White, Nobuyuki Otozawa, Tomoyasu Hirai, Atsushi Takahara, Preparation of High-Density Polymer Brushes with a Multihelical Structure, Langmuir, 10.1021/acs.langmuir.7b04167, 34, 10, 3283-3288, 2018.03, It is well-known that a mixture of isotactic and syndiotactic polymethyl methacrylate (PMMA) forms a stereocomplex consisting of a multihelical structure in which an isotactic chain is surrounded by a syndiotactic chain. Here, we report the basic structure of the stereocomplex formed when the syndiotactic PMMA chains are tethered to a silicon substrate and form a high-density polymer brush. The influence of geometric confinement was investigated by preparing the high-density polymer brushes on a flat and spherical substrate. In both cases, mixing the untethered isotactic PMMA with the grafted syndiotactic PMMA led to the formation of a stereocomplex with a multihelical structure. Static contact angle measurements showed a hindered surface mobility at the outermost surface of the polymer brush, indicating that the stereocomplex forms a crystalline structure. A syndiotactic polymer brush with substituted fluoroalkyl groups was prepared to increase the contrast for grazing incidence wide-angle X-ray diffraction (GIWAXD) measurements. The GIWAXD results verified that the stereocomplex forms a crystalline structure oriented perpendicular to the substrate with a relatively low degree of orientation..
44.	Ashwini Wali, Yucheng Zhang, Poulomi Sengupta, Yuji Higaki, Atsushi Takahara, Manohar V. Badiger, Electrospinning of non-ionic cellulose ethers/polyvinyl alcohol nanofibers Characterization and applications, Carbohydrate Polymers, 10.1016/j.carbpol.2017.10.070, 181, 175-182, 2018.02, The morphology of spin-coated films and electrospun fibers of ethyl hydroxy ethyl cellulose (EHEC), hydrophobically modified ethyl hydroxy ethyl cellulose (HM-EHEC) and their blends with Poly(vinyl alcohol) (PVA) was examined by AFM, SEM and contact angle measurements. These polysaccharides upon blending with PVA exhibited smooth surface which was evidenced by Atomic Force Microscopy (AFM) observation. The electrospinnability of above polysaccharides with PVA was demonstrated for the first time. The oriented fibers could be obtained using a rotating disc collector. Contact angles of spin-coated films and electrospun fibers were discussed in terms of hydrophobicity and wetting characteristics. Further, The nanofibers of EHEC/PVA were in-situ crosslinked using citric acid and were used for controlled release of an antibacterial drug, Chlorhexidine Digluconate (ChD). In-vitro studies of cytotoxicity, cell growth and cell proliferation were performed using L929 mouse fibroblast cells. These nanofiber mats show potential in drug delivery and as scaffolds in tissue engineering applications..
45.	Masanao Sato, Tomoki Kato, Hitoshi Shimamoto, Kazutaka Kamitani, Noboru Ohta, Tomoyasu Hirai, Atsushi Takahara, Design of High-Density Helical Polymer Brush on Silica Nanoparticles for the Size Recognition of Fullerene Molecules, ACS Macro Letters, 10.1021/acsmacrolett.7b00906, 7, 2, 148-152, 2018.02, High-density syndiotactic poly(methyl methacrylate) (st-PMMA) brushes form a helical structure and encapsulate fullerene molecules in their helical cavities, leading to a PMMA brush/fullerene inclusion complex. The brushes recognize the size of guest molecules and spontaneously adapt their helical diameter to the guest molecules. Both polymer brush/C₆₀ and polymer brush/C₇₀ inclusion complex on the flat substrate were characterized on the basis of grazing incidence wide-angle X-ray diffraction (GIWAXD) measurements, and it is revealed that the main chains oriented perpendicular to the substrate. Moreover, high-density st-PMMA brushes grafted onto nanoparticles efficiently separate C₇₀ molecules from the mixture of C₆₀ and C₇₀ solution. Even after 5× repeating process, the selectivity for C₇₀ molecules remains at 99%..
46.	Yucheng Zhang, Tomoyasu Hirai, Wei Ma, Yuji Higaki, Ken Kojio, Atsushi Takahara, Synthesis of a bio-inspired catechol/phosphorylcholine surface modifier and characterization of its surface properties, Journal of Polymer Science, Part A: Polymer Chemistry, 10.1002/pola.28858, 56, 1, 38-49, 2018.01, Biocompatible and blood-compatible surface modification is urgently needed for stainless steel (SUS)-based human implant devices to avoid inflammation and biofouling. To this end, the use of polymeric surface modifiers, whose surface properties are specifically tailored, is a promising approach since this approach minimizes the impact on device's mechanical properties. However, adhesion between the device and surface modifier is relatively weak, since van der Waals forces are employed, leading to low device durability. To address this issue, this work functionalized poly(ɛ-caprolactone)-b-[poly(α-chloride-ɛ-caprolactone)-b-poly(2-methacryloyloxyethyl phosphorylcholine)]₂ (PCL-b-(PCL-Cl-b-PMPC)₂) with catechol groups via a nucleophilic substitution, whereby the catechol functionalization was optimized. The resultant surface modifier showed strong adhesion toward SUS surfaces, forming a smooth and uniform hydrophilic polymeric film that reduced SUS fouling (i.e., protein). Notably, no significant changes of adhesion between the SUS and thin films (thin film) were observed after immersion for 45 days in a pH 7.4 phosphate buffer solution..
47.	Yuji Higaki, Motoyasu Kobayashi, Atsushi Takahara, Direct Hydrophilic Modification of Polymer Surfaces via Surface-Initiated ATRP, Reversible Deactivation Radical Polymerization Materials and Applications, 10.1021/bk-2018-1285.ch009, 157-168, 2018.01, Various hydrophilic modification approaches for solid polymer articles have been proposed. However, most methods scarcely ensure the long-term stability of the hydrophilicity due to the surface reorganization. The direct surface modification of polymer fibers and films by surface-initiated atom transfer radical polymerization (SI-ATRP) of charged monomers was investigated to achieve the stable surface modification of polymer articles. 2-(Methacryloyloxy)ethyl phosphorylcholine (MPC) was polymerized in the presence of compression molded sheets of bromo-functionalized polyethylene or polypropylene macroinitiators under mild conditions to provide a superhydrophilic PMPC-grafted surface layer. The PMPC-grafted polyolefin sheets showed excellent wettability and oil-detachment behavior in water. The PMPC-grafted PP sheets retained a water contact angle of less than 10° for over three years in air. A facile surface modification procedure for electrospun poly(butylene terephthalate) (PBT) fibers by SI-ATRP was proposed. ATRP initiators were introduced on the surface of the PBT fibers through aminolysis and subsequent chemical vapor adsorption. Poly[3-(N-2-methacryloyloxyethyl-N,N-dimethyl)ammonatopropanesulfonate)] (PMAPS) was grafted to the PBT fibers via SI-ATRP without altering the fiber geometry. After modification with zwitterionic poly(sulfobetaine) brushes, the surface became superhydrophilic. The surface properties were thermally stable due to the high melting temperature of the PBT crystallites, and were maintained for a prolonged period..
48.	Yuji Higaki, Motoyasu Kobayashi, Tomoyasu Hirai, Atsushi Takahara, Direct polymer brush grafting to polymer fibers and films by surface-initiated polymerization, Polymer Journal, 10.1038/pj.2017.61, 50, 1, 101-108, 2018.01, Direct surface modification of polymer fibers and films by surface-initiated polymerization has been investigated. The introduction of initiating sites on polymer materials and their successive polymerization produce surface-tethered polymer chains on the polymer surface. The surface-selective modification controls the surface properties, such as wetting, lubrication and antifouling, without sacrificing bulk performance. Among the various procedures for introduction of initiating groups and subsequent polymerization proposed to date, this focused review article highlights our studies on polymer brush grafting to electrospun polymer fibers and polymer films through surface-initiated polymerization. We review studies focusing on grafting polymer chains to five different types of solid polymers: Poly(methyl methacrylate)-based copolymers, Br-containing polyolefins, poly(vinylidene fluoride-co-trifluoroethylene), poly(butylene terephthalate), and poly(ether-ether ketone)..
49.	Yucheng Zhang, Tomoyasu Hirai, Yuji Higaki, Atsushi Takahara, Effect of polycaprolactone crystalline block on surface reorganization of a phosphorylcholine-based amphiphilic block copolymer surface modifier, Chemistry Letters, 10.1246/cl.171036, 47, 2, 247-250, 2018.01, The surface reorganization behavior of a crystalline ABCBA-type copolymer and a non-crystalline ABA-type copolymer including poly(2-methacryloyloxyethyl phosphorylcholine) was investigated. The crystalline domain in the block copolymer suppressed the surface reorganization when exposed to either hydrophilic or hydrophobic condition..
50.	Ken Kojio, Chigusa Nagano, Aya Fujimoto, Shuhei Nozaki, Kazutoshi Yokomachi, Kazutaka Kamitani, Hirohmi Watanabe, Atsushi Takahara, In situ synchrotron radiation X-ray diffraction studies on molecular aggregation structure of nylon 12 films during bulge testing, Soft Matter, 10.1039/c7sm01842h, 14, 9, 1659-1664, 2018.01, It is desirable to establish a method for evaluating mechanical properties, such as modulus and strength, of micrometer and sub-micrometer thick polymer films. Bulge tests, where bulge deformation is imposed on films by the pressure of an inert gas, are suitable for satisfying this demand. However, very few studies on polymer films exist in the literature. In this study, bulge testing equipment for in situ synchrotron radiation wide-angle X-ray diffraction (WAXD) measurements is designed and used to study the relationship between the molecular aggregation structure and the mechanical properties of a crystalline nylon 12 (Ny12) film during bulge testing. Isothermally crystallized and quenched Ny12 films exhibited stress-strain curves similar to those obtained by conventional uniaxial elongation. In situ WAXD measurements during bulge testing revealed that the lattice extension of the crystallites is clearly dependent on crystallinity. Concretely, crystallites in the isothermally crystallized film show higher elastic properties than those in the quenched one. The results of the molecular aggregation structure, including the crystal structure and the amorphous chain surrounding the crystallites, of the films during bulge deformation firstly obtained in this study must be useful for designing toughened polymer films..
51.	Xinxing Lin, Wei Ma, Lihui Chen, Liulian Huang, Hui Wu, Atsushi Takahara, Self-healing cellulose nanocrystal-stabilized droplets for water collection under oil, Soft Matter, 10.1039/c8sm01852a, 14, 46, 9308-9311, 2018.01, The removal of small water droplets from oils is imperative because oils can easily be contaminated or deteriorated by water during transportation, storage and usage. Here, we report superhydrophobic magnetic cellulose nanocrystal (CNC) nanoparticles, which are capable of removing tiny water droplets from oil by forming under oil particle-stabilized droplets. These particle-stabilized droplets can be collected and moved by a magnetic force, and self-healed upon damage by an external force..
52.	Masaru Mukai, Yuji Higaki, Tomoyasu Hirai, Atsushi Takahara, Separation of endo-cyclic 2-methacryloyloxyethyl choline phosphate by anion exchange approach, Chemistry Letters, 10.1246/cl.180787, 47, 12, 1509-1511, 2018.01, 2-Methacryloyloxyethyl choline phosphate (MCP) was synthesized by a ring-opening reaction of cyclic phosphates with 2-(dimethylaminoethyl methacrylate). The crude MCP consisted of an endo-cyclic desired product and an exo-cyclic byproduct. The exo-cyclic byproduct was completely removed by anion-exchange and subsequent open-column chromatography. We successfully obtained pure MCP without the exo-cyclic byproduct, and synthesized MCP polymers by free radical polymerization..
53.	Wei Ma, Yuji Higaki, Atsushi Takahara, Superamphiphobic Coatings from Combination of a Biomimetic Catechol-Bearing Fluoropolymer and Halloysite Nanotubes, Advanced Materials Interfaces, 10.1002/admi.201700907, 4, 23, 2017.12, Superamphiphobic coatings with remarkable water and oil repellency are prepared by the combination of a biomimetic catechol-bearing fluoropolymer, poly{2-(perfluorooctyl)ethyl acrylate-co-N-(3,4-dihydroxyphenethyl) acrylamide} (P(FAC ₈ -co-DOPAm)), and naturally available halloysite nanotubes (HNTs). They are based on surface modification of HNTs with P(FAC ₈ -co-DOPAm). A procedure to attain stable affinity between silica and the copolymer is established, and used for surface modification of HNTs. Superamphiphobic coatings are obtained by casting the suspension of P(FAC ₈ -co-DOPAm)-modified HNTs onto substrates. The superamphiphobic coatings exhibit Cassie–Baxter's wetting to liquids with a wide range of surface tension, because of the extremely low surface free energy and the unique micro-/nanohierarchical surface topography, as well as the re-entrant curvature of HNTs. These superamphiphobic coatings are environmentally and chemically durable, and can resist water scouring. The abundance of HNTs in nature and the easily controlled process of this method ensure an efficient approach for large-scale production of superamphiphobic coatings for various applications..
54.	Tomoyasu Hirai, Motoyasu Kobayashi, Atsushi Takahara, Control of the primary and secondary structure of polymer brushes by surface-initiated living/controlled polymerization, Polymer Chemistry, 10.1039/c7py00956a, 8, 36, 5456-5468, 2017.09, Characterization of the molecular structure of high-density well-defined polymer brushes with predictable number-average molecular weight (M_n), narrow molecular weight dispersity (MWD), and highly ordered tacticity, prepared by surface-initiated controlled radical polymerization or living anionic polymerization, is described. Ionic monomers, such as 3-(N-2-methacryloyloxyethyl-N,N-dimethyl)ammonatopropanesulfonate (MAPS), were polymerized by atom transfer radical polymerization in 2,2,2-trifluoroethanol in the presence of imidazolium chloride to give a polymer with M_n greater than 2 × 10⁵ g mol^-1 maintaining a narrower MWD (M_w/M_n 88%). Grazing incidence wide-angle X-ray diffraction (GIWAXD) measurements indicated that the stereoregular PMMA brushes formed helical structures with about 1 nm diameter and encapsulated fullerenes in the cavities..
55.	Yuji Higaki, Yoshihiro Inutsuka, Tatsunori Sakamaki, Yuki Terayama, Ai Takenaka, Keiko Higaki, Norifumi L. Yamada, Taro Moriwaki, Yuka Ikemoto, Atsushi Takahara, Effect of Charged Group Spacer Length on Hydration State in Zwitterionic Poly(sulfobetaine) Brushes, Langmuir, 10.1021/acs.langmuir.7b01935, 33, 34, 8404-8412, 2017.08, Effect of alkyl chain spacer length between the charged groups (CSL) in zwitterionic poly(sulfobetaine) (PSB) brushes on the hydration state was investigated. PSB brushes with ethyl (PMAES), propyl (PMAPS), or butyl (PMABS) CSL were prepared by surface-initiated atom transfer radical polymerization on silicon wafers. Hydration states of the PSB brushes in aqueous solutions and/or humid vapor were investigated by contact angle measurement, infrared spectroscopy, AFM observation, and neutron reflectivity. The PSB brushes are swollen in humid air and deionized water due to the hydration of the charged groups leading to the reduction of hydrated PSB brushes/water interfacial free energy. The hydrated PSB brushes exhibit clear interface with low interfacial roughness due to networking of the PSB brush chains through association of the SBs. The hydrated PSB brushes produce diffusive swollen layer in the presence of NaCl because of the charge screening followed by SB dissociation by the bound ions. The ionic strength sensitivity in the hydration got more significant with increasing the CSL in SBs because of the augmentation in partial charge by charged group separation..
56.	Yuji Higaki, Ken Suzuki, Yudai Kiyoshima, Tomoyuki Toda, Masayoshi Nishiura, Noboru Ohta, Hiroyasu Masunaga, Zhaomin Hou, Atsushi Takahara, Molecular Aggregation States and Physical Properties of Syndiotactic Polystyrene/Hydrogenated Polyisoprene Multiblock Copolymers with Crystalline Hard Domain, Macromolecules, 10.1021/acs.macromol.7b01193, 50, 16, 6184-6191, 2017.08, Molecular aggregation structure and mechanical as well as thermal properties of novel well-defined multiblock copolymers consisting of crystalline syndiotactic polystyrene (sPS) and rubbery hydrogenated polyisoprene (hPIp) were investigated. The morphology and crystalline ordered structure of the multiblock copolymer films prepared by solvent casting from 1,2-dichlorobenzene solution depended on the volume fraction of sPS (VF_sPS) and number of blocks. The multiblock copolymer films exhibited ordered morphology with low crystallinity. The crystallinity of the sPS reduced with decreasing the VF_sPS. The pentablock copolymer produced more ordered morphology and less crystallinity than the triblock copolymers. The anisotropic orientation and mechanical stability of the δ form sPS crystals in the spherical sPS domains during uniaxial stretching were demonstrated. Tensile testing and dynamic mechanical analysis indicated that these multiblock copolymer films with appropriate sPS fraction are strong, tough, and elastic and thus could be potential candidates for a new type of thermoplastic elastomer with discrete crystalline hard domains..
57.	Shuhei Nozaki, Tomoyasu Hirai, Yuji Higaki, Kohji Yoshinaga, Ken Kojio, Atsushi Takahara, Effect of chain architecture of polyol with secondary hydroxyl group on aggregation structure and mechanical properties of polyurethane elastomer, Polymer, 10.1016/j.polymer.2017.03.031, 116, 423-428, 2017.05, Polyurethane elastomers (PUEs) based on poly(2-ethyl-1,3-hexamethylene adipate) glycol (PEHA), poly(2,4-diethyl-1,5-pentamethylene adipate) glycol (PDEPA) and poly(2-butyl-2-ethyl-1,3-trimethylene adipate) glycol (PBETA) were synthesized with 4,4’-diphenylmethane diisocyanate (MDI) and 1,4-butane diol (BD)/1,1,1-trimethylol propane (TMP). PEHA has one primary and one secondary hydroxyl groups, but PDEPA or PBETA has two primary hydroxyl groups. The effect of low reactive secondary OH group on molecular aggregation structure and mechanical properties of the PUEs was investigated using Fourier transform infrared spectroscopy (FT-IR), differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS), dynamic viscoelastic measurement and tensile testing. The study demonstrates that PEHA-based PUE has lower cross-linking density and lower degree of microphase separation than PDEPA- and PBETA-based PUEs. As a result, PEHA-based PUE has lower dynamic storage modulus value at the rubbery plateau region and Young's modulus..
58.	K. Imato, J. C. Natterodt, J. Sapkota, R. Goseki, C. Weder, Atsushi Takahara, H. Otsuka, Dynamic covalent diarylbibenzofuranone-modified nanocellulose Mechanochromic behaviour and application in self-healing polymer composites, Polymer Chemistry, 10.1039/c7py00074j, 8, 13, 2115-2122, 2017.04, The surface of cellulose nanocrystals (CNCs) was modified with a scissile but reversibly recombinable dynamic covalent mechanophore, and the activation of the mechanophore on the CNC surface in bulk was investigated. The recombination behaviour of the activated surface-modified mechanophore exhibited high sensitivity to mechanical stress because of the limited molecular mobility. The modified CNCs could be used to effectively reinforce a self-healable polymer containing similar dynamic covalent linkages through the formation of reversible covalent bonds between the CNC surfaces and the polymer matrix, while the nanocomposite retained the ability to heal. The results of the present study appear to be broadly useful for designing composite materials with fascinating functional properties such as damage self-reporting and self-healing..
59.	Kosuke Yamazoe, Yuji Higaki, Yoshihiro Inutsuka, Jun Miyawaki, Yi Tao Cui, Atsushi Takahara, Yoshihisa Harada, Enhancement of the Hydrogen-Bonding Network of Water Confined in a Polyelectrolyte Brush, Langmuir, 10.1021/acs.langmuir.7b00243, 33, 16, 3954-3959, 2017.04, Water existing in the vicinity of polyelectrolytes exhibits unique structural properties, which demonstrate key roles in chemistry, biology, and geoscience. In this study, X-ray absorption and emission spectroscopy was employed to observe the local hydrogen-bonding structure of water confined in a charged polyelectrolyte brush. Even at room temperature, a majority of the water molecules confined in the polyelectrolyte brush exhibited one type of hydrogen-bonding configuration: a slightly distorted, albeit ordered, configuration. The findings from this study provide new insight in terms of the correlation between the function and local structure of water at the interface of biological materials under physiological conditions..
60.	Chien Wei Chu, Yuji Higaki, Chao Hung Cheng, Ming Hsiang Cheng, Chun Wei Chang, Jiun Tai Chen, Atsushi Takahara, Zwitterionic polymer brush grafting on anodic aluminum oxide membranes by surface-initiated atom transfer radical polymerization, Polymer Chemistry, 10.1039/c7py00045f, 8, 15, 2309-2316, 2017.04, A feasible processing of zwitterionic polymer-grafted anodic aluminum oxide (AAO) membranes by surface-initiated atom transfer radical polymerization (SI-ATRP) and the geometric effect on the polymer chain growth in the confined nanopores were investigated. A zwitterionic poly(3-(N-2-methacryloyloxyethyl-N,N-dimethyl)ammonatopropanesulfonate) (PMAPS) brush was produced on an AAO membrane via introduction of an initiator with a phosphonate group and subsequent SI-ATRP. The PMAPS-grafted AAO membranes were characterized by water droplet contact angle measurement, size exclusion chromatography (SEC), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), and laser Raman micro-spectroscopy. The linear relationship between the grafting yield (Y) of the PMAPS brush and number-average molecular weight (M_n) of the unbound PMAPS indicates that there is no significant geometric effect on the chain growth under the spatial confinement inside the nanopores with diameters of ∼200 nm. The PMAPS brushes were diminished near the center section along the nanopores because the monomer supply was retarded. The capability of the PMAPS-grafted AAO membranes for inorganic nanoparticle immobilization was also demonstrated using gold nanoparticles (AuNPs) through ion-exchange and reduction processes..
61.	Atsushi Takahara, (Organic/Inorganic) hybrids based on natural inorganic nanotubes, Sen'i Gakkaishi, 73, 5, 204-205, 2017.04.
62.	Hiroki Ogawa, Kouta Tsujioka, Mikihito Takenaka, Kazutaka Kamitani, Takeharu Sugiyama, Toshiji Kanaya, Atsushi Takahara, Depth-dependent structural analyses in PS-b-P2VP thin films as revealed by grazing incidence small angle scattering in the tender energy region, Kobunshi Ronbunshu, 10.1295/koron.2016-0058, 74, 2, 109-113, 2017.03, We report depth-resolved structural measurements in symmetric PS-b-P2VP thin films, using grazing incidence small angle X-ray scattering (GISAXS) in the tender X-ray region. The nanostructures in thin films show cylindrical structures although lamellar structures are expected, thermodynamically, as equilibrium state. It has been reported that, when the thin films are annealed at temperatures greater than the T_g, lamellar structures formed, parallel to the substrate. We prepared as-cast and annealed thin films on silicon substrates. From GISAXS measurements, we concluded that vertical cylindrical nanostructures in as-cast thin films are formed, oriented from surface toward substrate interface. Annealing changed the vertical cylindrical nanostructures at the surface. Even after very long annealing, like 12 hours above T_g, we found that vertical nanostructures still remained at the substrate interface, due to the lower mobility of polymer chains near the substrate interface..
63.	Daigo Kobayashi, Atsushi Takahara, Interphase structure of oxidized carbon fiber reinforced polyamide 6 revealed by synchrotron microbeam x-ray diffraction and infrared-spectroscopy, Kobunshi Ronbunshu, 10.1295/koron.2016-0054, 74, 2, 91-98, 2017.03, Interphase molecular aggregation states of carbon fiber reinforced polyamide 6 (PA6) films were studied. DSC measurement of composites revealed that high modulus carbon fibers (HMCF(-)) and oxidized high modulus carbon fibers (HMCF(+)) effectively acted as nucleation sites in PA6 matrices during cooling from melt. Polarized optical microscopy (POM) observation revealed the presence of a ca. 2μm thick polyamide 6 transcrystalline layer with positive birefringence at the interphase region of PA6 and HMCF(-), while no clear crystal interphase layer was observed at that of PA6 and HMCF(+). The crystal form and orientation at the interphase region was further confirmed by microbeam wide angle X-ray diffraction (μWAXD) and microbeam infrared spectroscopy (μIR). The μWAXD and μIR results show that that the a axis of α crystals in the transcrystalline layer are perpendicular to the HMCF(-) fiber direction, while α-type crystals grows randomly in case of HMCF(+) interphase. One reason might be that during the oxidization process, the orientation of the HMCF surface graphite crystal may become disordered..
64.	Yuji Higaki, Benjamin Fröhlich, Akihisa Yamamoto, Ryo Murakami, Makoto Kaneko, Atsushi Takahara, Motomu Tanaka, Ion-Specific Modulation of Interfacial Interaction Potentials between Solid Substrates and Cell-Sized Particles Mediated via Zwitterionic, Super-Hydrophilic Poly(sulfobetaine) Brushes, Journal of Physical Chemistry B, 10.1021/acs.jpcb.6b11540, 121, 6, 1396-1404, 2017.02, Zwitterionic polymer brushes draw increasing attention not only because of their superhydrophilic, self-cleaning capability but also due to their excellent antifouling capacity. We investigated the ion-specific modulation of the interfacial interaction potential via densely packed, uniform poly(sulfobetaine) brushes. The vertical Brownian motion of a cell-sized latex particle was monitored by microinterferometry, yielding the effective interfacial interaction potentials V(Δh) and the autocorrelation function of height fluctuation. The potential curvature V″(Δh) exhibited a monotonic increase according to the increase in monovalent salt concentrations, implying the sharpening of the potential confinement. An opposite tendency was observed in CaCl₂ solutions, suggesting that the ion specific modulation cannot be explained by the classical Hofmeister series. When the particle fluctuation was monitored in the presence of free sulfobetaine molecules, the increase in [sulfobetaine] resulted in a distinct increase in hydrodynamic friction. This was never observed in all the other salt solutions, suggesting the interference of zwitterionic pairing of sulfobetaine side chains by the intercalation of sulfobetaine molecules into the brush layer. Furthermore, poly(sulfobetaine) brushes exhibited a very low V″(Δh) and hydrodynamic friction to human erythrocytes, which seems to explain the excellent blood repellency of zwitterionic polymer materials..
65.	Shuhei Nozaki, Shiori Masuda, Kazutaka Kamitani, Ken Kojio, Atsushi Takahara, Goro Kuwamura, Daisuke Hasegawa, Krzysztof Moorthi, Kazuki Mita, Satoshi Yamasaki, Superior Properties of Polyurethane Elastomers Synthesized with Aliphatic Diisocyanate Bearing a Symmetric Structure, Macromolecules, 10.1021/acs.macromol.6b02044, 50, 3, 1008-1015, 2017.02, Polyurethane elastomers (PUEs) containing trans-1,4-bis(isocyanatomethyl)cyclohexane (1,4-H₆XDI) have been synthesized by polymerizing 1,4-H₆XDI with poly(oxytetramethylene) glycol and 1,4-butanediol. The molecular aggregation state and mechanical properties of these PUEs have been compared with those exhibited by PUE analogues made of MDI and diols. The hard segment chains in the 1,4-H₆XDI-based PUEs are found to readily crystallize and form strong hydrogen bonds due to a high symmetry of 1,4-H₆XDI molecule. Consequently, the 1,4-H₆XDI-based PUEs exhibit well-organized hard segment domains. This leads to their generally superior mechanical properties as compared to those of the well-known MDI-based PUEs. 1,4-H₆XDI’s lack of aromatic moieties is expected to greatly enhance color stability of resulting PUEs. All the above features suggest 1,4-H₆XDI could replace MDI in a range of applications..
66.	Daisuke Matsukuma, Hirohmi Watanabe, Hui Wu, Shigesaburo Ogawa, Hiroshi Jinnai, Atsushi Takahara, Liquid marbles from polymer particles Formation mechanism, physical characterizations, and applications, Kobunshi Ronbunshu, 10.1295/koron.2016-0050, 74, 1, 26-35, 2017.01, A liquid marble is a small liquid droplet with a diameter of several mm, for which the surface is covered by hydrophobic nano- (or micro-) particles. This coverage by hydrophobic particles decreases the apparent surface tension of the liquid, and it allows the liquid to keep a spherical shape on any substrate. Liquid marbles shows many unique characteristics such as smooth movement on any substrate without any leakage of liquid. Many researchers have focused on the understanding of their unique physical properties as well as the demonstration of potential applications. Here we discuss the formation mechanism and physical characterization of this unique colloidal material. From the interpretation based on the surface chemistry and the direct observation using X-ray computed tomography, we shed light on the formation mechanism of liquid marbles, and the design of functional liquid marbles. Additionally, we introduce the wrapping of liquid droplet by using poly(lactic acid) particles, robust liquid marbles using inorganic nanotubes, and monolayer particle coating with monodisperse polymer particles..
67.	Kyung Lynne Park, Wei Ma, Yuji Higaki, Atsushi Takahara, Mechanically enhanced hyaluronic acid hybrid hydrogels with halloysite nanotubes, Chemistry Letters, 10.1246/cl.170484, 46, 8, 1217-1219, 2017.01, Hybrid hydrogels composed of hyaluronic acid (HA) and halloysite nanotubes (HNTs) were prepared via photocross-linking of HA and HNTs functionalized with vinyl groups. These hybrid hydrogels showed enhanced mechanical properties without sacrificing good swelling capability, which is crucial for biomedical applications..
68.	Satoshi Yamasaki, Goro Kuwamura, Hirokazu Morita, Daisuke Hasegawa, Ken Kojio, Atsushi Takahara, High performance polyurethane elastomers using new cyclaliphatic diisocyanate, Nihon Reoroji Gakkaishi, 10.1678/rheology.45.261, 45, 5, 261-268, 2017.01, Trans-1,4-bis (isocyanatomethyl) cyclohexane (1,4-H₆XDI) has been newly developed as a novel cycloaliphatic diisocyanate with a high symmetric chemical structure. The PUEs were prepared with 1,4-H₆XDI, polyesterpolyol as a long chain polyol and 1,4-butanediol (BD) as a chain extender. As the representative aromatic and aliphatic diisocyanates, 4,4'-diphenylmethane diisocyanate (MDI) and dicyclohexyl methane-4,4'-diisocyanate (H12MDI) were also used as the control. As a result, it was revealed that 1,4-H₆XDI-based PUEs achieved high elasticity such as higher impact resilience, lower compression set, improved heat resistant, and good light stability which was not able to be realized with the existing diisocyanates. The reason is explained that the hard segment chains of the 1,4-H₆XDI-based PUEs crystallized well with formation of hydrogen bonds in the PUEs due to the symmetric structure of 1,4-H₆XDI. Thus, the 1,4-H₆XDI-based PUEs can provide superior properties such as mechanical and thermal properties and excellent light stability compared to existing diisocyanate-based PUEs by rheological evaluation..
69.	Atsushi Takahara, Yuji Higaki, Design and Physicochemical Characterization of Novel Organic-Inorganic Hybrids from Natural Aluminosilicate Nanotubes, Self-Cleaning Coatings Structure, Fabrication and Application, 10.1039/9781782626725-00131, 2017-January, 131-156, 2017, Surface functionalization of tubular nano-clays of imogolite and halloysite using the selective binding of organophosphonic acids and organosilane compounds, and the use of the surface modified nanotubes in polymer hybrids were studied. Surface modification of imogolite with alkyl phosphonic acid salt through the specific interaction of phosphonic acid and the exterior alumina sites of imogolite was presented. SI-ATRP was performed with the selectively adsorbed phosphonic acid functionalized ATRP-initiator to prepare polymer brushes on the imogolite surface. Selective modification of halloysite nanotube exterior and inner surfaces was demonstrated. Aqueous phosphonic acid binds to alumina sites at the tube lumen to make the lumen hydrophobic. Subsequent modification with organosilane affords bifunctionalized halloysites with both the lumen and exterior surface modified. Loading of hydrophobic organic compound to the modified lumen was confirmed. SI-ATRP was performed through the selectively adsorbed DOPA-functionalized ATRP-initiator to prepare polymer brushes on the nanotube lumen. Also, surface modified halloysite was applied for preparation of novel intelligent polyurethane nanocomposites with improved thermal stability and mechanical properties..
70.	Moriya Kikuchi, Atsushi Takahara, Seigou Kawaguchi, Dimensional characterizations from rod stars to brushes of polymers with a low degree of polymerization, Macromolecules, 10.1021/acs.macromol.6b02251, 50, 1, 324-331, 2017, Dimensional characterizations from rod stars to brushes (PSt-g-HIC-32) with a relatively low degree of polymerization of the main chain have been studied in tetrahydrofuran (THF) at 25 °C by employing synchrotron radiation small-angle X-ray scattering, static and dynamic light scatterings, and viscosity measurements. The rod stars and brushes consist of a flexible linear polystyrene (PSt) main chain and 32 n-hexyl isocyanate (HIC) units in each side chain. Eight PSt-g-HIC-32 samples with a weightaverage degree of polymerization (N_M) of 11-495 of the main chain and a narrow molecular weight distribution (M_w/M_n) of 1.08-1.17 were prepared using a recycling preparative size-exclusion chromatography (SEC) system. The mean-square radius of gyration (〈S²〉), hydrodynamic radius (R_H), and intrinsic viscosity ([η]) of the stars and brushes were tabulated. The absolute calibration curve obtained in SEC analysis, scattering form factor, and ρ (==〈S²〉^1/2/R_H) parameter indicated a continuous change in the shape from the rod star to rod brush on increasing the aspect ratio of the main chain to the side chain. The N_M dependences of 〈S²〉, R_H, and [η] were consistently and quantitatively described using the current theories based on a wormlike (sphero-) cylinder model by taking into account the effective protruding effects of the side chains near the ends of the main chain..
71.	Yuji Higaki, Yudai Kiyoshima, Ken Suzuki, Hirofumi Kabayama, Noboru Ohta, Yongsok Seo, Atsushi Takahara, Elastomers built up through the π-π Stacking association of polycyclic planar aromatic diimides, RSC Advances, 10.1039/c7ra08910d, 7, 73, 46195-46200, 2017, Polymers composed of polycyclic aromatic planar diimide (PCAD) units and flexible rubbery poly(propylene glycol) (PPG) chains were synthesized, and the morphology and viscoelasticity were investigated. The polymers were synthesized by polycondensation of naphthalene or perylene tetracarboxylic dianhydrides with PPG-diamines and subsequent thermal imidization. The thermal and viscoelastic properties were measured by differential scanning calorimetry and dynamic mechanical analysis, respectively. The molecular aggregation structure was explored by infrared spectroscopy, wide-angle X-ray diffraction and small-angle X-ray scattering measurements. The PCAD units associate in the PPG continuum by the electromagnetic interaction of π electrons on the planar aromatic rings to build a stacked structure. The morphology and viscoelastic characteristics depend on the PCAD structure and molecular weight of the PPG segments, and the polymers composed of perylene diimide units and high molecular weight PPG chains show rubber elasticity because of the well-segregated morphology. The thermal stability was enhanced by PPG chain end capping by thermally stable PCAD units..
72.	Atsushi Takahara, Historic perspectives on the research of fiber and polymeric materials in Kyushu University, Sen'i Gakkaishi, 73, 5, 190-191, 2017.
73.	Hui Wu, Yuji Higaki, Atsushi Takahara, Molecular self-assembly of one-dimensional polymer nanostructures in nanopores of anodic alumina oxide templates, Progress in Polymer Science, 10.1016/j.progpolymsci.2017.10.004, 2017, One-dimensional (1-D) polymer nanostructures have attracted much attention due to their unique properties and many potential applications in areas such as sensors, transistors, separation, storage, and photovoltaic cells. This is a review of research activities on 1-D polymer nanostructures fabricated by anodic aluminum oxide (AAO) templates. The preparation methods of polymer nanostructures by AAO templates including polymer melt infiltration, polymer solution infiltration, and chemical synthesis are introduced. According to the molecular structure of polymers, the morphology, and properties of seven types of polymers, amorphous homopolymers, amorphous-amorphous block copolymers, amorphous/amorphous polymer blends, semicrystalline homopolymers, semicrystalline/amorphous polymer blends, semicrystalline-amorphous block copolymers, and semicrystalline-semicrystalline block copolymers in nanopores are demonstrated..
74.	Nichaphat Thongsai, Yusuke Nagae, Tomoyasu Hirai, Atsushi Takahara, Tomoki Uchiyama, Kazutaka Kamitani, Peerasak Paoprasert, Multifunctional nitrogen-doped carbon dots from maleic anhydride and tetraethylenepentamine via pyrolysis for sensing, adsorbance, and imaging applications, Sensors and Actuators, B: Chemical, 10.1016/j.snb.2017.07.051, 253, 1026-1033, 2017, Carbon dots are materials with fascinating optical and electronic properties that can replace organic dyes and fluorescent semiconductor nanocrystals. In this work, we developed a one-step pyrolysis for producing fluorescent, water-soluble, and highly nitrogen-doped carbon dots (NCDs) from the readily available chemical precursors: tetraethylenepentamine and maleic anhydride. NCDs exhibited blue fluorescent emission with a relatively high quantum yield of 21% and average diameter of approximately 8 nm. These NCDs were found to be selective sensors for Cu²⁺, with a limit of detection of 0.62 μM. A simple NCD-coated, paper-based sensor demonstrated that the NCDs were highly responsive to and selective of Cu²⁺. Furthermore, X-ray absorption fine structure measurements showed the unique coordinating properties of the NCDs. The copper complex changed from a distorted octahedral to a square planar structure upon the addition of NCDs. The NCDs were also found to be an excellent adsorbent for Cu²⁺, with a surface coverage of 1.5 ions nm⁻², equivalent to 214 mg g⁻¹ adsorption capacity. In addition, NCDs were used to image a human fingerprint and for the preparation of fluorescent plastics. These results demonstrated that the multifunctional NCDs with excellent optical properties and water solubility produced in this work can be used in a range of applications, including sensors, adsorbents, imaging, and forensic science..
75.	Hui Wu, Yuji Higaki, Shiki Nojima, Atsushi Takahara, Orientation and crystallization of regioregular poly(3-dodecylthiophene) in alumina nanopores, Soft Matter, 10.1039/c7sm00859g, 13, 26, 4661-4666, 2017, The orientation and crystallization of regioregular poly(3-dodecylthiophene) (P3DDT) in different diameter nanopores were investigated. P3DDT nanowires were prepared by a melt-wetting nonporous alumina template with P3DDT melts. The microstructure of the nanowires was analyzed by micro-Fourier transform infrared spectroscopy, grazing incidence wide angle X-ray diffraction, and differential scanning calorimetry. Although Form I modification prevails in all the nanowires, Form I crystals decrease and Form II crystals increase as the pore diameter decreases. The crystallites developed in the nanowires preferentially aligned with π-π stacking (b-axis) along the long axis of the wire and this orientation is marked as the wire diameter decreases. These results could provide guidance on designing polymeric nanomaterials for functional nanodevices in high performance organic photovoltaic cells, sensors, and electrodes..
76.	Atsushi Takahara, Stephen Z D Cheng, Tribute to Tisato Kajiyama, Polymer, 10.1016/j.polymer.2017.03.038, 2017.
77.	Patcharida Chouwatat, Tomoyasu Hirai, Keiko Higaki, Yuji Higaki, Hung Jue Sue, Atsushi Takahara, Aqueous lubrication of poly(etheretherketone) via surface-initiated polymerization of electrolyte monomers, Polymer, 10.1016/j.polymer.2017.02.085, 2016.12, Poly(etheretherketone) (PEEK) substrate surface was modified with charged cationic poly(2-(methacryloyloxy) ethyltrimethylammonium chloride) (PMTAC) and anionic poly(3-sulfopropyl methacrylate potassium salt) (PSPMK) polymer brushes through surface-initiated radical polymerization triggered by UV light exposure of benzophenone groups in PEEK backbone as an initiator. After extensive UV light exposure, the PEEK surface was covered with grafted polyelectrolyte chains and exhibited swollen polyelectrolyte brushes with high roughness under water, indicating high graft density and wide molecular weight distributions of PMTAC and PSPMK brushes. The hydrated polyelectrolyte brushes on PEEK surface induce significant air bubble repellency in water. Thus, thickening of swollen polyelectrolyte brushes dramatically reduces the friction coefficient of PEEK surface under a wet condition..
78.	Shiki Nojima, Yuji Higaki, Katsuhiro Kaetsu, Ryohei Ishige, Noboru Ohta, Hiroyasu Masunaga, Tomoyasu Hirai, Ken Kojio, Atsushi Takahara, Effect of molecular mobility of pre-ordered phase on crystallization in microphase-separated lamellar morphology of strongly segregated crystalline-crystalline diblock copolymers, Polymer, 10.1016/j.polymer.2017.02.086, 2016.12, The effect of molecular mobility of a pre-crystallized phase on the isothermal crystallization in the microphase-separated lamellar morphology of a strongly segregated crystalline-crystalline block copolymer, poly(ethylene glycol)-block-poly(perfluorooctylethyl acrylate) (PEG-b-PFA-C₈), was investigated. The diblock copolymer produced a microphase-separated lamellar morphology in the melt state, and the precedent crystallization of PFA-C₈ blocks provided the lamellar confinement field. The counter PEG block crystallized within the lamellar confinement field. The molecular mobility of the pre-crystallized PFA-C₈ phase was modulated by the thermal history. The structural evolution was monitored by a complementary combination of in situ time-resolved simultaneous small-angle X-ray scattering/wide-angle X-ray diffraction measurements and thermal analyses. The degree of crystallinity and the melting temperature of the PEG crystals were associated with the molecular mobility of the pre-crystallized PFA-C₈ phase. The highly packed PFA-C₈ phase (higher-ordered phase) constrained the PEG crystallization, whereas the loosely packed PFA-C₈ phase (lower-ordered phase) caused a weak restriction in the PEG crystallization to give relatively ordered PEG crystals. Subsequent crystallization in a confinement field of crystalline-crystalline block copolymers was controlled by adjusting the molecular mobility of the pre-crystallized phase..
79.	W. Ma, Yuji Higaki, Atsushi Takahara, Imogolite Polymer Nanocomposites, Nanosized Tubular Clay Minerals Halloysite and Imogolite, 2016, 10.1016/B978-0-08-100293-3.00024-8, 7, 628-671, 2016.12, Imogolite is a naturally occurring aluminosilicate nanotube consisting of a single-walled with a composition of (OH)₃Al₂O₃SiOH, with Al–OH and Si–OH groups distributed on the external and internal surfaces of the tube wall, respectively. The recent progress in surface modification of imogolite utilizing specific interaction between Al–OH and phosphonic acid is reported in this chapter, and the preparation procedures of novel imogolite-based polymer nanocomposites are introduced..
80.	Yuji Higaki, Atsushi Takahara, Versatile anti-fouling surface design through nature-inspired approaches, Green Materials, 10.1680/jgrma.16.00011, 5, 1, 2016.12, Nature-inspired artificial anti-fouling systems, including a superhydrophobic surface, a liquid-infused omniphobic slippery surface, and an underwater oleophobic surface, were previously proposed and are reviewed herein. An alumina gel film was applied as a platform for a superhydrophobic and an omniphobic slippery surfaces to insure the mechanical durability of the surface geometry and easy processing. The superhydrophobicity of the alumina gel film with hierarchically micro/nano-structure was demonstrated. Infusion of fluorinated non-volatile fluid into the nano-structured alumina gel film gave omniphobic slippery surfaces for both polar and non-polar liquids. A substrate-independent underwater oleophobic surface processing was accomplished with a primer coating of mussel mimetic versatile adhesive copolymer containing catechol groups and subsequent LbL deposition of polyelectrolytes..
81.	Makoto Kido, Shiki Nojima, Ryohei Ishige, Kevin L. White, Kazutaka Kamitani, Noboru Ohta, Tomoyasu Hirai, Atsushi Takahara, Effect of molecular weight on microcrystalline structure formation in polymer with perylenediimide side chain, Journal of Polymer Science, Part B: Polymer Physics, 10.1002/polb.24115, 54, 22, 2275-2283, 2016.11, The effect of molecular weight on the molecular aggregation structure of polymers bearing a pendant perylenediimide (PDI) side chain, designated PAc12PDI, was investigated using synchrotron radiation X-ray diffraction measurements. It was found that depending on molecular weight, either the main chain axis or the side chain axis behaves as the longitudinal axis in fiber samples and was aligned parallel to the fiber axis. A similar phenomenon is present in thin film samples, but was complicated by the additional influence of the interfacial free energy of the side chain group. Even in the case of the polymer with lower molecular weight, the face plane of PDI was found to show both parallel and perpendicular orientations to the substrate (i.e., flat-on and edge-on orientations). On the other hand, if the length of the main chain is sufficiently long with respect to the length of the side chain, the face plane of PDI was oriented perpendicular to the substrate, leading to an edge-on orientation in the thin film. Â.
82.	Taiki Hoshino, Shiki Nojima, Masanao Sato, Tomoyasu Hirai, Yuji Higaki, So Fujinami, Daiki Murakami, Shigesaburo Ogawa, Hiroshi Jinnai, Atsushi Takahara, Masaki Takata, Observation of constraint surface dynamics of polystyrene thin films by functionalization of a silsesquioxane cage, Polymer, 10.1016/j.polymer.2016.08.040, 105, 487-499, 2016.11, The surface dynamics of polyhedral oligomeric silsesquioxane (POSS)-functionalized polystyrene (PS-POSS) thin films above the glass transition temperature were studied by grazing-incidence X-ray photon correlation spectroscopy in order to elucidate the effects of POSS at the end of the polystyrene chains. Much slower fluctuations were observed in the surface of PS-POSS thin films than in the polystyrene thin films, despite the negligible difference in their bulk viscosity. Quantitative analysis based on fluctuation-dissipation theorem indicated that there is a high-viscosity layer at the surface of the PS-POSS films, and that the substrate interface originated from POSS segregation..
83.	Yuji Higaki, Ken Suzuki, Noboru Ohta, Atsushi Takahara, Strain-induced molecular aggregation states around a crack tip in a segmented polyurethane film under uniaxial stretching, Polymer, 10.1016/j.polymer.2016.12.033, 2016.11, The development of molecular aggregation structures during stretching deformation and local structure mapping around a crack tip of a segmented polyurethane elastomer film were investigated by in situ simultaneous small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD) and by micro-beam WAXD, respectively. Both the hard segment (HS) domain orientation and the strain-induced crystallization of poly(ε-caprolactone) chains were tracked by the WAXD pattern due to the high crystallinity of the symmetric non-bulky aliphatic HS structure. Strain-induced crystallization occurred locally at the vicinity of the crack tip, and the crystallinity immediately decayed in the exterior, whereas the HS domain orientation was observed throughout the stretched film. The mechanisms underlying crack arrest and the mechanical strength of polyurethane elastomer films are associated with the local strain-induced crystallization at the crack tip, the mechanical stability of the HS domains, and the avoidance of local stress concentration through the HS domain orientation..
84.	Shiki Nojima, Yuji Higaki, Ryohei Ishige, Hirofumi Kabayama, Noboru Ohta, Hiroyasu Masunaga, Tomoyasu Hirai, Ken Kojio, Atsushi Takahara, Crystallization-induced structure fluctuation of crystallized microdomain structure composed of strongly segregated crystalline-crystalline diblock copolymers, Polymer, 10.1016/j.polymer.2016.09.024, 102, 256-265, 2016.10, Crystallization-induced structure fluctuations in the layer thickness direction and disordering of pre-crystallized structure in crystallized microdomain structure that consist of a strongly segregated crystalline-crystalline diblock copolymer, poly(ethylene glycol)-block-poly(perfluorooctyl ethyl acrylate) (PEG-b-PFA-C₈), were investigated. The structure formation process during isothermal crystallization was monitored by in-situ time-resolved simultaneous SAXS/WAXD measurements and thermal analysis. At early stage of isothermal crystallization, three dimensional growth of the PEG lamellar crystals within lamellar microphase-separated morphology induced the volume shrinkage of PEG phase, resulting in the reduction of PEG layer thickness, increase of PFA-C₈ layer thickness and disordering of pre-crystallized PFA-C₈ crystals. At late stage of isothermal crystallization, one dimensional growth, thickening of PEG lamellar crystals induced the increase of PEG layer thickness and reduction of PFA-C₈ layer thickness. The structure fluctuation in the crystallized microdomain structure depends on the crystal growth dimension..
85.	Kyung Lynne Park, Wei Ma, Yuji Higaki, Atsushi Takahara, Design and characterization of hybrid hydrogels composed of imogolite fibrous nanotubular clay and hyaluronic acid, Polymer, 10.1016/j.polymer.2016.08.018, 100, 238-243, 2016.09, Hybrid hydrogels composed of imogolite fibrous nanotube (IG) and hyaluronic acid (HA) were prepared. Hexamethylenediamine (HMDA) was used as a non-toxic chemical cross-linker. The homogeneous dispersion of IG in the HA solution was accomplished by careful pH control, and subsequent chemical cross-linking provided mechanically stable self-standing hybrid hydrogels. The IG/HA hybrid hydrogels were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), swelling test, compression test, oscillatory rheological analysis, and enzymatic degradation test. The IG/HA hybrid hydrogels show better mechanical properties and lower degradation rate than native HA-based hydrogels without IG hybridization because the cross-linking density increases by incorporation of additional IG network into chemically cross-linked HA network..
86.	Ryohei Ishige, Noboru Ohta, Hiroki Ogawa, Masatoshi Tokita, Atsushi Takahara, Fully Liquid-Crystalline ABA Triblock Copolymer of Fluorinated Side-Chain Liquid-Crystalline A Block and Main-Chain Liquid-Crystalline B Block Higher Order Structure in Bulk and Thin Film States, Macromolecules, 10.1021/acs.macromol.6b00855, 49, 16, 6061-6074, 2016.08, Fully liquid-crystalline (LC) ABA-type triblock copolymers were synthesized by atom transfer radical polymerization; the A block was a fluorinated side-chain LC polymer, PFA-C₈, and the B block was a main-chain LC polyester, BB-5(3-Me). The volume fraction of the A block (ψ_A) was 0.11-0.70, and the B block had a constant molecular weight. Nanometer-scale segregated structures in the bulk and thin film states were investigated by synchrotron X-ray diffraction (XRD) in transmission and grazing-incidence (GI) geometries to examine the effect of competition between the LC orientation and polymer chain dimensions on the morphology. When ψ_A is 0.11, matching of the mesogen orientation in the A and B blocks dominates the main-chain orientation, whereas when ψ_A exceeds 0.28, matching of the lateral dimensions of the A and B blocks dominates the mesogen orientation, although all the polymers showed lamellar structure before isotropization of BB-5(3-Me). GI-XRD revealed that the lamellar structure in the thin film with ψ_A = 0.70 was completely perpendicular to the Si substrate without surface modification or solvent annealing..
87.	Daigo Kobayashi, Atsushi Takahara, Interphase crystal structure of polyamide 6 on carbon materials revealed by grazing incidence X-ray diffraction with synchrotron radiation, Polymer, 10.1016/j.polymer.2016.05.028, 97, 174-178, 2016.08, The orientation of polyamide6 (PA6) crystallites on the surface of carbon materials was investigated through grazing incidence wide-angle X-ray diffraction (GIWAXD) on the BL46XU beam line at SPring-8. PA6 films on graphite and amorphous carbon were implemented to model the interphase of the composite with PA6 and the carbon materials. Only the α crystal was observed in the in-plane GIWAXD profile of PA6 on a graphite plate. Further, it was found that the highly oriented graphite structure induced the α crystalline form of PA6 and made the methylene chains align/orient themselves epitaxially..
88.	Daiki Murakami, Yuki Norizoe, Yuji Higaki, Atsushi Takahara, Hiroshi Jinnai, Direct Characterization of In-Plane Phase Separation in Polystyrene Brush/Cyclohexane System, Macromolecules, 10.1021/acs.macromol.6b00151, 49, 13, 4862-4866, 2016.07, The phase behavior of polystyrene (PS) brushes in cyclohexane (CHX) was investigated, for the first time, by environmental atomic force microscopy as a function of the graft density and temperature. The polystyrene brushes of three different graft densities exhibited island-, bicontinuous-, and hole-shape microdomains in the direction parallel to the substrate. The size of such "in-plane" microdomains is close to the end-to-end distance of PS brush chain due to the anchoring of one of the chain ends of PS brushes to the substrate. The microdomain structure disappeared as the temperature increased, and new structure with same morphological features reappeared by lowering temperature. This reversible temperature response corresponds to the in-plane phase separation of the PS brush/CHX system. The UCST type binodal line shifted toward slightly lower temperature in the PS brush/CHX system compared to that of the corresponding nongrafted polymer solution, i.e., PS/CHX system, in excellent agreement with our previous Monte Carlo simulation study..
89.	Yoshio Furusho, Takeshi Endo, Keiko Higaki, Katsuhiro Kaetsu, Yuji Higaki, Ken Kojio, Atsushi Takahara, Supramolecular network polymers formed from polyamidine and carboxy-terminated telechelic poly(n-butyl acrylate) via amidinium-carboxylate salt bridges, Journal of Polymer Science, Part A: Polymer Chemistry, 10.1002/pola.28082, 54, 14, 2148-2155, 2016.07, We have prepared the amidinium-carboxylate salt bridge-based supramolecular network polymers from a carboxy-terminated telechelic poly(n-butyl acrylate) and a linear polyamidine having N,N′-di-substituted acetamidine group in the main chain. FTIR measurements indicated that the salt bridge was attributed to the three-dimensional network formation. Virtually, no fluidity was observed for the blend containing equimolar amounts of the carboxyl group and the amidine group, which showed a high G′ value of about 1 MPa at -5 Â°C. For comparison, the supramolecular network polymers crosslinked by ammonium-carboxylate salt were prepared using a linear polyethyleneimine instead of the polyamidine. The blend with equimolar amounts of the carboxyl group and the secondary amino group showed liquid-like fluidity with a G′ value of about 0.01 MPa at -5 Â°C, which was attributed to the fact that a certain amount of the carboxyl group remained as its free form, as evidenced by FTIR analysis..
90.	Yuji Higaki, Motoyasu Kobayashi, Daiki Murakami, Atsushi Takahara, Anti-fouling behavior of polymer brush immobilized surfaces, Polymer Journal, 10.1038/pj.2015.137, 48, 4, 325-331, 2016.04, Polymer brushes have been utilized as a proper model interface for the investigation of wetting, lubrication, hydrated chain dimension and the structure of hydrated water at hydrated polymer interfaces. Zwitterionic polyelectrolyte-tethered surfaces represent significant anti-fouling materials for bio-macromolecules, marine fouling organisms and pipeline foulants. Systematic anti-fouling tests for various polymer brushes were performed to demonstrate the critical factors for universal anti-fouling properties. In this focused review, material design concepts and recent progress on anti-fouling polymer materials are reviewed, and our recent research on anti-fouling studies using polymer brushes is provided..
91.	Rina Maeda, Takeshi Higuchi, Kenta Okuhara, Ryohei Kikuchi, Atsushi Takahara, Christopher K. Ober, Hiroshi Jinnai, Teruaki Hayakawa, Interface manipulated two-phase nanostructure in a triblock terpolymer with a short middle segment, Polymer Journal, 10.1038/pj.2016.25, 48, 4, 533-538, 2016.04, Interface manipulation to pursue unusual nanostructures was performed using a strategically designed triblock terpolymer with a short middle segment, poly(styrene-b-methyl methacrylate-b-2,2,2-trifluoroethyl methacrylate). A short middle segment of poly(methyl methacrylate) (PMMA) that does not form any distinct domains was found to play an important role in manipulating the interface between the polystyrene (PS) and poly(2,2,2-trifluoroethyl methacrylate) (PTFEMA) domains and forming unconventional partially continuous oblate cylinders with an oblique lattice, as confirmed by small angle X-ray scattering (SAXS) and dual-axis transmission electron microtomography (TEMT)..
92.	Daigo Kobayashi, Ya Ting Hsieh, Atsushi Takahara, Interphase structure of carbon fiber reinforced polyamide 6 revealed by microbeam X-ray diffraction with synchrotron radiation, Polymer, 10.1016/j.polymer.2016.02.057, 89, 154-158, 2016.04, Carbon fiber reinforced polyamide 6 (PA6) films were fabricated in this study. A 2 microns polyamide 6 (PA6) transcrystalline layer with positive type birefringence was observed at the interphase region of PA6 and high modulus carbon fiber (HMCF) by using polarized optical microscopy, while no crystal layer was observed at that of PA6 and standard modulus carbon fiber (SMCF). HMCF exhibited higher nucleation efficacy in PA6 matrix than SMCF during cooling process, investigated by differential scanning calorimetry. The crystal form and orientation at the interphase region was further confirmed by microbeam wide angle X-ray diffraction (μWAXD). The μWAXD results show that α phase is the major crystalline fraction in PA6/HMCF and PA6/SMCF composites and the α crystalline percentage is slightly increase at the transcrystalline layer of PA6/HMCF composite. The μWAXD results also suggest that the a axis of α crystals in the transcrystalline layer are predominantly perpendicular to the fiber direction..
93.	Motoyasu Kobayashi, Masataka Kaido, Atsushi Suzuki, Atsushi Takahara, Tribological properties of cross-linked oleophilic polymer brushes on diamond-like carbon films, Polymer, 10.1016/j.polymer.2016.02.040, 89, 128-134, 2016.04, Surface-initiated atom transfer radical copolymerization of hexyl methacrylate (HMA) and 3-ethyl-3-oxetanylmethyl methacrylate (OxMA) was carried out on the surfaces of block- and ring-type steel pieces covered with silicon-incorporated diamond-like carbon (DLC-Si) in order to generate an oleophilic copolymer brush layer at the outermost surface. The sample was then immersed in a 1% BF₃OEt₂ solution to form cross-linkages between oxetane groups in the polymer brush chains. The thickness of the polymer brush layer was confirmed to be 50 nm through transmission electron microscope images of the focused ion beam (FIB)-fabricated cross section. The friction properties of the composite films were evaluated using block-on-ring tests under a load of 49 N (130 MPa), using a base oil at 353 K for 30 min. Although the brush layer was partially scratched from the substrate surface during the friction test, the polymer brush-immobilized DLC-Si exhibited a low friction coefficient of 0.02, while the friction coefficient of the non-modified steel substrate was 0.12. It is supposed that the oleophilic polymer brush was swollen in the oil to form a stable lubrication layer, thus preventing the direct contact of the DLC-Si substrate. The dependency of the tribological properties on normal load, sliding velocity, wear depth, and the silicon content of the DLC-Si substrate was also investigated..
94.	Masanao Sato, Tomoki Kato, Tomoyuki Ohishi, Ryohei Ishige, Noboru Ohta, Kevin L. White, Tomoyasu Hirai, Atsushi Takahara, Precise Synthesis of Poly(methyl methacrylate) Brush with Well-Controlled Stereoregularity Using a Surface-Initiated Living Anionic Polymerization Method, Macromolecules, 10.1021/acs.macromol.5b02773, 49, 6, 2071-2076, 2016.03, Densely grafted polymer brushes, which consist of end-tethered chains that are predominantly oriented perpendicular to the substrate, show a number of unique functional properties due to their highly organized structure. Controlling the stereoregularity of the main chain while maintaining a high grafting density offers further opportunities to increase the density of functional sites through the formation of cavities within the brush structure. Concentrated poly(methyl methacrylate) (PMMA) brushes with well-controlled stereoregularity and polydispersity index (PDI) were prepared on flat and spherical substrates using a surface-initiated living anionic polymerization method in the presence of triethylaluminum (AlEt₃). The syndiotactic PMMA brush forms with helical chains and is able to encapsulate C₆₀ molecules within the formed cavities..
95.	Patcharida Chouwatat, Shiki Nojima, Yuji Higaki, Ken Kojio, Tomoyasu Hirai, Masaya Kotaki, Atsushi Takahara, An effect of surface segregation of polyhedral oligomeric silsesquioxanes on surface physical properties of acrylic hard coating materials, Polymer, 10.1016/j.polymer.2015.12.037, 84, 81-88, 2016.02, An effect of surface segregation of polyhedral oligomeric silsesquioxanes (POSS) on surface physical properties was investigated. Hard coating layer with various MA₈POSS loadings was prepared on a bilayer of soft layer and PMMA substrate via a UV curing process. The scratch resistance of the coating layer showed specific properties. When MA₈POSS loadings in the coating layers were less than 10 wt %, the coating layers showed a great performance in scratch resistance. While MA₈POSS loadings were higher than 10 wt %, the surface performance was deteriorated. This is because the outermost surface of the coating layer was covered by MA₈POSS molecules when the MA₈POSS loadings were higher than 10 wt %, resulting in uncompleted curing reaction caused by large steric hindrance of MA₈POSS..
96.	Tomoya Sato, Tomoyuki Ohishi, Yuji Higaki, Atsushi Takahara, Hideyuki Otsuka, Radical crossover reactions of alkoxyamine-based dynamic covalent polymer brushes on nanoparticles and the effect on their dispersibility, Polymer Journal, 10.1038/pj.2015.94, 48, 2, 147-155, 2016.02, The dynamic covalent exchange reactions of side chains in polymer brushes on nanoparticles were successfully demonstrated, and the dispersibility of the nanoparticles after the exchange reactions was investigated in some solvents. A polymer brush with exchangeable alkoxyamine side chains was prepared by surface-initiated atom transfer radical polymerization on silica nanoparticles. Fluorinated and ionic polymers were grafted to the polymer brush via radical exchange reactions of alkoxyamine moieties. The chemical composition of the polymer brushes on nanoparticles before and after the exchange reactions was investigated by X-ray photoelectron spectroscopy (XPS). The XPS measurements indicated that the side chains of the polymer brushes were converted to the corresponding polymers. In addition, the grafted side chains could be detached from the surface of the nanoparticles through a further radical exchange process by treating with alkoxyamines. The XPS results indicate that the structure of the de-grafted polymer brush is nearly the same as the original, thus demonstrating the reversibility of the reactions. Furthermore, the dispersibility of the nanoparticles in solution could be changed by the reversible grafting reactions..
97.	Daiki Murakami, Motoyasu Kobayashi, Yuji Higaki, Hiroshi Jinnai, Atsushi Takahara, Swollen structure and electrostatic interactions of polyelectrolyte brush in aqueous solution, Polymer, 10.1016/j.polymer.2016.04.041, 2016.02, Surface grafting of polyelectrolytes on materials brings about various significant changes in surface properties such as wettability, adhesion, and friction, because of their excellent hydrophilicity and unique intermolecular interactions that depend on the ionic strength of the solution. This review paper describes the characterization of the swollen structure and electrostatic interaction of polyelectrolyte brushes in aqueous solution by use of optical tweezers and neutron reflectivity, in order to discuss the dissociation of ionic groups and charge distribution in the polyelectrolyte brush. In addition, the spreading and structure of water on the polyelectrolyte brush surface were characterized by high spatial resolution IR spectroscopy..
98.	Rina Yoneyama, Tomoya Sato, Keiichi Imato, Takahiro Kosuge, Tomoyuki Ohishi, Yuji Higaki, Atsushi Takahara, Hideyuki Otsuka, Autonomously Substitutable Organosilane Thin Films Based on Dynamic Covalent Diarylbibenzofuranone Units, Chemistry Letters, 10.1246/cl.150917, 45, 1, 36-38, 2016.01, Autonomously substitutable organosilane thin films based on diarylbibenzofuranone (DABBF) units were prepared, and the radical exchange reactions of the DABBF units at the surface resulted in chemically reversible surface character changes without external stimuli. The reversible changes of the surface properties were confirmed by X-ray photoelectron spectroscopy and water contact angle measurements..
99.	Chen Shi, Bin Yan, Lei Xie, Ling Zhang, Jingyi Wang, Atsushi Takahara, Hongbo Zeng, Long-Range Hydrophilic Attraction between Water and Polyelectrolyte Surfaces in Oil, Angewandte Chemie - International Edition, 10.1002/anie.201608219, 55, 48, 15017-15021, 2016.01, The outstanding water wettability and the capability of polyelectrolyte surfaces to spontaneously clean oil fouling are determined by their wetting mechanism in the surrounding medium. Here, we have quantified the nanomechanics between three types of polyelectrolyte surfaces (i.e. zwitterionic, cationic, and anionic) and water or oil drops using an atomic force microscope (AFM) drop probe technique, and elucidated the intrinsic wetting mechanisms of the polyelectrolyte surfaces in oil and water media. The measured forces between oil drops and polyelectrolyte surfaces in water can be described by the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. Surprisingly, strong long-range attraction was discovered between polyelectrolyte surfaces and water drops in oil, and the strongest interaction was measured for the polyzwitterion. This unexpected long-range “hydrophilic” attraction in oil could be attributed to a strong dipolar interaction because of the large dipole moment of the polyelectrolytes. Our results provide new nanomechanical insights into the development of novel polyelectrolyte-based materials and coatings for a wide range of engineering, bioengineering, and environmental applications..
100.	Tomoyasu Hirai, Y. Nagae, K. L. White, K. Kamitani, M. Kido, T. Uchiyama, Maiko Nishibori, Y. Konishi, K. Yokomachi, R. Sugimoto, K. Saigo, T. Ohishi, Yuji Higaki, Ken Kojio, Atsushi Takahara, Solvent free oxidative coupling polymerization of 3-hexylthiophene (3HT) in the presence of FeCl₃ particles, RSC Advances, 10.1039/c6ra23178k, 6, 113, 111993-111996, 2016.01, A solvent free oxidative coupling reaction of 3-hexylthiophene (3HT) within a nanocavity is reported. It is found that 3HT can be encapsulated in nanocavities larger than 1 nm, which corresponds to the size of the molecule. In this case, the side reaction at the 4-position in 3HT is regulated..
101.	Yutaka Yamada, Koji Takahashi, Tatsuya Ikuta, Takashi Nishiyama, Yasuyuki Takata, Wei Ma, Atsushi Takahara, Tuning Surface Wettability at the Submicron-Scale Effect of Focused Ion Beam Irradiation on a Self-Assembled Monolayer, Journal of Physical Chemistry C, 10.1021/acs.jpcc.5b09019, 120, 1, 274-280, 2016.01, Realizing surface wettability tuning at the submicron-scale resolution is expected to enable the fabrication of micro/nano-structured fluidic devices and is particularly important in nanobiotechnology and high-resolution printing. Herein, we propose an approach to modify the wettability of self-assembled monolayer surfaces using focused ion beam (FIB) irradiation. The contact angle of the irradiated region changed from hydrophobic to hydrophilic by increasing the ion dosage. The chemical composition and associated depth profile of the sample surfaces were analyzed by glow discharge-optical emission spectroscopy. The results indicated that the content of fluorine at the surface decreased after FIB irradiation of the samples. A submicron-scale hydrophobic-hydrophilic hybrid surface was then fabricated by forming hydrophilic dots with diameters of ∼110 nm on a hydrophobic surface by FIB irradiation. The difference in wettability of the hydrophobic and hydrophilic areas on the surface was confirmed by microscale condensation and evaporation experiments. Condensed droplets with diameters of ∼300 nm appeared on the surface according to the fabricated pattern, thus suggesting that condensation preferentially occurred on the hydrophilic dots than on the hydrophobic surface. Furthermore, tiny droplets remained on the hydrophilic dots following evaporation of the larger droplets. The current approach provides a means to control wettability-driven phenomena..
102.	Hirohmi Watanabe, Aya Fujimoto, Jin Nishida, Tomoyuki Ohishi, Atsushi Takahara, Biobased polymer coating using catechol derivative urushiol, Langmuir, 10.1021/acs.langmuir.6b00484, 32, 18, 4619-4623, 2016, We have investigated the mechanism of the superior mechanical robustness of coated thin films of the catechol derivative urushiol. We synthesized hydrogenated urushiol (h-urushiol) by hydrogenating the double bonds in the long alkyl side chain of urushiol, and the physical properties of thin films of mixtures of urushiol and h-urushiol were evaluated. Atomic force microscopy observations revealed that these coated thin films have a homogeneous surface with no phase separation, regardless of the h-urushiol content, arising from the similarity of the chemical structures. The films showed good adhesive properties because the adhesion originates from the catechol structure. In contrast, curing time depended strongly upon the h-urushiol content. The curing of the h-urushiol thin film took 12 h, whereas the urushiol thin film was cured within 10 min. Moreover, the strain-induced elastic buckling instability for mechanical measurements test and the bulge test confirmed that the increase in the h-urushiol content decreased the mechanical strength. Because the double bonds in the urushiol side chain contribute to forming the highly cross-linked structure, the lack of double bonds in hurushiol resulted in the slow curing and low mechanical strength. Interestingly, the mechanical robustness started to increase over 80 mol % h-urushiol. The saturated long alkyl side chain of h-urushiol faced the surface, and the regular structure of the uniform side chain may improve the mechanical properties of the coated film. Our results will help to develop biomimetic catechol-based coatings..
103.	Motoyasu Kobayashi, Yuji Higaki, Taichi Kimura, Frédéric Boschet, Atsushi Takahara, Bruno Ameduri, Direct surface modification of poly(VDF- Co -TrFE) films by surface-initiated ATRP without pretreatment, RSC Advances, 10.1039/c6ra18397b, 6, 89, 86373-86384, 2016, The direct surface modification of poly(vinylidene fluoride-co-trifluoroethylene) (VDF-co-TrFE) copolymer films via surface-initiated atom transfer radical polymerization (ATRP) is presented. The surface-initiated ATRP of tert-butyl acrylate (tBA) and styrene was carried out on poly(VDF-co-TrFE) films containing 75 mol% VDF at 383 K. Such a reaction was monitored by ¹H and ¹⁹F NMR, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and by water contact angle measurements. First, the ¹⁹F NMR spectra of poly(VDF-co-TrFE)-g-poly(tBA) graft copolymers revealed a reduction in the signal intensity at -123 ppm compared with that of the poly(VDF-co-TrFE) copolymer, indicating that the polymerization of tBA occurred exclusively by fluorine abstraction from the TrFE units. ATR-FTIR spectra of the resulting poly(VDF-co-TrFE)-g-poly(tBA) and poly(VDF-co-TrFE)-g-polystyrene (PS) films evidenced the characteristic absorption frequencies assigned to carbonyl and aromatic C-H stretching. The atomic ratio on the surface of polymer-grafted poly(VDF-co-TrFE) film observed by XPS well agreed with theoretical value of poly(tBA) and PS hompolymers. These results indicated that poly(tBA) and PS were successfully grafted onto the poly(VDF-co-TrFE) film surfaces forming grafting layers, the thickness of which was over 10 nm. The poly(VDF-co-TrFE)-g-poly(tBA) film was subsequently treated with p-toluenesulfonic acid and sodium hydrogen carbonate to modify the grafted chains into poly(acrylic acid sodium salt). Surface-grafted polystyrene was also converted to poly(styrene sulfonic acid sodium salt) by treatment with sulfonic acid. Each reaction step was characterized by ATR-IR and XPS. The static water contact angle of poly(VDF-co-TrFE) copolymer was remarkably reduced from 91 to 15° by hydrolysis of the tBA chains, sulfonation of the styrene chains and their neutralization. A hydrophilic surface was successfully achieved on the poly(VDF-co-TrFE) film by direct surface-initiated polymerization from the outermost surface of the TrFE unit without any change in the bulk physical properties..
104.	Ryohei Ishige, Gregory A. Williams, Yuji Higaki, Noboru Ohta, Masugu Sato, Atsushi Takahara, Zhibin Guan, In situ ultra-small-angle X-ray scattering study under uniaxial stretching of colloidal crystals prepared by silica nanoparticles bearing hydrogen-bonding polymer grafts, IUCrJ, 10.1107/S205225251600556X, 3, 211-218, 2016, A molded film of single-component polymer-grafted nanoparticles (SPNP), consisting of a spherical silica core and densely grafted polymer chains bearing hydrogen-bonding side groups capable of physical crosslinking, was investigated by in situ ultra-small-angle X-ray scattering (USAXS) measurement during a uniaxial stretching process. Static USAXS revealed that the molded SPNP formed a highly oriented twinned face-centered cubic (f.c.c.) lattice structure with the [11-1] plane aligned nearly parallel to the film surface in the initial state. Structural analysis of in situ USAXS using a model of uniaxial deformation induced by rearrangement of the nanoparticles revealed that the f.c.c. lattice was distorted in the stretching direction in proportion to the macroscopic strain until the strain reached 35%, and subsequently changed into other f.c.c. lattices with different orientations. The lattice distortion and structural transition behavior corresponded well to the elastic and plastic deformation regimes, respectively, observed in the stress-strain curve. The attractive interaction of the hydrogen bond is considered to form only at the top surface of the shell and then plays an effective role in cross-linking between nanoparticles. The rearrangement mechanism of the nanoparticles is well accounted for by a strong repulsive interaction between the densely grafted polymer shells of neighboring particles..
105.	Preparation of Novel Functional Interface using Polymethyl Methacrylate (PMMA) Brush with Well-Controlled Stereoregularity.
106.	Keiichi Imato, Takeshi Kanehara, Shiki Nojima, Tomoyuki Ohishi, Yuji Higaki, Atsushi Takahara, Hideyuki Otsuka, Repeatable mechanochemical activation of dynamic covalent bonds in thermoplastic elastomers, Chemical Communications, 10.1039/c6cc04767j, 52, 69, 10482-10485, 2016, Repeated mechanical scission and recombination of dynamic covalent bonds incorporated in segmented polyurethane elastomers are demonstrated by utilizing a diarylbibenzofuranone-based mechanophore and by the design of the segmented polymer structures. The repeated mechanochemical reactions can accompany clear colouration and simultaneous fading..
107.	Yuji Higaki, Takahiro Yano, Di Tao, Hirofumi Kabayama, Atsushi Takahara, Surface modification of non-woven electrospun fine fiber mats through surface-initiated atom transfer radical polymerization, Kobunshi Ronbunshu, 10.1295/koron.2016-0085, 73, 3, 225-232, 2016, Electrospun fine fibers were surface-modified by surface-initiated atom transfer radical polymerization (SI-ATRP) to reform their surface character without sacrificing their bulk properties. Electrospun fibers of two types of polymers, poly(methyl methacrylate)-based copolymers and semicrystalline poly(butylene terephthalate), that have ATRP initiating units attached to them were modified by poly(sulfobetaine) brushes or fluorinated polymer brushes. The fluorinated polymer brushes make the electrospun fiber mat super-hydrophobic, whereas the poly(sulfobetaine) brushes make the electrospun fiber super-hydrophilic. These mats can be used for water/oil separation and exhibit non-fouling properties. The semi-crystalline polyester fibers keep these properties even at elevated temperatures..
108.	高原淳, K. L. White, S. Hawkins, M. Miyamoto, H.-J. Sue, Effects of aspect ratio and concentration on rheology of epoxy suspensions containing model plate-like nanoparticles , Phys. Fluids, 10.1063/1.4937145, 27, 12, 123306/1-123306/23, 2015.12.
109.	Xinxing Lin, Wei Ma, Hui Wu, Shilin Cao, Liulian Huang, Lihui Chen, Atsushi Takahara, Superhydrophobic magnetic poly(DOPAm-co-PFOEA)/Fe₃O₄/cellulose microspheres for stable liquid marbles, Chemical Communications, 10.1039/c5cc08842a, 52, 9, 1895-1898, 2015.12, Novel magnetic superhydrophobic cellulose-based microspheres were fabricated using poly(DOPAm-co-PFOEA), which provide remarkable stability to liquid marbles with various liquids for liquid droplet transportation and manipulation..
110.	高原淳, 今任　景一, 金原　武志, 大石智之, 西原　正通, Hirofumi Yajima, Masayoshi Ito, 大塚英幸, Mechanochromic Dynamic Covalent Elastomers: Quantitative Stress Evaluation and Autonomous Recovery, ACS Macro Lett., 10.1021/acsmacrolett.5b00717, 4, 11, 1307-1311, 2015.11.
111.	Stephen Matthew Lyth, Wei Ma, Jianfeng Liu, Takeshi Daio, Kazunari Sasaki, Atsushi Takahara, Bruno Ameduri, Solvothermal Synthesis of Superhydrophobic Hollow Carbon Nanoparticles from Fluorinated Alcohol, Nanoscale, 10.1039/C5NR03484A, 7, 16087-16093, 2015.10.
112.	Tisato Kajiyama, Hirohiko Yakabe, Daisuke Kawaguchi, Atsushi Takahara, Keiji Tanaka, Melting behavior of thin polyethylene films, JOURNAL OF PLASTIC FILM & SHEETING, 10.1177/8756087915594418, 31, 4, 401-413, 2015.10.
113.	Shota Fujii, Makoto Kido, Masanao Sato, Noboru Ohta, Yuji Higaki, Tomoyasu Hirai, Ken Kojio, Atsushi Takahara, pH-Responsive and Selective Protein Adsorption on an Amino Acid-Based Zwitterionic Polymer Surface, Polymer Chemistry, 10.1039/c5py00783f, 6, 7053-7059, 2015.10.
114.	Stephen Matthew Lyth, W. Ma, J. Liu, T. Daio, Kazunari Sasaki, Atsushi Takahara, B. Ameduri, Solvothermal synthesis of superhydrophobic hollow carbon nanoparticles from a fluorinated alcohol, Nanoscale, 10.1039/c5nr03484a, 7, 38, 16087-16093, 2015.10, A new and simple method of synthesizing fluorinated carbon at the gram scale is presented by reacting a fluorinated alcohol with sodium at elevated temperatures in a sealed Teflon reactor. The resulting carbon nanoparticles are around 100 nm in diameter, and display a hollow shell morphology, with a significant amount of fluorine doped into the carbon. The nanoparticles disperse easily in ethanol, and are thermally stable up to 400°C and 450°C under air and nitrogen, respectively. The nanoparticle dispersion was printed onto various substrates (paper, cloth, silicon), inducing superhydrophobicity..
115.	Tomoyasu Hirai, Masanao Sato, Makoto Kido, Yusuke Nagae, Katsuhiro Kaetsu, Yudai Kiyoshima, Shota Fujii, Tomoyuki Ohishi, Kevin L. White, Yuji Higaki, Yasutake Teraoka, Maiko Nishibori, Kazutaka Kamitani, Kenji Hanada, Takeharu Sugiyama, Ryuichi Sugimoto, Kazuhiko Saigo, Ken Kojio, and Atsushi Takahara, X-ray Absorption Fine Structure Study on the Role of Solvent on Polymerization of 3-Hexylthiophene with Solid FeCl3 Particles, J.　Polym. Sci. , Polym. Chem. , 10.1002/pola.27720, 53, 18, 2035-2078, 2015.09.
116.	高原淳, Di Tao, Yuji Higaki, Wei Ma, Halloysite Nanotubes/Polyelectrolyte Hybrids as Adsorbents for Quick Removal of Dyes from Aqueous Solution, Chemistry Letters, 10.1246/cl.150727, 11, 1572-1574, 2015.09.
117.	高原淳, Yuji Higaki, 西田仁, 竹中　愛, 吉松　梨加, 小林元康, Versatile Marine Organism Settlement Inhibition of Zwitterionic Polymer Brushes, Polymer Journal, 10.1038/pj.2015.77, 47, 12, 811-818, 2015.09.
118.	Atsushi Takahara, N. L. Yamada, K. Mitamura, H. Sagehashi, N. Torikai, S. Sato, H.Seto, M. Furusaka, T. Oda, M. Hino, T. Fujiwara, M. Kobayash, Development of Sample Environments for the SOFIA Reflectometer for Seconds-Order Time-Slicing Measurements, JPS Conference Proceedings , 10.7566/JPSCP.8.036003, 8, 036003, 2015.09.
119.	Keiichi Imato, Atsushi Takahara, Hideyuki Otsuka, Self-Healing of a Cross-Linked Polymer with Dynamic Covalent Linkages at Mild Temperature and Evaluation at Macroscopic and Molecular Levels, MACROMOLECULES, 10.1021/acs.macromol.5b00809, 48, 16, 5632-5639, 2015.08.
120.	Sudu Siqing, Hui Wu, Atsushi Takahara, Molecular Reorientation of Polyimide Film Induced by Thermal Nanoimprint Lithography and Liquid Crystals Alignment on It, Polymer, 10.1016/j.polymer.2015.06.062, 72, 113-117, 2015.08.
121.	J.Nishida, Y. Higaki, A. Takahara, Synthesis and Characterization of Barnacle Adhesive Mimetic towards the Underwater Adhesion, Chem . Lett., 10.1246/cl.150311, 44, 8, 1047-1049, 2015.08.
122.	Atsushi Takahara, Young Yong Kim, Brian J. Ree, 城戸　信人, Yong-Gi Ko, 石毛亮平, Tomoyasu Hirai, Dongwoo Wi, Jehan Kim, Won Jong Kim, High Performance n-Type Electrical Memory and Morphology-Induced Memory-Mode Tuning of A Well-Defined Brush Polymer Bearing Perylene Diimide Moieties, Advanced Electronic Materials, 10.1002/aelm.201500197, 1, 10, 1500197/1-1500197/15, 2015.08.
123.	Masanao Sato, Xinyue Zheng, Tomoyasu Hirai, Atsushi Takahara, Precise Synthesis of Poly(α-methylene-γ-butyrolactone) and Evaluation of Its Characteristics, Koubunshi Ronbunshu, 10.1295/koron.2014-0101, 72, 7, 447-452, 2015.07.
124.	Keiichi Imato, Masamichi Nishihara, Atsushi Irie, Atsushi Takahara, Hideyuki Otsuka, Diarylbibenzofuranone-Based Dynamic Covalent Polymer Gels Prepared via Radical Polymerization and Subsequent Polymer Reaction, Gels, 10.3390/gels1010058, 1, 1, 58-68, 2015.07.
125.	Takashi Uemura, Tetsuya Kaseda, Yotaro Sasaki, Munehiro Inukai, Takaaki Toriyama, Atsushi Takahara, Hiroshi Jinnai, and Susumu Kitagawa, Mixing of immiscible polymers using nanoporous coordination templates, Nature Communications, 10.1038/ncomms8473, 6, 7473, 2015.07.
126.	G. A. Williams, R.Ishige, J. Chung, O. R. Cromwell, A. Takahara, Z. Guan, Mechanically robust and self-healable superlattice nanocomposites by self-assembly of single-component “sticky” polymer-grafted nanoparticles, Advanced Materials, 10.1002/adma.201500927, 27, 26, 3934-3941, 2015.07.
127.	T. Shinohara, Y. Higaki, S. Nojima, H Masunaga. H. Ogawa, Y. Okamoto,. T. Aoki, A. Takahara, Molecular Aggregation States and Wetting Behavior of a Poly{2-(perfluorooctyl)ethyl acrylate} Brush-Immobilized Nano-imprinted Surface, Polymer, 10.1016/j.polymer.2015.05.042, 69, 10-16, 2015.07.
128.	T. Sato, K. Akamine, A, Takahara, H. Otsuka, Macromolecular Design of Alkoxyamine-containing Radically Reactive Polymers Based on Dynamic Covalent Chemistry, Kobunshi Ronbunshu, 10.1295/koron.2015-0006, 72, 6, 341-353, 2015.06.
129.	T. Higuchi, H. Nishiyama, M. Suga, H. Watanabe, A. Takahara, H. Jinnai, One-step nanopatterning of conjugated polymers by electron-beam-assisted electropolymerization, Microscopy, 10.1093/jmicro/dfv013, 64, 3, 205-212, 2015.06.
130.	T. Shirahase, M. Kikuchi, T. Shinohara, M. Kobayashi, A. Takahara, Effect of Nanoparticle SiO2 grafted Poly methacryl methyl on Poly (L-lactic) acid Crystallization, Polym. Bull, 10.1007/s00289-015-1336-1, 72, 6, 1247-1263, 2015.06.
131.	Keita Kuroda, Hiromi Miyoshi, Shota Fujii, Tomoyasu Hirai, Atsushi Takahara, Aiko Nakao, Yasuhiko Iwasaki, Kenichi Morigaki, Kazuhiko Ishihara and Shin-ichi Yusa, Poly(dimethylsiloxane) (PDMS) surface patterning by biocompatible photo-crosslinking block copolymers, RSC Advances, 10.1039/C5RA08843G, 5, 46686-46693, 2015.05.
132.	H. Jing, Y. Higaki, T Ishikawa, K L. White, H Otsuka, A. Takahara, Polyurethane Nanocomposites Reinforced with Surface Modified Halloysite Nanotubes, Sci. Adv. Mater. , 10.1166/sam.2015.2040, 7, 5, 974-980, 2015.05.
133.	K. Imato, A. Irie, T.　Kosuge, T. Ohishi, M. Nishihara, A. Takahara, H. Otsuka, Mechanophores with a Reversible Radical System and Freezing-Induced Mechanochemistry in Polymer Solutions and Gels, Ang. Chem., 10.1002/anie.201412413, 54, 21, 6168-6172, 2015.05.
134.	Y.Higaki, H. Kabayama, D. Tao, A. Takahara, Surface Functionalization of Electrospun Poly(butylene terephthalate) Fibers by Surface-initiated Radical Polymerization, Macromolecular Chemistry and Physics, 10.1002/macp.201500066, 216, 10, 1103-1108, 2015.05.
135.	R. Ishige, T. Higuchi, X. Jiang, K. Mita, H. Ogawa, H. Yokoyama, A.Takahara, H. Jinnai, Structural Analysis of Microphase Separated Interface in an ABC-Type Triblock Terpolymer by Combining Methods of Synchrotron-Radiation Grazing Incidence Small-angle X-ray Scattering and Electron Microtomography, Macromolecules, 10.1021/ma502596a, 48, 8, 2697-2705, 2015.04.
136.	M. Kanahara, H. Satoh, T. Higuchi, A. Takahara, H. Jinnai, K. Harano, S. Okada, E. Nakamura, Y. Matsuo, H. Yabu, Fabrication of NIR-Excitable SERS-Active Composite Particles Comprised of Densely-Packed Au Nanoparticles on Polymer Microparticles, Part. Part. Syst. Char., 10.1002/ppsc.201400191, 32, 4, 441-447, 2015.04.
137.	H. Watanabe, A. Fujimoto, A. Takahara, Spray-assisted Nano-coating of the Bio-based Material Urushiol, Langmuir, 10.1021/acs.langmuir.5b00131, 31, 8, 2360-2365, 2015.03.
138.	K. P. Mineart, X. Jiang, H. Jinnai, A. Takahara, R. J. Spontak, Morphological Investigation of Midblock-Sulfonated Block Ionomers Prepared from Solvents Differing in Polarity, Macromol. Rapid Comm., 10.1002/marc.201400627, 36, 5, 432-438, 2015.03.
139.	K. L. White, M. Wong, P. Li, M. Miyamoto, Y. Higaki, A. Takahara, H.-J. Sue, Interlayer structure and self-healing in suspensions of brush-stabilized nanoplatelets in smectic order, Soft Matter, 10.1039/C4SM01855A, 11, 954-971, 2015.02.
140.	K. L. White, M. Wong, P. Li, M. Miyamoto, Yuji Higaki, Atsushi Takahara, H. J. Sue, Interlayer structure and self-healing in suspensions of brush-stabilized nanoplatelets with smectic order, Soft Matter, 10.1039/c4sm01855a, 11, 5, 954-971, 2015.02, We have investigated the rheology of an uncured epoxy fluid containing high aspect ratio (length/thickness ≈ 160) α-zirconium phosphate (ZrP) nanoplatelets with smectic order. The nanoplatelets were exfoliated into monocrystalline sheets with uniform thickness using a monoamine-terminated oligomer. The oligomers were densely grafted to the plate surfaces and behave as a molecular brush. Suspensions containing ∼2 vol.% ZrP and above show liquid crystalline order with scattering peaks characteristic of a smectic (layered) mesophase. At much higher loading, ∼4 vol.% ZrP, there is a sharp transition in visual appearance, steady shear rheology, and linear and non-linear viscoelasticity that is attributed to the reversible interdigitation of oligomer chains between closely spaced layers. The oligomers are proposed to serve as inter-lamellar bridges that store elastic stresses for intermediate rates of deformation, but are able to relax on longer time scales. Under steady shearing conditions, the smectic suspensions with "overlapped" microstructure show a discontinuous flow curve characteristic of shear banding that is attributed to the dynamic pull-out of oligomer chains from the overlap region. At high shear rates, the limiting viscosity of the concentrated suspensions is on the same order of magnitude as the unfilled suspending fluid. When the rate of deformation is reduced below a critical time scale, the original network strength, and corresponding microstructure, is recovered through a passive self-healing process. The unique combination of concentration-dependent yield stress, low post-yield viscosity, and self-healing is potentially useful for various applications in the liquid state, and desirable for scalable processing of nanocomposite materials for structural applications..
141.	Di Tao, Yuji Higaki, Wei Ma, Hui Wu, Takamichi Shinohara, Takahiro Yano, Atsushi Takahara, Chain orientation in poly(glycolic acid)/halloysite nanotube hybrid electrospun fibers, Polymer, 10.1016/j.polymer.2015.01.048, 60, 284-291, 2015.01.
142.	D. Matsukuma, H. Watanabe, A. Fujimoto, K. Uesugi, A. Takeuchi, Y. Suzuki, H. Jinnai, A. Takahara, X-ray computerized tomography observation of the interfacial structure of liquid marbles, Bull. Chem. Soc. Japan, 10.1246/bcsj.20140260, 88, 1, 84-88, 2015.01.
143.	Y. Higaki, K. Suzuki, K. Kojio, A. Takahara, Molecular Aggregation Structure of a Segmented Poly(urethane-urea) Elastomer Derived from Amino Acid-based Diisocyanate, Kobunshi Ronbunshu, 10.1295/koron.2014-0074, 72, 1, 31-36, 2015.01.
144.	Atsushi Takahara, New year's message from the SPSJ president Globarization and siceuce education, Kobunshi, 64, 1, 10, 2015.01.
145.	Keita Kuroda, Hiromi Miyoshi, Shota Fujii, Tomoyasu Hirai, Atsushi Takahara, Aiko Nakao, Yasuhiko Iwasaki, Kenichi Morigaki, Kazuhiko Ishihara, Shin Ichi Yusa, Poly(dimethylsiloxane) (PDMS) surface patterning by biocompatible photo-crosslinking block copolymers, RSC Advances, 10.1039/c5ra08843g, 5, 58, 46686-46693, 2015.01, Poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) possesses protein antifouling properties. Diblock copolymers (PMPC₁₂₀-b-P(TSM/CEAx)_y) composed of a PMPC block and random copolymer block with 3-(tris(trimethylsiloxy)silyl)propyl methacrylate (TSM) and 2-cinnamoylethyl acrylate (CEA) were prepared via reversible addition-fragmentation chain transfer (RAFT) radical polymerization. A thin film of PMPC₁₂₀-P(TSM/CEAx)_y formed on the surface of the poly(dimethylsiloxane) (PDMS) substrate due to physical adsorption of the TSM units to poly(dimethylsiloxane) (PDMS) and photo-crosslinking of the CEA units. A lattice pattern of PMPC₁₂₀-P(TSM/CEAx)_y on the PDMS surface was prepared using UV irradiation through a photomask. PMPC₁₂₀-P(TSM/CEAx)_y-coated PDMS demonstrated protein antifouling activity. Cell patterning could be achieved by culturing on the PMPC-patterned PDMS substrate..
146.	Y-T. Hsieh, R. Ishige, Y. Higaki, E. M. Woo, A. Takahara, Microscopy and microbeam X-ray analyses in poly(3-hydroxybutyrate-co- 3-hydroxyvalerate) with amorphous poly(vinyl acetate), Polymer, 55.0, 26, 6906-6914, 2014.12.
147.	Y.Higaki, R. Okazaki, T. Ishikawa, M. Kikuchi, N. Ohta, A. Takahara, Chain Stiffness and Chain Conformation of Poly(α-methylene-γ-butyrolactone) in Dilute Solutions, Polymer, 55.0, 25, 6539-6545, 2014.12.
148.	N. Morishige, R.Shin-gyou-uchi, H. Azumi, H.i Ohta, Y. Morita, N. Yamada, K.Kimura, A.Takahara, K.-H. Sonoda, Quantitative Analysis of Collagen Lamellae in the Normal and Keratoconic Human Cornea by Second Harmonic Generation Imaging Microscopy, IOVS, 55.0, 12, 8377-8385, 2014.12.
149.	Yuji Higaki, Ryosuke Okazaki, Tatsuya Ishikawa, Moriya Kikuchi, Noboru Ohta, Atsushi Takahara, Chain stiffness and chain conformation of poly(α-methylene-γ-butyrolactone) in dilute solutions, Polymer, 10.1016/j.polymer.2014.10.026, 55, 25, 6539-6545, 2014.12, The chain stiffness and local chain conformation of atactic poly(α-methylene-γ-butyrolactone) (PMBL), which is a side chain cyclic structural analog of poly(methyl methacrylate) (PMMA), with a weight-average molecular weight (M_w) ranging from 2.8 × 10³ to 2.6 × 10⁶ in N,N-dimethylformamide (DMF) and γ-butyrolactone (GBL) were characterized by size exclusion chromatography with a multi-angle light-scattering detector (SEC-MALS) and synchrotron radiation small-angle X-ray scattering (SAXS). Based on the Kratky-Porod worm-like chain model, the scattering functions and the M_w dependence of z-average root-mean-square radius of gyration 2>_z^1/2 yielded the Kuhn segment lengths λ^-1, the diameter of the PMBL chains d, and the excluded-volume strengths in DMF and GBL. The local conformation of atactic PMBL in DMF and GBL were slightly larger than those of atactic PMMA, due to the presence of the conformationally rigid lactone ring structure..
150.	Ya Ting Hsieh, Ryohei Ishige, Yuji Higaki, Eamor M. Woo, Atsushi Takahara, Microscopy and microbeam X-ray analyses in poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with amorphous poly(vinyl acetate), Polymer, 10.1016/j.polymer.2014.10.058, 55, 26, 6906-6914, 2014.12, Double ring-banded spherulites of biodegradable poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV with 12 wt% 3HV) blending with 30 wt% amorphous poly(vinyl acetate) (PVAc) were examined using polarized light optical microscopy (POM), scanning electron microscopy (SEM), atomic-force microscopy (AFM) and micro-beam X-ray diffraction. A ring-banded spherulite of PHBV/PVAc 70/30 blend was linearly scanned across the bands in 5 μm steps by means of micro-beam X-ray diffraction. Solvent-etching and fracturing were utilized for probing the interior lamellar textures of the blend samples. Detail interior lamellar orientations in bulk film of PHBV three-dimensional ring-banded spherulites were revealed. SEM and micro-beam X-ray diffraction results suggest that the PHBV lamellar orientation gradually change along the radial growth direction with right-handed rotation sense. The blending effect in band pattern (width and regularity) of PHBV/PVAc blend was discussed..
151.	K. Kojio, S. Matsumura, S. Nozaki, M.Furukawa, S. Motokucho, K. Yoshinaga , A. Takahara, ポリウレタンエラストマー中のハードセグメント鎖の結晶化挙動 Crystallization Behavior of Hard Segment in Polyurethane Elastomers, Kobunshi Ronbunshu, 71.0, 11, 608-614, 2014.11.
152.	T. Maeda, S. Kamimura, T. Ohishi, A. Takahara, H. Otsuka, Synthesis of polyethylene/polyester copolymers through main chain exchange reactions via olefin metathesis, Polymer, 55.0, 24, 6245-6251, 2014.11.
153.	K. Honda, I. Yamamoto, M. Morita, H. Yamaguchi, H. Arita, R. Ishige, Y. Higaki, A. Takahara, Effect of α-substituents on Molecular Motion and Wetting Behaviors of Poly(fluoroalkyl acrylate) Thin Films with Short Fluoroalkyl Side Chains, Polymer, 55.0, 24, 6303-6308, 2014.11.
154.	S. Fujii, K.Nishina, S. Yamada, S. Mochizuki, N. Ohta, A. Takahara, K. Sakurai, Micelles Consisting of Choline Phosphate-Bearing Calix[4]arene Lipid, Soft Matter, 10.0, 8216-8223, 2014.11.
155.	Y, Higaki, K. Hatae, T, Ishikawa, T. Takanohashi, J. Hayashi, A. Takahara, Adsorption and Desorption Behavior of Asphaltene on Polymer Brush Immobilized Surfaces, ACS Appl. Mater. Interfaces, 6.0, 22, 20385-20389, 2014.11.
156.	G. Kubo, S. Sakamoto, S. Fujii, Y. Sanada, T. Yasunaga, A. Takahara, K. Sakurai, Transformation from Multi- to Single-lamellar Vesicle by Addition of a Cationic Lipid to 1,2-Dilauroyl-sn-glycero-3-phosphocholine Explored with SAXS and TEM, Chem. Lett., 43.0, 1785-1787, 2014.11.
157.	Hirohmi Watanabe, Aya Fujimoto, Rika Yamamoto, Jin Nishida, Yuji Higaki, Atsushi Takahara, Polymer Brush Growth from Surface-textured Urushiol Thin Films, Chemistry Letters, 43.0, 11, 1776-1778, 2014.11.
158.	Yuji Higaki, Kaoru Hatae, Tatsuya Ishikawa, Toshimasa Takanohashi, Hayashi Jun-Ichiro, Atsushi Takahara, Adsorption and desorption behavior of asphaltene on polymer-brush-immobilized surfaces, ACS applied materials & interfaces, 10.1021/am505904b, 6, 22, 20385-20389, 2014.11, The adsorption behavior of a model compound for surface-active component of asphaltenes, N-(1-hexylheptyl)-N′-(12-carboxylicdodecyl) perylene-3,4,9,10-tetracarboxylic bisimide (C5Pe), and detachment behavior of asphaltene deposit fi lms for high-density polymer brushes were investigated. Zwitterionic poly(3-(N-2-methacryloyloxyethyl-N,N-dimethyl)ammonatopropanesulfonate (PMAPS) brushes and hydrophobic poly(n-hexyl methacrylate) (PHMA) brushes exhibit less C5Pe adsorption than poly(methyl methacrylate) (PMMA). The asphaltene deposit films on the PHMA brush detached in a model oil (toluene/n-heptane = 1/4 (v/v)), and the asphaltene films on the PMAPS brush detached in water. The antifouling character was explained by the interface free energy for the polymer-brush/asphaltenes (γ_SA) and polymer-brush/toluene (γ_SO). (Figure Presented)..
159.	Koji Honda, Ikuo Yamamoto, Masamichi Morita, Hiroki Yamaguchi, Hiroshi Arita, Ryohei Ishige, Yuji Higaki, Atsushi Takahara, Effect of α-substituents on molecular motion and wetting behaviors of poly(fluoroalkyl acrylate) thin films with short fluoroalkyl side chains, Polymer, 10.1016/j.polymer.2014.09.054, 55, 24, 6303-6308, 2014.11, The effect of α-substituent on the molecular motion and wetting behavior of poly{2-(perfluorobutyl)ethyl acrylate} [PFA-C₄], poly{2-(perfluorobutyl)ethyl methacrylate} [PFMA-C₄], poly{2-(perfluorobutyl)ethyl α-fluoroacrylate} [PFFA-C₄], and poly{2-(perfluorobutyl)ethyl α-chloroacrylate} [PFClA-C₄] films were characterized by dynamic contact angle measurement, lateral force microscopy (LFM), wide angle X-ray diffraction (WAXD), and X-ray photoelectron spectroscopy (XPS). WAXD of oriented PFClA-C₄ fiber suggested the presence of rod-like chain due to the presence of bulky α-substituent. The glass transition temperature (T_g) of PFFA-C₄ and PFClA-C₄ were well above the room temperature. The water repellencies of PFFA-C₄ and PFClA-C₄ were as high as that of PFMA-C₄ and their oil repellency of PFFA-C₄ and PFClA-C₄ was higher than the PFMA-C_4. This result was originated from the low main chain mobility of PFFA-C₄ and PFClA-C₄ due to the presence of bulky α-substituents. The effect of molecular motion on water repellency was clarified by the results of temperature dependence studies of dynamic contact angle, LFM, and surface chemical composition measured by XPS..
160.	Motoyasu Kobayashi, Hiroyoshi Tanaka, Myo Minn, Joichi Sugimura, Atsushi Takahara, Interferometry study of aqueous lubrication on the surface of polyelectrolyte brush, ACS applied materials & interfaces, 10.1021/am505906h, 6, 22, 20365-20371, 2014.11, The water lubrication behavior of a polyelectrolyte brush was investigated by using double-spacer-layer ultra-thin-film interferometry to determine the thickness of the aqueous lubrication layer present at the interface between the brush and a spherical glass lens. A hydrophilic poly{[2-(methacryloyloxy)ethyl]trimethylammonium chloride} brush was prepared on an optical glass disk coated with layers of semireflective chromium and silica. The thickness of the hydrodynamic lubrication layer was estimated interferometrically. On increasing the sliding velocity from 10^-5 to 10^-1 m·s^-1, the gap between the rotating disk and loading sphere glass lens showed a marked increase to 130 nm at 2 × 10^-2 m·s-1, and the friction coefficient simultaneously decreased to 0.01-0.02, indicating that the polyelectrolyte brush promoted the formation of a fluid lubrication layer that separates the rubbing surfaces, preventing direct contact and providing a low friction coefficient. (Chemical Equation Presented)..
161.	Shota Fujii, Koichi Nishina, Shimpei Yamada, Shinichi Mochizuki, Noboru Ohta, Atsushi Takahara, Kazuo Sakurai, Micelles consisting of choline phosphate-bearing Calix[4]arene lipids, Soft Matter, 10.1039/c4sm01355g, 10, 41, 8216-8223, 2014.11, We synthesized new calix[4]arene-based lipids, denoted by CPCaLn, bearing the choline phosphate (CP) group which is an inverse phosphoryl choline (PC) structure. Small-angle X-ray scattering and multi-angle light scattering coupled with field flow fractionation showed that these lipids form monodisperse micelles with a fixed aggregation number and diameters of 1.9 and 2.6 nm for lipids bearing C₃ and C₆ alkyl tails, respectively. Furthermore, when CPCaLn was mixed with the fluorescein isothiocyanate (FITC)-bearing lipids and added to cells, strong fluorescence was observed at 37 °C, but not at 4°C, indicating that the micelles were taken up by the cells through endocytosis. Recent studies have shown that replacement of polymer-attached PC groups with CP groups markedly promotes cellular uptake, even though the surface charge is neutral. On the basis of the idea, CPCaLn micelles interacted with cells in the same way, suggesting that the micelles bearing CP groups are expected to use as carriers in the drug delivery system. This journal is.
162.	Takeshi Maeda, Shigehisa Kamimura, Tomoyuki Ohishi, Atsushi Takahara, Hideyuki Otsuka, Synthesis of polyethylene/polyester copolymers through main chain exchange reactions via olefin metathesis, Polymer, 10.1016/j.polymer.2014.10.001, 55, 24, 6245-6251, 2014.11, The synthesis and characterization of linear polyethylene/polyester copolymers produced by olefin cross metathesis and subsequent catalytic hydrogenation are described. The success of the scrambling reaction between 1,4-polybutadiene and unsaturated polyester via olefin cross metathesis was confirmed by ¹H NMR. Differential scanning calorimetric (DSC) measurements indicated that the size of the copolymer blocks varied gradually with the exchange ratio. Catalytic hydrogenation of the unsaturated copolymers with different exchange ratios was carried out using Pd-Al₂O₃. The crystallinity of the resulting hydrogenated polymers depended on the exchange ratios achieved during olefin cross metathesis. This suggests that the unique sequential structure imparted to the unsaturated polymers during metathesis was retained during the hydrogenation process..
163.	M. Kobayashi, H. Tanaka, M. Minn, J. Sugimura, A. Takahara, Interferometry Study of Aqueous Lubrication on the Surface of Polyelectrolyte Brushes, ACS Appl. Mater. Interfaces, 6.0, 22, 20365-20371, 2014.10.
164.	Y. Cao, H. Wu, Y. Higaki , H. Jinnai, A. Takahara, Curvature-dependent Molecular Self-assembly of Nylon-12 Nanorod Confined to Nanoporous Alumina, IUCrJ, 1.0, 6, 439-445, 2014.10.
165.	Ryusuke Enomoto, Masanao Sato, Shota Fujii, Tomoyasu Hirai, Atsushi Takahara, Kazuhiko Ishihara, Shin-ichi Yusa, Surface Patterned Graft Copolymerization of Hydrophilic Monomers onto Hydrophobic Polymer Film upon UV Irradiation, Journal of Polymer Science Part A: Polymer Chemistry, 52.0, 19, 2822-2829, 2014.10.
166.	Yan Cao, Hui Wu, Yuji Higaki, Hiroshi Jinnai, Atsushi Takahara, Molecular self-assembly of nylon-12 nanorods cylindrically confined to nanoporous alumina, IUCrJ, 10.1107/S2052252514020132, 1, 439-445, 2014.10, Molecular self-assembly of nylon-12 rods in self-organized nanoporous alumina cylinders with two different diameters (65 and 300 nm) is studied with transmission electron microscopy (TEM) and wide-angle X-ray diffraction (WAXD) in symmetrical reflection mode. In a rod with a 300 nm diameter, the tendency of the hydrogen-bonding direction of a γ-form crystal parallel to the long axis of the rod is not clear because of weak two-dimensional confinement. In a rod with a diameter of 65 nm, the tendency of the hydrogen-bonding direction of a γ-form crystal parallel to the long axis of the rod is more distinct because of strong two-dimensional confinement. For the first time, selected-area electron diffraction (SAED) is applied in a transmission electron microscope to a polymer nanorod in order to determine the hydrogen-bond sheet and lamellar orientations. Results of TEM-SAED and WAXD showed that the crystals within the rod possess the γ-form of nylon-12 and that the b axis (stem axis) of the γ-form crystals is perpendicular to the long axis of the rod. These results revealed that only lamellae with h0l directions are able to grow inside the nanopores and the growth of lamellae with hkl (k ≠ 0) directions is stopped owing to impingements against the cylinder walls. The dominant crystal growth direction of the 65 nm rod in stronger two-dimensional confinement is in between the [-201] and [001] directions due to the development of a hydrogen-bonded sheet restricted along the long axis of the rod..
167.	Motoyasu Kobayashi, Kazuhiko Ishihara, Atsushi Takahara, Neutron reflectivity study of the swollen structure of polyzwitterion and polyeletrolyte brushes in aqueous solution, Journal of Biomaterials Science, Polymer Edition, 10.1080/09205063.2014.952992, 25, 14-15, 1673-1686, 2014.10, The swollen brush structures of polycation and zwitterionic polymer brushes, such as poly(2-methacryloyloxyethyltrimethylammonium chloride) (PMTAC), poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC), and poly[3-(N-2-methacryloyloxyethyl-N,N-dimethyl)ammonatopropanesulfonate] (PMAPS), in aqueous solutions of various ionic strengths were characterized by neutron reflectivity (NR) measurements. A series of the polyelectrolyte brushes were prepared by surface-initiated controlled radical polymerization on silicon substrates. A high-graft-density PMTAC brush in salt-free water (D2O) adopted a two-region step-like structure consisting of a shrunk region near the Si substrate surface and a diffuse brush region with a relatively stretched chain structure at the solution interface. The diffuse region of PMTAC was reduced with increase in salt (NaCl) concentration. The PMAPS brush in D2O formed a collapsed structure due to the strong molecular interaction between betaine groups, while significant increase in the swollen thickness was observed in salt aqueous solution. In contrast, no change was observed in the depth profile of the swollen PMPC brush in D2O with various salt concentrations. The unique solution behaviors of zwitterionic polymer brushes were described..
168.	Jing Su, Keiichi Imato, Tomoya Sato, Tomoyuki Ohishi, Atsushi Takahara, Hideyuki Otsuka, Plasticizer-Promoted Thermal Cross-linking of a Dynamic Covalent Polymer with Complementarily Reactive Alkoxyamine Units in the Side Chain under Bulk Conditions, Bulletin of the Chemical Society of Japan, 87.0, 9, 1023-1025, 2014.09.
169.	M. Kobayashi, K. Ishihara, A. Takahara, Neutron Reflectivity Study of the Swollen Structure of Zwitterionic Polymer Brushes in Aqueous Solution Compared with Cationic Polymer Brush, Journal of Biomaterials Science: Polymer Edition, 25.0, 14-15, 1673-1686, 2014.09.
170.	Tomoya Sato, Yoshifumi Amamoto, Tomoyuki Ohishi, Yuji Higaki, Atsushi Takahara, Hideyuki Otsuka, Radical crossover reactions of a dynamic covalent polymer brush for reversible hydrophilicity controｌ , Polymer, 55.0, 18.0, 4586-4592, 2014.09.
171.	Yasuhiro Matsuda, Yasunori Shiokawa, Moriya Kikuchi, Atsushi Takahara, Shigeru Tasaka, Structure of Insoluble Complex Formed by a Block Copolymer of 2-Ethyl-2-Oxazoline and Ethylene Oxide and Poly(Methacrylic Acid) , Polymer, 55.0, 18, 4757-4764, 2014.09.
172.	Tomoya Sato, Yoshifumi Amamoto, Tomoyuki Ohishi, Yuji Higaki, Atsushi Takahara, Hideyuki Otsuka, Radical crossover reactions of a dynamic covalent polymer brush for reversible hydrophilicity control, Polymer, 10.1016/j.polymer.2014.07.010, 55, 18, 4586-4592, 2014.09, Reversible hydrophilicity control of a radically exchangeable polymer brush with dynamic covalent linkages was successfully demonstrated. A polymer brush with alkoxyamine units was prepared via surface-initiated atom transfer radical polymerization, and reversible surface hydrophilicity control was achieved via dynamic covalent exchange reactions of alkoxyamines. Exchange reactions between alkoxyamine units in the side chains of the polymer brush and the terminal of poly(4-vinylpyridine) (P4VP) were carried out in order to prepare a side-chain functionalized polymer brush. Subsequent quaternization of P4VP chains with iodomethane was carried out to prepare a more hydrophilic surface. In addition, a de-grafting reaction of the quaternized P4VP side chains was performed to confirm reversibility of the alkoxyamine via radical exchange reactions on the surface. All the composition and wettability changes were investigated via X-ray photoelectron spectroscopy and contact angle measurements..
173.	Yasuhiro Matsuda, Yasunori Shiokawa, Moriya Kikuchi, Atsushi Takahara, Shigeru Tasaka, Structure of insoluble complex formed by a block copolymer of 2-ethyl-2-oxazoline and ethylene oxide and poly(methacrylic acid), Polymer, 10.1016/j.polymer.2014.07.020, 55, 18, 4757-4764, 2014.09, Complexes that were insoluble in water were formed by mixing aqueous solutions of a block copolymer of 2-ethtyl-2-oxazoline (EOX) and ethylene oxide (EO) and those of poly(methacrylic acid) (PMAA). The structures of these complexes were investigated by the results obtained mainly by infrared spectroscopy, X-ray diffraction, and differential scanning calorimetry. The molar ratio of MAA in the complexes was also estimated by analyzing the infrared spectra. Whereas homopolymers of EOX and EO formed nearly equimolar complexes with PMAA irrespective of the feed molar ratio, the molar ratio of MAA in the complexes formed by the block copolymer and PMAA depended on the feed molar ratio. Although the infrared spectra indicated structural differences between the homopolymer of EOX and EOX in the block copolymer before forming complexes, the spectra obtained for the complexes formed by the homopolymer and the block copolymer were similar to each other..
174.	Shinichiro Sakurai, Hirohmi Watanabe, Atsushi Takahara, Preparation and Characterization of Looped Polydimethylsiloxane Brushes, Polymer Journal, 46.0, 117-122, 2014.08.
175.	K. Imato, T. Ohishi, M. Nishihara, A. Takahara, H. Otsuka, Network Reorganization of Dynamic Covalent Polymer Gels with Exchangeable Diarylbibenzofuranone at Ambient Temperature, J. Am. Chem. Soc., 136.0, 33, 11839-11845, 2014.08.
176.	Taihei Yamada, Kenta Kokado, Yuji Higaki, Atsushi Takahara, Kazuki Sada, Preparation and Morphology Variation of Lipophilic Polyelectrolyte Brush Functioning in Non-Polar Solvents, Chemistry Letters, 43.0, 8, 1300-1302, 2014.08.
177.	Shigesaburo Ogawa, Hirohmi Watanabe, Liming Wang, Hiroshi Jinnai, Thomas J. McCarthy, Atsushi Takahara, Liquid marbles supported by monodisperse poly(methylsilsesquioxane) particles, Langmuir, 10.1021/la5017142, 30, 30, 9071-9075, 2014.08, The preparation of model, well-controlled colloidal assemblies has been a central approach to understanding and optimizing the characteristics and functionality of complex colloidal dispersion systems. This approach, which has created a significant literature and rather deep understanding for emulsions and foams, has yet to be established for the liquid marble (water-in-Air) motif. In this article we report the preparation of well-controlled liquid marbles using monodisperse micron-size particles of poly(methylsilsesquioxane) (PMSQ). The low cohesive nature of the stabilizing particles, their narrow size distribution, and their hydrophobicity permit the formation of liquid marbles containing a particulate monolayer with a hexagonally close-packed (HCP) structure. The "cleaning process" by rolling of liquid marbles under a flow of air on a hydrophobic substrate was useful to obtain the monolayer structure. Moreover, the monolayer structure was only obtained from liquids with high surface energy, whereas the others were not useful even though multilayered structure was formed from liquids that have intermediate surface energy..
178.	Keiichi Imato, Tomoyuki Ohishi, Masamichi Nishihara, Atsushi Takahara, Hideyuki Otsuka, Network reorganization of dynamic covalent polymer gels with exchangeable diarylbibenzofuranone at ambient temperature, Journal of the American Chemical Society, 10.1021/ja5065075, 136, 33, 11839-11845, 2014.08, Reversible bonds and interactions have been utilized to build stimuli-responsive and reorganizable polymer networks that show recyclability, plasticity, and self-healing. In addition, reorganization of polymer gels at ambient temperature, such as room or body temperature, is expected to lead to several biomedical applications. Although these stimuli-responsive properties originate from the reorganization of the polymer networks, not such microscopic structural changes but instead only macroscopic properties have been the focus of previous work. In the present work, the reorganization of gel networks with diarylbibenzofuranone (DABBF)-based dynamic covalent linkages in response to the ambient temperature was systematically investigated from the perspective of both macroscopic and microscopic changes. The gels continued to swell in suitable solvents above room temperature but attained equilibrium swelling in nonsolvents or below room temperature because of the equilibrium of DABBF linkages, as supported by electron paramagnetic resonance measurements. Small-angle X-ray scattering measurements revealed the mesh sizes of the gels to be expanded and the network structures reorganized under control at ambient temperature..
179.	Tomoyasu Hirai, Shota Osumi, Hiroki Ogawa, Teruaki Hayakawa, Atsushi Takahara, Keiji Tanaka, Precise synthesis and surface wettability of a polymer with liquid crystalline side chains, Macromolecules, 10.1021/ma5010265, 47, 15, 4901-4907, 2014.08, Well-defined poly(methacrylate)s with liquid crystal side chains, designated as PPHM, were synthesized by a living anionic polymerization method. Introducing a short-length alkyl chain at the end of the side chain, the solubility of the polymer was improved, resulting in higher molecular weight polymers. While the highest weight-average molecular weight (M_w) of PPHM was 68k, it exceeded 100k for a slight-polydisperse PPHM. Wide-angle X-ray diffraction (WAXD) revealed that PPHM formed a smectic A phase with 2.7 nm layer spacing and that the layer structure is present even in the glassy state at room temperature. Molecular aggregation states of PPHM in surface regions of films were characterized by sum-frequency generation, grazing-incidence WAXD, and contact angle measurements. The results show that the PPHM with a larger M_w formed a layer structure parallel to the film plane. Although low M_w PPHM also maintained a layer structure, the structure became more random within internal regions. The surface reorganization of PPHM with larger M_w was suppressed in comparison with smaller ones..
180.	Atsushi Takahara, Toward bright future of SPSJ, Kobunshi, 63, 8, 509-510, 2014.08.
181.	Tomoyasu Hirai, Shota Osumi, Hiroki Ogawa, Teruaki Hayakawa, Atsushi Takahara, Keiji Tanaka, Precise Synthesis and Surface Wettability of a Polymer with Liquid Crystalline Side Chains, Macromolecules, 47.0, 15, 4901-4907, 2014.07.
182.	Shigesaburo Ogawa, Hirohmi Watanabe, Liming Wang, Hiroshi Jinnai, Thomas J. McCarthy, Atsushi Takahara, Liquid Marbles Supported by Monodisperse Poly(methylsilsesquioxane) Particles, Langmuir, 30.0, 30, 9071-9075, 2014.07.
183.	Shinki Nojima, Takamichi Shinohara, Yuji Higaki, Ryohei Ishige, Tomoyuki Ohishi, Daigo Kobayashi, Hiroyuki Setoyama, Atsushi Takahara, Precise Characterization of Outermost Surface of Crystalline-Crystalline Diblock Copolymer Thin Films Using Synchrotron Radiation Soft X-ray Photoelectron Spectroscopy, Polymer Journal, 46.0, 637-640, 2014.07.
184.	Ryohei Ishige, Takamichi Shinohara, Kevin Lee White, Ahmed Meskini, Mustapha Raihane, Atsushi Takahara, Bruno Ameduri, Unique Difference in Transition Temperature of Two Similar Fluorinated Side Chain Polymers Forming Hexatic Smectic phase: Poly{2-(Perfluorooctyl) Ethyl Acrylate} and Poly{2-(Perfluorooctyl) Ethyl Vinyl Ether}, Macromolecules, 47.0, 12, 3860-3870, 2014.06.
185.	Wei Ma, Hang Xu, Atsushi Takahara, Substrate-Independent Underwater Superoleophobic Surfaces Inspired by Fish-Skin and Mussel-Adhesives, Advanced Materials Interfaces, 10.1002/admi.201300092, 1, 3, 2014.06, Substrate-independent underwater superoleophobic surfaces are designed by combining two bio-inspirations: the remarkable oil-repellence of fish skin and the versatile anchoring ability of mussel-adhesive proteins. A mussel-inspired polymer is synthesized, showing strong underwater adhesion to various substrates. A fish-skin inspired top layer is then assembled on this polymer coating through a layer-by-layer process..
186.	Ryohei Ishige, Takamichi Shinohara, Kevin L. White, Ahmed Meskini, Mustapha Raihane, Atsushi Takahara, Bruno Ameduri, Unique difference in transition temperature of two similar fluorinated side chain polymers forming hexatic smectic phase Poly{2-(perfluorooctyl)ethyl acrylate} and Poly{2-(perfluorooctyl)ethyl vinyl ether}, Macromolecules, 10.1021/ma500503z, 47, 12, 3860-3870, 2014.06, The surface properties of comb-shaped polymers with perfluorooctyl ethyl side-chains are strongly related to the ordered structure of the side-chains at the surface. In this work, the thermal behavior, liquid-crystalline structure, and functional group orientation of comb-shaped polymers containing perfluorooctyl side-chains with poly(acrylate) (PFA-C₈) and poly(vinyl ether) (PFAVE8) backbones are discussed based on DSC, synchrotron-source X-ray diffraction, and FTIR measurements. Despite the similar tilted hexatic smectic structures and packing entropies, the isotropization temperature, T_i, of the PFA-C₈ is significantly higher than the PFAVE8. Detailed characterization of the conformation, alignment, and organization of the perfluorooctyl side-chains indicate that the difference in T_i is related to the configuration of side-chains and interactions between the carbonyl groups along the acrylate backbone. The present findings show that the type of the linkage between the polymer backbone and fluorinated side-chain mesogens affects the conformation and plays an important role in determining thermal behavior..
187.	Atsushi Takahara, Toshiro Takeda, Toshiji Kanaya, Nobuaki Kido, Kazuo Sakurai, Hiroyasu Masunaga, Hiroki Ogawag, Masaki Takata, Advanced Soft Material Beamline Consortium at SPring-8 (FSBL), Synchrotron Radiation News, 27.0, 3, 19-23, 2014.05.
188.	Takeshi Higuchi, Daiki Murakami, Hidetoshi Nishiyama, Mitsuo Suga, Atsushi Takahara, Hiroshi Jinnai, Nanometer-scale Real-space Observation and Material Processing for Polymer Materials under Atmospheric Pressure: Application of Atmospheric Scanning Electron Microscopy, Electrochemistry, 82.0, 5, 359-363, 2014.05.
189.	Myo Minn, Motoyasu Kobayashi, Hiroshi Jinnai, Hirohmi Watanabe, Atsushi Takahara, Effect of Water Swelling on the Tribological Properties of PMMA Spin-Cast Film and Brush in Aqueous Environment, Tribology Letters, 55, 1.0, 121-129, 2014.05.
190.	Atsushi Takahara, Toshiro Takeda, Toshiji Kanaya, Nobuaki Kido, Kazuo Sakurai, Hiroyasu Masunaga, Hiroki Ogawa, Masaki Takata, Advanced Soft Material Beamline Consortium at SPring-8 (FSBL), Synchrotron Radiation News, 10.1080/08940886.2014.908759, 27, 3, 19-23, 2014.05, Soft materials, such as polymers and fibers, are key industries in Japan and play a significant role in our daily lives [1-3]. These materials also contribute to our modern society in a wide range of applications, such as in aircrafts and automobiles, and in a diverse variety of medical, electronic, and optical devices. In the future, it is expected that polymer science and technology will continue to expand and play an important role in research related to the environment [4], energy science [5], green technology [6], and biotechnology [7]. Copyright Taylor & Francis..
191.	Yuji Higaki, Ryohei Ishige, Atsushi Takahara, Fluoropolymer Surfaces/Interfaces, Handbook of Fluoropolymer Science and Technology, 10.1002/9781118850220.ch19, 433-450, 2014.05, Polymers with perfluoroalkyl (Rf) groups have surface characteristics that differ greatly from those of comparable hydrogenated structures, for example, excellent chemical and thermal stability, nonadhesive properties, low friction coefficients, low surface free energies, and antifouling behavior. Fluoropolymers with Rf groups have been extensively studied in various research fields and applied as very meaningful and valuable chemicals in industry. This chapter introduces the recent investigation relating to the surface molecular aggregation structure and surface molecular motion of the fluoro(co)polymers with Rf side group. Grazing-incidence wide-angle X-ray diffraction (GI-WAXD) measurement and X-ray photoelectron spectroscopy (XPS) using C60 ion beam were applied to the surface molecular aggregation structure analysis and the depth analysis of the fluoropolymer films, respectively. In situ neutron reflectivity (NR) measurement affords detail insights of the swelling state of semicrystalline CO2-philic fluoropolymer brushes in supercritical carbon dioxide..
192.	Takamichi Shinohara, Yuji Higaki, Taiki Hoshino, Hiroyasu Masunaga, Hiroki Ogawa, Yasushi Okamoto, Takashi Aoki, Atsushi Takahara, "Buried" Nano-structure and Molecular Aggregation State in Ordered in ordered heterojunction poly(3-hexylthiophene)-based photovoltaics , Japanese Journal of Applied Physics, 53.0, 05FH09, 2014.04.
193.	Minhao Wong, Ryohei Ishige, Kevin White, Peng Li Daehak Kim, Ramanan Krishnamoorti, Robert Gunther, Takeshi Higuchi, Hiroshi Jinnai, Atsushi Takahara, Riichi Nishimura, Hung-Jue Sue, Large-scale Self-assembled Zirconium Phosphate Smectic Layers Via a Simple Spray-coating Process, Nature Communications, 5.0, 3589, 2014.04, 無機平板状結晶集合体を厚み0.7ナノメートル（nm）の無機ナノシートに剥離するための簡便な手法を確立した。さらに無機ナノシートを混ぜたエポキシ樹脂分散液をスプレー塗布するという極めて簡易かつ省エネルギーな方法で、無機ナノシートが等間隔で積層した構造をもつ透明性の高い樹脂フィルムを作製することに成功した。無機ナノシートの積層構造により、この樹脂フィルムは極めて高いガスバリア性を示した。.
194.	Minhao Wong, Ryohei Ishige, Kevin L. White, Peng Li, Daehak Kim, Ramanan Krishnamoorti, Robert Gunther, Takeshi Higuchi, Hiroshi Jinnai, Atsushi Takahara, Riichi Nishimura, Hung Jue Sue, Large-scale self-assembled zirconium phosphate smectic layers via a simple spray-coating process, Nature Communications, 10.1038/ncomms4589, 5, 2014.04, The large-scale assembly of asymmetric colloidal particles is used in creating high-performance fibres. A similar concept is extended to the manufacturing of thin films of self-assembled two-dimensional crystal-type materials with enhanced and tunable properties. Here we present a spray-coating method to manufacture thin, flexible and transparent epoxy films containing zirconium phosphate nanoplatelets self-assembled into a lamellar arrangement aligned parallel to the substrate. The self-assembled mesophase of zirconium phosphate nanoplatelets is stabilized by epoxy pre-polymer and exhibits rheology favourable towards large-scale manufacturing. The thermally cured film forms a mechanically robust coating and shows excellent gas barrier properties at both low- and high humidity levels as a result of the highly aligned and overlapping arrangement of nanoplatelets. This work shows that the large-scale ordering of high aspect ratio nanoplatelets is easier to achieve than previously thought and may have implications in the technological applications for similar materials..
195.	Hongkun He, Brian Adzima, Mingjiang Zhong, Saadyah Averick, Richard Koepsel, Hironobu Murata, Alan Russell, David Luebke, Atsushi Takahara, Hunaid Nulwala, Krzysztof Matyjaszewski, Multifunctional photo-crosslinked polymeric ionic hydrogel films, Polymer Chemistry, 10.1039/c3py01708g, 5, 8, 2824-2835, 2014.04, A facile approach was developed to prepare crosslinked ionic polymer hydrogel films by photo-crosslinking utilizing p-vinylbenzyl trimethylammonium chloride (VBTMACl) or p-vinylbenzyl trimethylammonium hydroxide (VBTMAOH) as the monomer and poly(ethylene oxide) dimethacrylate (PEODMA, M_n = 750) as the crosslinker. The films with different crosslinking degrees (20%, 40%, 60%, 80%, and 100%) were prepared and characterized by swelling measurements, scanning electron microscopy (SEM), UV-visible spectroscopy, attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, dynamic mechanical analysis (DMA), thermogravimetric analysis (TGA), and small-angle X-ray scattering (SAXS). It was found that the mechanical and thermal properties of the films were largely influenced by the contents of the crosslinker in the films. By ion-exchange of the anions in the films with various other anions, the hydrophobicity/hydrophilicity of the films was changed. In addition, fluorescent films were prepared by treatment with fluorescein, and paramagnetic films with FeCl₄^- as a counter anion showed catalytic activity for Friedel-Crafts alkylation. The ionic films with quaternary ammonium chloride groups displayed antimicrobial activity against Escherichia coli (E. coli) with almost 100% killing efficiency. Multifunctional films with various tunable properties have significant potential for a wide range of applications..
196.	Hoik Lee, Yangjun Jeon, Youngil Lee, Sang Uck Lee, Atsushi Takahara, Daewon Sohn, Thermodynamic control of diameter-modulated aluminosilicate nanotubes, Journal of Physical Chemistry C, 10.1021/jp411725z, 118, 15, 8148-8152, 2014.04, The diameter of imogolite nanotubes was regulated by altering the synthesis temperature and was characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, and ²⁹Si cross-polarization magic angle spinning nuclear magnetic resonance (CP-MAS NMR). Imogolite diameter modulation via thermodynamic control was induced by curvature formation of the proto-imogolite cluster, which was dependent on the degree of silanol (SiOH) substitution. At lower temperature, 323 K, the amount of SiOH substitution in the proto-imogolite clusters decreases and accordingly reduces the hydrogen bonding among SiOH substituents. In contrast, at higher temperature, 371 K, the large amount of SiOH substitution in the proto-imogolite clusters increases the hydrogen bonding among silanol groups, which also increases the degree of the curvature. The proto-imogolite clusters with a larger curvature can quickly create tubular structures by forming a circle with a smaller diameter..
197.	Hoik Lee, Yangjun Jeon, Youngil Lee, Sang Uck Lee, Atsushi Takahara, Daewon Sohn , Thermodynamic Control of Diameter-Modulated Aluminosilicate Nanotubes, The Journal of Physical Chemistry C, 118.0, 15, 8148-8152, 2014.03.
198.	Jing Su, Yoshifumi Amamoto, Tomoya Sato, Masashi Kume, Taro Inada, Tomoyuki Ohishi, Yuji Higaki, Atsushi Takahara, Hideyuki Otsuka, Reversible cross-linking reactions of alkoxyamine-appended polymers under bulk conditions for transition between flow and rubber-like states, Polymer, 55.0, 6, 1474-1480, 2014.03.
199.	Jing Su, Yoshifumi Amamoto, Tomoya Sato, Masashi Kume, Taro Inada, Tomoyuki Ohishi, Yuji Higaki, Atsushi Takahara, Hideyuki Otsuka, Reversible cross-linking reactions of alkoxyamine-appended polymers under bulk conditions for transition between flow and rubber-like states, Polymer, 10.1016/j.polymer.2014.01.055, 55, 6, 1474-1480, 2014.03, Reversible cross-linking reactions of alkoxyamine-appended polymers with low glass transition temperature (T_g) were successfully carried out under bulk conditions. The low-T_g polymers with alkoxyamine units in the side chains were synthesised by radical copolymerisation of 2-ethylhexyl acrylate and two kinds of alkoxyamine-containing acrylate monomers. By heating the low-T_g polymers under bulk conditions at 100 C, cross-linked polymers were formed by radical exchange reactions between alkoxyamine units, and a transition from a liquid-like flowable polymer state to a rubber-like polymer state was confirmed. A de-cross-linking reaction was also accomplished by radical exchange reactions between the cross-linked polymers and an added alkoxyamine-containing small molecule or stable nitroxyl radical, which resulted in transition to the flowable state again. The structural transition between low-T_g linear polymers and cross-linked polymers were characterised by ¹H and ¹³C NMR spectroscopy, Fourier transform infrared spectroscopy, rheology measurement, swelling experiment, and gel permeation chromatography measurement..
200.	Hirohmi Watanabe, Aya Fujimoto, Rika Yamamoto, Jin Nishida, Motoyasu Kobayashi, Atsushi Takahara, Scaffold for growing dense polymer brushes from a versatile substrate, ACS applied materials & interfaces, 10.1021/am405965s, 6, 5, 3648-3653, 2014.03, We have demonstrated a universal approach to growing polymer brushes from various substrates. Urushiol was mixed with initiator-containing catechol, and it was spin-coated or cast on various substrates. Because urushiol is strongly adhered to various substrates, the thin film can serve as a general scaffold for grafting polymer brushes from various substrates. Note that the film was formed even onto the surface of polyolefins and thermosetting resins that are known as chemically inert materials to functionalize the surface. Moreover, the initiator-immobilized scaffold showed mechanical robustness and chemical inertness because of the flexible long unsaturated hydrocarbon side chain of urushiol. After the grafting of polyelectrolyte PMTAC polymer brushes, the material obtained exhibited hydrophilicity, typical of PMTAC. The concept shown here could provide a general approach for grafting practical polymer brushes from various substrates..
201.	Daiki Murakami, Hiroshi Jinnai, Atsushi Takahara, Wetting transition from the cassie-baxter state to the wenzel state on textured polymer surfaces, Langmuir, 10.1021/la4049067, 30, 8, 2061-2067, 2014.03, The wetting transition from the Cassie-Baxter state to the Wenzel state on textured surfaces was investigated. Nano- to microscale hexagonal pillared lattices were prepared by nanoimprint lithography on fluorinated cycloolefin polymer substrates. The transition was clearly observed for water and some ionic liquids through contact angle measurements and optical microscopy. A simple model clearly demonstrated that the energy barrier in the wetting transition from the Cassie-Baxter state to the Wenzel state was dominated by the competition between the energy barrier and external forces, particularly the Laplace pressure in the present case..
202.	Zihui Li, Kahyun Hur, Hiroaki Sai, Takeshi Higuchi, Atsushi Takahara, Hiroshi Jinnai, Sol M. Gruner, Ulrich Wiesner, Linking Experiment and Theory for Three-dimensional Networked Binary Metal Nanoparticle–triblock Terpolymer Superstructures, Nature Communications, 5.0, 3247, 2014.02.
203.	Wei Ma, Hang Xu, Atsushi Takahara , Substrate-Independent Underwater Superoleophobic Surfaces Inspired by Fish-Skin and Mussel-Adhesives, Advanced Materials Interfaces, 1.0, 3, 1300092, 2014.02.
204.	Daiki Murakami, Hiroshi Jinnai, Atsushi Takahara, Wetting transition from the Cassie-Baxter state to the Wenzel state on textured polymer surfaces, Langmuir, 30.0, 8, 2061-2067, 2014.02.
205.	小林元康、高原淳, バイオミメティック表面の分子トライボロジー Molecular tribology of biomimetic surface, 日本機械学会誌, 117.0, 1143, 18-21, 2014.02.
206.	Hirohmi Watanabe, Aya Fujimoto, Rika Yamamoto, Jin Nishida, Motoyasu Kobayashi, Atsushi Takahara, Scaffold for Growing Dense Polymer Brushes from a Versatile Substrate, Applied Materials & Interfaces, 6.0, 5, 3648-3653, 2014.02.
207.	Shinichiro Sakurai、Hirohmi Watanabe、Atsushi Takahara, Preparation and Characterization of Looped Polydimethylsiloxane Brushes, Polymer Journal, 46, 2, 117-122, 2014.02.
208.	Zihui Li, Kahyun Hur, Hiroaki Sai, Takeshi Higuchi, Atsushi Takahara, Hiroshi Jinnai, Sol M. Gruner, Ulrich Wiesner, Linking experiment and theory for three-dimensional networked binary metal nanoparticle-triblock terpolymer superstructures, Nature Communications, 10.1038/ncomms4247, 5, 2014.02, Controlling superstructure of binary nanoparticle mixtures in three dimensions from self-assembly opens enormous opportunities for the design of materials with unique properties. Here we report on how the intimate coupling of synthesis, in-depth electron tomographic characterization and theory enables exquisite control of superstructure in highly ordered porous three-dimensional continuous networks from single and binary mixtures of metal nanoparticles with a triblock terpolymer. Poly(isoprene-block-styrene-block-(N,N-dimethylamino)ethyl methacrylate) is synthesized and used as structure-directing agent for ligand-stabilized platinum and gold nanoparticles. Quantitative analysis provides insights into short-and long-range nanoparticle-nanoparticle correlations, and local and global contributions to structural chirality in the networks. Results provide synthesis criteria for next-generation mesoporous network superstructures from binary nanoparticle mixtures for potential applications in areas including catalysis..
209.	Shinichiro Sakurai, Hirohmi Watanabe, Atsushi Takahara, Preparation and characterization of looped polydimethylsiloxane brushes, Polymer Journal, 10.1038/pj.2013.69, 46, 2, 117-122, 2014.02, We have synthesized and characterized a looped polymer that is covalently bonded to a surface at both chain termini. We used the 'grafting to' method to anchor polydimethylsiloxane (PDMS) onto a Si substrate by making use of triethoxysilyl terminal units. Atomic force microscopy revealed that a linear polymer brush provides a rough surface in water. As water is a poor solvent for PDMS, linear polymer brushes tend to be dewetted, forming aggregates. In contrast, a looped polymer brush surface is smooth in air and water. Aggregation was suppressed in the looped polymer brushes because both ends were tethered to the surface. As surface characteristics, the looped polymer brushes shows low water contact angle hysteresis and low sliding angle. Technologically useful surface properties are provided on the surface by the PDMS coatings..
210.	Minhao Wong, Ryohei Ishige, Taiki Hoshino, Spencer Hawkins, Peng Li, Atsushi Takahara, Hung Jue Sue, Solution processable iridescent self-assembled nanoplatelets with finely tunable interlayer distances using charge- and sterically stabilizing oligomeric polyoxyalkyleneamine surfactants, Chemistry of Materials, 10.1021/cm402991c, 26, 4, 1528-1537, 2014.02, Photonic structures that are processable in organic solvents are critical to large-scale fabrication of device components. To provide a viable alternative to traditional lithographic methods, solution processable photonic structures are required to demonstrate fine control over critical device dimensions in the fabrication process. Photonic structures typically require long-range electrostatic forces that are effective only in aqueous solutions. Here we report a novel strategy of using oligomeric polyoxyalkyleneamine surfactants to prepare charge- and sterically stabilized nanoplatelets that can self-assemble into lamellar phases in nonaqueous solutions with finely tunable large interlamellar distances that can exceed 100 nm. Brilliant iridescence in the visible spectrum with tunable colors is demonstrated. The nanoplatelets are shown to circumvent the typical phase transition behavior from isotropic to nematic to columnar phase and transitioned into smectic phase at concentrations of
211.	Hui Jing, Yuji Higaki, Wei Ma, Jiang Xi, Hiroshi Jinnai, Hideyuki Otsuka, Atsushi Takahara, Preparation and Characterization of Polycarbonate Nanocomposites Based on Surface-modified Halloysite Nanotubes, Polymer Journal, 46.0, 307-312, 2014.01.
212.	Minhao Wong, Ryohei Ishige, Taiki Hoshino, Spencer Hawkins, Peng Li, Atsushi Takahara, Hung-Jue Sue , Solution Processable Iridescent Self-Assembled Nanoplatelets with Finely Tunable Interlayer Distances Using Charge- and Sterically Stabilizing Oligomeric Polyoxyalkyleneamine Surfactants, Chemistry of Materials, 26.0, 4, 1528-1537, 2014.01.
213.	Yuki Norizoe, Hiroshi Jinnai, Atsushi Takahara, Two-dimensional Percolation Phenomena of Single-component Linear Homopolymer Brushes, Journal of Chemical Physics, 140.0, 054904, 2014.01.
214.	Hongkun He, Brian Adzima, Mingjiang Zhong, Saadyah Averick, Richard Koepsel, Hironobu Murata, Alan Russell, David Luebke, Atsushi Takahara, Hunaid Nulwala, Krzysztof Matyjaszewski, Multifunctional Photo-crosslinked Polymeric Ionic Hydrogel Films, Polymer Chemistry, 5.0, 2824-2835, 2014.01.
215.	Myo Minn, Motoyasu Kobayashi, Hiroshi Jinnai, Hirohmi Watanabe, Atsushi Takahara, Effect of water swelling on the tribological properties of pmma spin-cast film and brush in aqueous environment, Tribology Letters, 10.1007/s11249-014-0339-7, 55, 1, 121-129, 2014.01, Due to their light weight, low corrosion and good tribological properties, polymer films have been widely studied in dry condition as well as recently in aqueous environment. Though the presence of water can further reduce the friction, it promotes the wear rate of the polymer films. As a remedy to decrease the wear rate of polymer films under aqueous condition, in this study, we used PMMA brush which is chemically anchored to a substrate and compared its friction and wear properties with those of conventional PMMA spin-cast film. Ellipsometry, contact angle measurements and atomic force microscopy are used to study the surface properties, e.g., wear mechanisms and wear depths of PMMA films. Under different sliding speeds and applied loads, PMMA brush showed lower friction than PMMA spin-cast film in aqueous. Moreover, it was shown that the swelling of water molecules is a dominant factor in determining the wear durability of PMMA films in which PMMA brush showed better wear performance than PMMA spin-cast film..
216.	Takeshi Higuchi, Daiki Murakami, Hidetoshi Nishiyama, Mitsuo Suga, Atsushi Takahara, Hiroshi Jinnai, Nanometer-scale real-space observation and material processing for polymer materials under atmospheric pressure Application of atmospheric scanning electron microscopy, Electrochemistry, 10.5796/electrochemistry.82.359, 82, 5, 359-363, 2014.01, Direct observation of phenomena occurring under atmospheric conditions, especially at the nanometer scale, would offer a unique opportunity to understand the dynamics of various processes. A novel electron microscope, the atmospheric scanning electron microscope (ASEM), has recently been developed and allows for the observation of nanoscale objects under atmospheric conditions. In this paper, we present some examples of dynamic phenomena in polymer materials observed using ASEM. The first example is phase separation of a binary polymer blend upon solvent evaporation, a representative example of a non-linear non-equilibrium phenomenon in physics. Phaseseparated structures were found to appear at the final stage of solvent evaporation. Also, we found that irradiation of organic liquids (e.g., dibenzyl ether) with the ASEM electron beam induced polymerization, and the resulting material showed interesting cathodoluminescence behavior. Thus, ASEM may be useful as a tool for simultaneous polymerization and fabrication, in addition to offering a means for direct nanoscale observation of materials under atmospheric conditions..
217.	Jing Su, Keiichi Imato, Tomoya Sato, Tomoyuki Ohishi, Atsushi Takahara, Hideyuki Otsuka, Plasticizer-promoted thermal crosslinking of a dynamic covalent polymer with complementarily reactive alkoxyamine units in the side chain under bulk conditions, Bulletin of the Chemical Society of Japan, 10.1246/bcsj.20140147, 87, 9, 1023-1025, 2014.01, Plasticizer-promoted thermal crosslinking reactions of an alkoxyamine-appended poly(methyl methacrylate)-based dynamic covalent polymer were successfully performed under bulk conditions. The films of the dynamic covalent polymer with complementarily reactive alkoxyamine side chains and dibutyl phthalate as a plasticizer were prepared and their crosslinking behavior was observed at 100 °C..
218.	Hirohmi Watanabe, Aya Fujimoto, Rika Yamamoto, Jin Nishida, Yuji Higaki, Atsushi Takahara, Polymer brush growth from surface-textured thin urushiol films, Chemistry Letters, 10.1246/cl.140670, 43, 11, 1776-1778, 2014.01, We have demonstrated the growth of polymer brushes from a surface-textured thin urushiol film. Thermal imprinting was done on an initiator-immobilized thin urushiol film, and surface-initiated atom-transfer radical polymerization (ATRP) of [2-(methacryloyloxy)ethyl]trimethylammonium chloride (MTAC) was conducted from it. The obtained surface showed superhydrophilicity because of the nature of polyelectrolyte polymer brushes on the textured surface. Since thin urushiol film can form on a variety of substrates, the concept shown here could be a universal approach for surface modifications of substrates..
219.	Shiki Nojima, Takamichi Shinohara, Yuji Higaki, Ryohei Ishige, Tomoyuki Ohishi, Daigo Kobayashi, Hiroyuki Setoyama, Atsushi Takahara, Precise characterization of outermost surface of crystalline-crystalline diblock copolymer thin films using synchrotron radiation soft X-ray photoelectron spectroscopy, Polymer Journal, 10.1038/pj.2014.51, 46, 10, 637-640, 2014.01, Conducting a spatially resolved chemical analysis of polymer thin film surfaces is therefore of great interest. Angle-resolved X-ray photoelectron spectroscopy has been used extensively to obtain depth profiles of the chemical composition near the polymer surface. The analytical depth depends on the photoelectron take-off angle with respect to the thin film surface, and the photoelectron take-off angle must be very low for an outermost surface analysis. The confined geometry of the PEG phase inhibits lamellar growth, which results in a decrease in crystallite size and crystalline perfection and thereby depresses the melting temperature of the PEG phase. The confined geometry of the PEG phase inhibits lamellar growth, which results in a decrease in crystallite size and crystalline perfection and thereby depresses the melting temperature of the PEG phase..
220.	Hirohmi Watanabe, Aya Fujimoto, Atsushi Takahara, Surface functionalization by decal-like transfer of thermally cross-linked urushiol thin films, ACS applied materials & interfaces, 10.1021/am5052284, 6, 21, 18517-18524, 2014.01, We have demonstrated surface functionalization through the decal-like transfer of thermally cross-linked urushiol thin films onto various substrates. Tensile adhesive strength measurements showed that the film adheres strongly to the surface of various substrates including chemically inert materials, such as polyolefins and thermosetting resins, because of the properties of urushiol. Furthermore, the highly cross-linked structure of urushiol made the films mechanically robust. These two properties allowed the fabrication of practicable thin films for indirect surface modification. Actually, the robust thin film served as a scaffold for an Au thin film, which was then bound to various substrates. Surface-texturing of nanodecal was also demonstrated as an application aspects..
221.	Hirohmi Watanabe, Aya Fujimoto, Atsushi Takahara, Surface texturing of natural 'urushi' thermosetting polymer thin films, Polymer Journal, 10.1038/pj.2013.91, 46, 4, 216-219, 2014.01, Japanese lacquer, known as urushi, is a traditional natural resin used for numerous applications, including tableware, art and furniture. The main component of urushi is urushiol, which is a catechol derivative with a long unsaturated hydrocarbon side chain. Utilizing the characteristics of urushiol as a thermoset, we have demonstrated the surface texturing of an urushi thin film with a thermal imprinting technique. Thermal imprinting was conducted at 100 °C for 10 min by pressing a patterned mold onto the film, and an indented surface that replicated the surface of the mold was obtained. The static water contact angle was changed from 70±0.5° to 112±3° after the fabrication of pillared patterns on the surface. Moreover, the imprinted line and space patterns caused strong anisotropic wetting depending on the direction. Our results demonstrate that the texturing of urushi thin films is a useful technique for controlling the wettability of natural thermoset urushi thin films..
222.	Peng Li, Minhao Wong, Xi Zhang, Haiqing Yao, Ryohei Ishige, Atsushi Takahara, Masahiro Miyamoto, Riichi Nishimura, Hung Jue Sue, Tunable Lyotropic Photonic Liquid Crystal Based on Graphene Oxide, ACS Photonics, 10.1021/ph400093c, 1, 1, 79-86, 2014.01, A direct colloidal self-assembly approach was utilized to prepare photonic crystals based on exfoliated graphene oxide (GO) in aqueous solution. The GO sheets form ordered photonic structure spontaneously without the need for multiple processing steps. The wavelength of light reflected by the GO photonic crystal dispersion can be controlled over the entire visible light spectrum simply by varying the GO concentration. The aspect ratio of the GO sheets and mediation of the intersheet forces are found to be the key factors influencing the stability of photonic crystal formation. The usefulness and limitations of the GO photonic crystals prepared in this study are discussed. (Graph Presented)..
223.	Yuji Higaki, Motoyasu Kobayashi, Atsushi Takahara, Macrotribology of semirigid poly(α- methylene- γ - butyrolactone) and poly(methyl methacrylate) brushes, Surfactants in Tribology, 10.1201/b17691, 4, 51-61, 2014.01, A surface-tethered brush film of bio-based polymer, poly(α-methylene-γ-butyrolactone) (PMBL), was fabricated on a silicon wafer by surface-initiated atom transfer radical polymerization of α-methylene-γ-butyrolactone (MBL), which is a biomass monomer extracted from plants. The PMBL brush films formed a smooth surface. The surface free energy of the PMBL brush films was higher than that of the poly(methyl methacrylate) (PMMA) brush films because of the absence of hydrophobic methyl groups in the polymer backbone. The PMBL brush films exhibited a larger elastic modulus and better wear resistance than the typical structurally analogous petroleum-based PMMA brush films due to the high graft density and molecular interaction between PMBL chains..
224.	Takamichi Shinohara, Yuji Higaki, Taiki Hoshino, Hiroyasu Masunaga, Hiroki Ogawa, Yasushi Okamoto, Takashi Aoki, Atsushi Takahara, Buried nano-structure and molecular aggregation state in ordered heterojunction poly(3-hexylthiophene)-based photovoltaics, Japanese Journal of Applied Physics, Part 1: Regular Papers & Short Notes, 10.7567/JJAP.53.05FH09, 53, 5 SPEC. ISSUE 1, 2014, The morphology of ordered heterojunction organic photovoltaics (OHJ-OPVs) interfaces was evaluated using synchrotron radiation small angle X-ray scattering and grazing incidence X-ray diffraction. [6,6$]-phenyl C61-butyric acid methyl ester (PCBM) was deposited on the line/space patterned poly(3-hexylthiophene-2,5-diyl) (P3HT) thin film fabricated by nano-imprinting. After deposition of the PCBM film, the P3HT thin film retained the rectangular edge features of the imprinted mold, with some Gaussian broadening due to interdiffusion and partial phase mixing at the P3HT/PCBM interface. The P3HT main chains were oriented vertically in the nano-imprinted line pattern and showed π-π stacking along the line direction. PCBM nano-crystals exist throughout the OHJ-OPV thin film..
225.	Ken Kojio, Shun Matsumura, Shuhei Nozaki, Suguru Motokucho, Mutsuhisa Furukawa, Kohji Yoshinaga, Atsushi Takahara, Crystallization behavior of hard segment in polyurethane elastomers, Kobunshi Ronbunshu, 71, 11, 608-614, 2014, The crystalline hard segment models of segmented polyurethane elastomers are made of 4,4'-diphenylmethane diisocyanate (MDI) and 1,4-butanediol (BD). Here we investigate the crystalline behavior of polyurethane that in addition contain 1,1,1-trimethylol propane (TMP), poly(oxytetramethylene) glycol (PTMG), and polyethylene glycol (PEG). The melting points (T_m) of crystallized MDI-BD units decreased with increasing TMP contents and increased with increasing PTMG contents, respectively. A decrease in molecular weight of PTMG and incorporation of PEG decreased T_m. These results indicate that incorporation of a third component would cause to form the well-ordered crystal being closed to equilibrium state..
226.	Atsushi Takahara, Fundamental science of polymer thin films, Kobunshi, 63, 2, 95, 2014.
227.	Hui Jing, Yuji Higaki, Wei Ma, Jiang Xi, Hiroshi Jinnai, Hideyuki Otsuka, Atsushi Takahara, Preparation and characterization of polycarbonate nanocomposites based on surface-modified halloysite nanotubes, Polymer Journal, 10.1038/pj.2013.100, 46, 5, 307-312, 2014, Halloysite nanotubes (HNTs) modified by a chemical vapor adsorption (CVA) process remarkably improve the thermal stability of polycarbonate nanocomposites. HNTs were modified with N-(2-aminoethyl)-3- aminopropyltrimethoxysilane (AEAPS) and n-octadecyltrimethoxysilane (OTMS) using a CVA process. Both Fourier-transform infrared spectroscopy and thermogravimetric analysis showed that the modifiers were immobilized on the HNT surfaces. Polycarbonate (PC)/HNT nanocomposites were prepared with the modified HNTs by a combination of solution mixing, precipitating and compression molding. The dispersion states of modified HNTs in PC nanocomposites were observed by optical microscopy, scanning electron microscopy and transmission electron microscopy. The storage modulus (E′) and thermal stability of the PC nanocomposites were enhanced by the modified HNTs. OTMS-modified HNT/PC nanocomposites showed higher performance than AEAPS-modified HNT/PC nanocomposites due to the stronger affinity of the hydrophobic alkyl groups of OTMS for the polymer matrix..
228.	Taihei Yamada, Kenta Kokado, Yuji Higaki, Atsushi Takahara, Kazuki Sada, Preparation and morphology variation of lipophilic polyelectrolyte brush functioning in nonpolar solvents, Chemistry Letters, 10.1246/cl.140341, 43, 8, 1300-1302, 2014, Herein, we describe the preparation of lipophilic polyelectrolyte brush (LPB) and its morphology variation induced by immersing in various organic solvents. In particular, the use of 1,2-dichloroethane resulted in twining of large fibers due to the extension of polymer chains, caused by both good compatibility of nonionic moiety and dissociation of ionic moiety. To our best knowledge, this is the first example for PE brush functioning in nonpolar organic media..
229.	Naoyuki Morishige, Ryutaro Shin-Gyou-Uchi, Haruya Azumi, Hiroaki Ohta, Yukiko Morita, Naoyuki Yamada, Kazuhiro Kimura, Atsushi Takahara, Kohei Sonoda, Quantitative analysis of collagen lamellae in the normal and keratoconic human cornea by second harmonic generation imaging microscopy, Investigative Ophthalmology and Visual Science, 10.1167/iovs.14-15348, 55, 12, 8377-8385, 2014, Purpose. To characterize the structural properties of collagen lamellae in the normal and keratoconic human corneal stroma, we measured their width and angle relative to Bowman's layer (BL). Methods. Thirteen normal and four keratoconic corneas were examined. Collagen lamellae in tissue blocks from the central cornea were visualized by second harmonic generation imaging microscopy. Images obtained in 1-μm steps from BL to Descemet's membrane (DM) were subjected to three-dimensional reconstruction. The reconstructed data sets were divided into 10 layers of equal depth (L1–L10) for analysis. The width of lamellae adherent to BL (L0) was also determined. Results. For the normal cornea, the width (mean ± SD) of collagen lamellae was 6.5 ± 1.7 μm at L0, decreased to 4.3 ± 1.3 μm at L1, and then increased gradually with progression toward DM to 122.2 ± 34.5 μm at L10, whereas the angle of lamellae was 20.9° ± 5.4° at L1 and decreased initially to 10.6° ± 3.2° at L2 before declining gradually to 2.7° ± 2.2° at L10. The width and angle of collagen lamellae in the keratoconic cornea were significantly larger and smaller, respectively, relative to those in the normal cornea. Conclusions. In the normal human cornea, collagen lamellae adjacent to BL are narrow and form a steep angle with BL, whereas they increase in width and their angle relative to BL flattens with progression toward DM. These properties of collagen lamellae are altered in keratoconus and are likely related to abnormalities of corneal shape..
230.	Ryusuke Enomoto, Masanao Sato, Shota Fujii, Tomoyasu Hirai, Atsushi Takahara, Kazuhiko Ishihara, Shin Ichi Yusa, Surface patterned graft copolymerization of hydrophilic monomers onto hydrophobic polymer film upon UV irradiation, Journal of Polymer Science, Part A: Polymer Chemistry, 10.1002/pola.27308, 52, 19, 2822-2829, 2014, A random copolymer [p(MMA/DMAB)] composed of methyl methacrylate (MMA) and 2,2-dimethoxy-1,2-di(4-methacryloyloxy)phenylethane-1-one (DMAB), which can simultaneously act as a photoradical initiator and crosslinkable monomer, was prepared by free radical random copolymerization. A hydrophobic film on quartz glass was prepared using p(MMA/DMAB) by a spin-coating technique. Hydrophilic methacrylic acid (MA) and 2-methacryloyloxyethyl phosphorylcholine (MPC) were graft-copolymerized from the hydrophobic p(MMA/DMAB) film in water by photo-cleavage of the DMAB unit. The graft copolymer of MA and MPC was characterized by infrared and X-ray photoelectron spectroscopies and contact angle measurements. To confirm that MPC can be grafted onto the surface of the film selectively at only UV-irradiated sites, photoinduced graft copolymerization of MPC using a photomask was performed to prepare a pMPC patterned p(MMA/DMAB) film. The film was stained using a rhodamine 6G dye that can absorb specifically to pMPC to confirm the pMPC pattern. The p(MMA/DMAB) film can be applied to various fields including photolithography and biomedical applications, because the film surface properties can be controlled using various vinyl monomers selectively on UV-irradiated sites..
231.	Genki Kubo, Shunsuke Sakamoto, Shota Fujii, Yusuke Sanada, Takuo Yasunaga, Atsushi Takahara, Kazuo Sakurai, Transformation from multi- To single-lamellar vesicle by addition of a cationic lipid to 1,2-dilauroyl-sn-glycero-3-phosphocholine explored with SAXS and TEM, Chemistry Letters, 10.1246/cl.140668, 43, 11, 1785-1787, 2014, 1,2-Dilauroyl-sn-glycero-3-phosphocholine (DLPC) is one of the major lipids constituting cellular membranes. When DLPC itself is dispersed in aqueous solutions, multilamellar vesicles are formed, although the cellular membranes are made of single bilayers. We found that the addition of a calix[4]arene derivative (CaL[4]C3) bearing four amine groups as the headgroup to the DLPC multilamellar vesicle induced the structural transformation to a single-lamellar vesicle, by use of small-angle X-ray scattering and electron microscopy, indicating that the highly condensed ionic groups of CaL[4]C3 are useful to control membrane morphology..
232.	Yuki Norizoe, Hiroshi Jinnai, Atsushi Takahara, Two-dimensional percolation phenomena of single-component linear homopolymer brushes, Journal of Chemical Physics, 10.1063/1.4863328, 140, 5, 2014, Percolation phenomena of homopolymer brushes on a planar substrate are simulated using the molecular Monte Carlo method in 3 dimensions. The grafted polymers are isolated from each other at extremely low grafting density, whereas a continuous polymer layer covers the whole substrate when the density rises to extremely high values. This indicates that percolation clusters of the grafted polymers, bridging both the edges of the substrate, appear at an intermediate density. We construct phase diagrams of this percolation phenomenon. Critical phenomena at the transition are also studied..
233.	Peng Li, Minhao Wong, Xi Zhang, Haiqing Yao, Ryohei Ishige, Atsushi Takahara, Masahiro Miyamoto, Riichi Nishimura, Hung-Jue Sue , Tunable Lyotropic Photonic Liquid Crystal Based on Graphene Oxide, ACS Photonics, 1.0, 1, 79-86, 2013.12.
234.	Hirohmi Watanabe, Aya Fujimoto, Atsushi Takahara, Surface Texturing of Natural ‘Urushi’ Thermosetting Polymer Thin Films, Polymer Journal , 46.0, 4, 216-219, 2013.12.
235.	Noriyuki Tanji, Hui Wu, Motoyasu Kobayashi, Atsushi Takahara, Direct measurement of chain diffusion at interfaces of PPO/PS bilayer films by nano-thermal analysis and time-of-flight secondary ion mass spectrometry, Macromolecules, 10.1021/ma401705v, 46, 24, 9722-9728, 2013.12, Chain diffusion at the polyphenylene oxide/polystyrene (PPO/PS) interface of bilayer films were investigated using nanothermal analysis (nano-TA) and time-of-flight secondary ion mass spectrometry (TOF-SIMS). An ultralow-angle slicing technique by the surface and interfacial cutting analysis system (SAICAS) was used to expand the size of the interfacial region effectively. The glass-transition temperature (T_g) at the interface was directly evaluated by nano-TA. The gradient of T_g at the PPO/PS interface became broad after annealing. An increase in annealing time caused an increase in the T_g of the initial PS layer, indicating that the PPO diffused across the interface. Since PPO/PS is a compatible blend system, the local chemical compositions were evaluated by Fox equation. The methodology presented here is useful for interfacial analyses of various polymer composite systems and is beneficial because the isotope labeling is not necessary..
236.	Tatsuya Ishikawa, Ai Takenaka, Moriya Kikuchi, Motoyasu Kobayashi, Atsushi Takahara, Effective addition of organic chloride salts on atom transfer radical polymerization in fluoroalcohols, Macromolecules, 10.1021/ma401857w, 46, 23, 9189-9196, 2013.12, Atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) in the presence of organic chloride salts, imidazolium chlorides, using alkyl bromide initiator was carried out in 2,2,2-trifluoroethanol (TFE) at 333 K. The ATRP using a sufficient large amount of chloride salts proceeded in a controlled manner to produce polymers with narrow molecular weight distributions (M _w/M_n
237.	Daiki Murakami, Ai Takenaka, Motoyasu Kobayashi, Hiroshi Jinnai, Atsushi Takahara, Measurement of the electrostatic interaction between polyelectrolyte brush surfaces by optical tweezers, Langmuir, 10.1021/la404133e, 29, 52, 16093-16097, 2013.12, We demonstrated an optical tweezers method to measure the electrostatic interaction between the strong polyelectrolyte brushes, poly(2-(methacryloyloxy) ethyltrimethylammonium chloride) (PMTAC), grafted on silica particles in aqueous media. The weak electrostatic interaction was successfully detected with a resolution of less than 0.1 μN m^-1. The apparent Debye length, including the charge distribution in the polymer brush and the surface potential, decreased as the salt concentration in the medium increased. The experimentally obtained surface charge density was much smaller than that estimated from the amount of polyelectrolyte on the surface. Furthermore, the dissociation of ionic groups was enhanced by decreasing the grafting density of the polyelectrolyte brush. The results suggest that the majority of chloride counterions was immobilized in the dense polyelectrolyte brush layer to neutralize the high charge density..
238.	Hui Wu, Hirohmi Watanabe, Wei Ma, Aya Fujimoto, Takeshi Higuchi, Kentaro Uesugi, Akihisa Takeuchi, Yoshio Suzuki, Hiroshi Jinnai, Atsushi Takahara, Robust liquid marbles stabilized with surface-modified halloysite nanotubes, Langmuir, 10.1021/la4041858, 29, 48, 14971-14975, 2013.12, We have demonstrated the fabrication of fluorine-free liquid marbles from halloysite nanotube. Halloysite is a naturally occurring inorganic nanotube that has a high aspect ratio, and the surface was modified with octadecyltrimethoxysilane. The surface-modified halloysite formed pincushion agglomerates on the surface of the liquid droplets, which create superhydrophobic surface similar to that of the plant gall surface prepared by aphids. As a result, the liquid marbles showed high mechanical strength upon impact without the use of low surface energy fluoroalkyl or fluorine-modified materials. Our results suggest a new strategy for designing novel materials for liquid marbles inspired by nature..
239.	Tatsuya Ishikawa、Ai Takenaka、Moriya Kikuchi、Motoyasu Kobayashi、Atsushi Takahara, Effective Addition of Organic Chloride Salts on Atom Transfer Radical Polymerization in Fluoroalcohols, Macromolecules, 46, 23, 9189-9196, 2013.11.
240.	Hui Wu, Hirohmi Watanabe, Wei Ma, Aya Fujimoto, Takeshi Higuchi, Kentaro Uesugi, Akihisa Takeuchi, Yoshio Suzuki, Hiroshi Jinnai, Atsushi Takahara, Robust Liquid Marbles Stabilized with Surface-Modified Halloysite Nanotube, Langmuir, 29, 48, 14971-14975, 2013.11.
241.	Tomoyuki Ohishi、Yoko Iki、Keiichi Imato、Yuji Higaki、Atsushi Takahara、Hideyuki Otsuka, Insertion Metathesis Depolymerization of Aromatic-Disulfide-Containing Dynamic Covalent Polymers under Weak Intensity Photoirradiatio, Chemistry Letters, 42, 11, 9189-9196, 2013.11.
242.	Shota Fujii, Kazuo Sakurai, Tadashi Okobira, Noboru Ohta, Atsushi Takahara, Synthesis and characterization of a calix[4]arene amphiphilie bearing cysteine and uniform au nanoparticle formation templated by its four cysteine moieties, Langmuir, 10.1021/la403377a, 29, 45, 13666-13675, 2013.11, A novel calix[4]arene amphiphilic molecule, denoted by CCaL3, was synthesized and found to form a spherical micelle consisting of 12 molecules at low pH in aqueous solution. Furthermore, uniform Au nanoparticles with 2.0 nm in diameter were synthesized in aqueous solution on the template consisting of the four cysteines of the upper rim of CCaL3. Asymmetric field flow fractionation coupled with light scattering showed that there was no dispersity in the CCaL3 micellar aggregation number. When AuCl₄ ^- ions were added into the CCaL3 micelle solution, induced circular dichroism (ICD) appeared, indicating appearance of the structural chirality of the CCaL3/AuCl ₄ ^- complex. A combination of electron microscopy and small-angle X-ray scattering showed that helically coiled bilayer sheets were formed upon addition of AuCl₄ ^-. Subsequent reduction with the amine of cysteine moieties led to uniform Au nanoparticles formation with 2.0 nm in diameter on the micellar plate surface. The nanoparticle size was almost equal to the size of cavity constructed by the four cysteines on the calix[4]arene upper rim, indicating that the growth of Au nanoparticles was spatially controlled by the host-guest interaction between the cysteines and Au..
243.	Shota Fujii、Kazuo Sakurai、Tadashi Okobira、Noboru Ohta、Atsushi Takahara, Synthesis and Characterization of a Calix[4]arene Amphiphilie Bearing Cysteine and Uniform Au Nanoparticle Formation Templated by its Four Cysteine Moietie, Langmuir, 29, 45, 13666-13675, 2013.10.
244.	Ryohei Ishige、Hiroki Yamaguchi、Takamichi Shinohara、Ahmed Meskini、Mustapha Raihane、Atsushi Takahara、Bruno Ameduri, Structural Analysis and Surface Wettability of Novel Alternated Vinylidene Cyanide with Fluorinated Vinyl Ether Copolymer, Polymer Journal, 45, 10, 1041-1046, 2013.10.
245.	Ryohei Ishige, Hiroki Yamaguchi, Takamichi Shinohara, Ahmed Meskini, Mustapha Raihane, Atsushi Takahara, Bruno Ameduri, Structural analysis and surface wettability of a novel alternated vinylidene cyanide with fluorinated vinyl ether copolymer, Polymer Journal, 10.1038/pj.2013.32, 45, 10, 1041-1046, 2013.10, The structure, thermal properties and surface wettability of a novel alternating poly(VCN-alt-FAVE8) copolymer based on vinylidene cyanide (VCN) and perfluorooctyl ethyl vinyl ether (FAVE8) were investigated via both temperature-variable wide-angle X-ray powder diffraction (WAXD) and thin-film WAXD using a small angle incidence synchrotron radiation source, differential scanning calorimetry and contact angle measurements, respectively. The results of the WAXD and thin-film WAXD indicated that the alternating copolymer possessed a smectic liquid-crystalline phase at ambient temperature with a couple of fluoroalkyl side chains forming a bilayer with a 3.24 nm spacing and that the fluoroalkyl side chains in a thin-film on a Si wafer align perpendicularly to the surface. The isotropization temperature of the alternating copolymer was 150 °C, which was higher than the 29.5 °C for the poly(FAVE8) homopolymer. The spin-coated poly(VCN-alt-FAVE8) copolymer thin-film yielded high static contact angles for both water and oil similar to those for poly(perfluorooctyl ethyl acrylate), which is known as a superhydrophobic polymer. Dynamic contact angle and X-ray photoelectron spectroscopy measurements in both the dry and hydrated states suggested that the polar cyano and ether groups are enriched at the surface in the wet state, and this reorganization of the surface polar groups caused a large hysteresis of the contact angle..
246.	Taiki Hoshino、Daiki Murakami、Yoshihito Tanaka、Masaki Takata、Hiroshi Jinnai、Atsushi Takahara, Dynamical crossover between hyperdiffusion and subdiffusion ofpolymer-grafted nanoparticles in a polymer matrix, Physical Review E, 88, 3, 032602-①-032602-④, 2013.09.
247.	Hirohmi Watanabe、Aya Fujimoto、Atsushi Takahara, Characterization of Catechol-Containing Natural Thermosetting Polymer "Urushiol" Thin Film, Journal of Polymer Science Part A: Polymer Chemistry, 51, 17, 3688-3692, 2013.09.
248.	Taiki Hoshino, Daiki Murakami, Yoshihito Tanaka, Masaki Takata, Hiroshi Jinnai, Atsushi Takahara, Dynamical crossover between hyperdiffusion and subdiffusion of polymer-grafted nanoparticles in a polymer matrix, Physical Review E - Statistical, Nonlinear, and Soft Matter Physics, 10.1103/PhysRevE.88.032602, 88, 3, 2013.09, The dynamical behavior of polystyrene-grafted silica nanoparticles dispersed in an atactic polystyrene matrix was studied using x-ray photon correlation spectroscopy. The time-autocorrelation functions were subjected to fitting analyses based on continuous-time random walk models. The nanoparticles exhibited non-Brownian behavior, and as the temperature increased, the crossover from hyperdiffusion to subdiffusion occurred at 1.25T_g, where T _g is the glass transition temperature of the matrix polystyrene. Hyperdiffusive behavior is caused by the dynamical heterogeneity of the polymer matrix associated with the glass transition. When the temperature was higher than 1.25T_g, the interaction of the grafted polymers with the polymer matrix became relatively significant, and caused a dramatic change in the dynamical behavior of the nanoparticles..
249.	Motoyasu Kobayashi, Atsushi Takahara, Environmentally friendly repeatable adhesion using a sulfobetaine-type polyzwitterion brush, Polymer Chemistry, 10.1039/c3py00146f, 4, 18, 4987-4992, 2013.09, A repeatable adhesion system is demonstrated using a zwitterionic poly[3-(N-2-methacryloyloxyethyl-N,N-dimethyl)ammonato propane sulfonate] (poly(MAPS)) brush. Two silicon wafers bearing poly(MAPS) brushes were joined in hot water at 333 K under 0.098 MPa of pressure for 1 min and dried under an air atmosphere for 3 h. A lap shear strength of 2.0 MPa was observed through the adhesion of the brush substrates due to attractive dipole-dipole interactions between the sulfobetaine units. Smooth debonding of the adhering substrates in hot water at 333 K was completed within 1 h due to swelling of the poly(MAPS) brushes above the upper critical solution temperature. Repeatable adhesion and debonding was successfully achieved by the poly(MAPS) brush on the substrate..
250.	Takeshi Higuchi, Hidekazu Sugimori, Xi Jiang, Song Hong, Kazuyuki Matsunaga, Takeshi Kaneko, Volker Abetz, Atsushi Takahara, Hiroshi Jinnai, Morphological control of helical structures of an ABC-type triblock terpolymer by distribution control of a blending homopolymer in a block copolymer microdomain, Macromolecules, 10.1021/ma401193u, 46, 17, 6991-6997, 2013.09, The control of microphase-separated structures in a poly(styrene-block- butadiene-block-methyl methacrylate) (SBM) was investigated in three dimensions by transmission electron microtomography. Neat SBM self-assembled into a double-helical structure of polybutadiene (PB) domains around hexagonally packed core polystyrene (PS) cylinders in a poly(methyl methacrylate) matrix. When PS homopolymer with a lower molecular weight than that of the PS block in SBM was added to the SBM, the PB domains transformed from double-helical structures to spherical domains, while maintaining the helical trajectories. In contrast, adding a higher molecular weight PS to the SBM changed the helical structures from double- to triple-stranded structures and even to four-stranded structures. The helical structures of the PB domains were strongly affected by the distribution of the blended polystyrenes in the core cylindrical PS domains..
251.	Takeshi Higuchi、Hidekazu Sugimori、Xi Jiang、Song Hong、Kazuyuki Matsunaga、Takeshi Kaneko、Volker Abetz、Atsushi Takahara、Hiroshi Jinnai, Morphological Control of Helical Structures of an ABC-Type Triblock Terpolymer by Distribution Control of a Blending Homopolymer in a Block Copolymer Microdomai, Macromolecules, 46, 17, 6991-6997, 2013.08.
252.	Ryohei Watari、Masamichi Nishihara、Hiroo Tajiri、Hideyuki Otsuka、Atsushi Takahara, Preparation of novel polyimide hybrid materials by multi-layered charge-transfer complex formation, Polymer Journal, 45, 8, 839-844, 2013.08.
253.	Ryohei Watari, Masamichi Nishihara, Hiroo Tajiri, Hideyuki Otsuka, Atsushi Takahara, Preparation of novel polyimide hybrid materials by multi-layered charge-transfer complex formation, Polymer Journal, 10.1038/pj.2012.222, 45, 8, 839-844, 2013.08, A versatile method for the post-modification of sulfonated polyimides by charge-transfer (CT) complex formation between electron-deficient naphthalenediimide units in polyimide and electron-rich dihydroxynaphthalene was developed. CT complex hybrid films whose physicochemical properties, such as mechanical strength, differed from those of the original polyimide films were successfully fabricated..
254.	Kyunghwan Oh, Youngwook P. Seo, Soon Man Hong, Atsushi Takahara, Kyoung Hwan Lee, Yongsok Seo, Dispersion and reaggregation of nanoparticles in the polypropylene copolymer foamed by supercritical carbon dioxide, Physical Chemistry Chemical Physics, 10.1039/c3cp51068a, 15, 26, 11061-11069, 2013.07, For the preparation of nanocomposites, we conducted environmentally benign foaming processing on polypropylene (PP) copolymer/clay nanocomposites via a batch process in an autoclave. We investigated the dispersion and the exfoliation of the nanoclay particles. Full exfoliation was achieved by the foamability of the matrix PP copolymer using supercritical carbon dioxide (sc CO₂) and subcritical carbon dioxide (sub CO₂). More and smaller cells were observed when the clay was blended as heterogeneous nuclei and sc CO₂ was used. Small angle X-ray scattering showed that highly dispersed states (exfoliation) of the clay particles were obtained by the foaming process. Since the clay particles provided more nucleating sites for the foaming of the polymer, a well dispersed (or fully exfoliated) nanocomposite exhibited a higher cell density and a smaller cell size at the same clay particle concentration. Expansion of the adsorbed CO₂ facilitated the exfoliation of the clay platelets; thus, sc CO₂ at lower temperature was more efficient for uniform foaming-cell production. Fully dispersed clay platelets were, however, re-aggregated when subjected to a further melting processing. The reprocessed nanocomposites still had some exfoliated platelets as well as some aggregated intercalates. The dual role of the nanoclay particles as foaming nucleus and a crystallization nucleus was confirmed by cell growth observation and nonisothermal crystallization kinetics analysis. A low foaming temperature and a high saturation pressure were more favorable for obtaining a uniform foam. The PP copolymer was found to be foamed more easily than polypropylene. A small amount of other olefin moieties in the backbone of the polymer facilitated better foamability than the neat polypropylene..
255.	Yoshihiko Oniki, Ken Suzuki, Yuji Higaki, Ryohei Ishige, Noboru Ohta, Atsushi Takahara, Molecular design of environmentally benign segmented polyurethane(urea)s Effect of the hard segment component on the molecular aggregation states and biodegradation behavior, Polymer Chemistry, 10.1039/c3py00172e, 4, 13, 3735-3743, 2013.07, We investigated the molecular aggregation states, mechanical properties, and biodegradability of environmentally benign segmented polyurethane(urea)s [SPU(U)s], which contained bio-based monomers of an α-amino acid lysine-based diisocyanate (LDI). The SPU(U)s consisted of an aliphatic diisocyanate (LDI or 1,4-butanediisocyanate (BDI)), a chain extender (1,4-butanediamine (BDA) or 1,4-butanediol (BDO)), and a poly-ε- caprolactone (PCL) segment. Four SPU(U)s, LDI-BDA, LDI-BDO, BDI-BDA, and BDI-BDO, were prepared by a standard two-step prepolymer method. Fourier transformed infrared spectroscopy (FT-IR), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and small-angle X-ray scattering (SAXS) measurement indicated that the LDI-series SPU(U)s formed weakly aggregated hard segment domains, which readily dissociated under mechanical deformation and heating. The diamine chain extender, BDA, enhanced the stability of the hard segment domains, and the BDA-series SPU(U)s exhibited better mechanical properties than the BDO-series. The LDI-series SPU(U)s have notable biodegradability, and the BDI-based hard segments delayed the degradation rate because of the strongly segregated hard segment..
256.	Yuji Higaki, Wei Ma, Motoyasu Kobayashi, Atsushi Takahara, Nature-inspired low adhesive antifouling surfaces, Kobunshi Ronbunshu, 10.1295/koron.70.301, 70, 7, 301-308, 2013.07, There are many natural materials with self-cleaning and anti-fouling surfaces. Their surface texture and the anti-fouling mechanisms are individually distinct, and depend on their environment and functionality. In this article, anti-fouling materials of high-density superhydrophilic polyelectrolyte brushes and fluoropolymer-infused nano-textured films were presented. Polyelectrolyte brushes repel n-hexadecane droplets under water, whereas the oil spreads in air. The oil repellent behavior in water was explained by hydration and swelling of the polyelectrolyte brushes in water as well as the low adhesion force between the brush and the oil due to the low interfacial tension. Nano-textured alumina gel films modified with low surface tension perfluoroalkyl phosphonic acid and infused with lubricating perfluoropolyether were fabricated. The liquid layer is stable, transparent, and slippery for both polar and non-polar liquids such as n-hexadecane and toluene. These materials have a potential for application as artificial anti-fouling coatings..
257.	Motoyasu Kobayashi, Yuki Terayama, Moriya Kikuchi, Atsushi Takahara, Chain dimensions and surface characterization of superhydrophilic polymer brushes with zwitterion side groups, Soft Matter, 10.1039/c3sm27700c, 9, 21, 5138-5148, 2013.06, Zwitterionic polymers constitute a unique class of polyelectrolytes which have not been studied systematically because of the difficulty in their controlled synthesis and precise physicochemical characterization. The salt-concentration dependence of the chain dimensions and swollen brush structures of polyzwitterions, namely poly(2- methacryloyloxyethylphosphorylcholine) (PMPC) and poly[3-(N-2- methacryloyloxyethyl-N,N-dimethyl)ammonatopropanesulfonate] (PMAPS), in aqueous solutions of various ionic strengths was characterized by static light scattering, dynamic light scattering, atomic force microscopy (AFM), neutron reflectivity (NR), contact angle measurements, and macroscopic friction tests by sliding a glass ball under a load of 0.49 N. The hydrodynamic radius R _H of PMPC was independent of NaCl concentration, whereas the R _H of PMAPS markedly increased with the ionic strength. AFM and NR measurements also showed the independence of NaCl concentration of the swollen thickness of the PMPC brush in aqueous solution and significant changes in the swollen thickness of the PMAPS brush in aqueous NaCl solution. Both PMPC and PMAPS brushes showed oil detachment behavior in water and aqueous NaCl solutions. The PMPC brush had a significantly low friction coefficient (0.02-005) at a sliding velocity of 10^-2 to 10^-1 m s ^-1 in water even under a high normal pressure of 139 MPa..
258.	Daisuke Matsukuma, Hirohmi Watanabe, Myo Minn, Aya Fujimoto, Takamichi Shinohara, Hiroshi Jinnai, Atsushi Takahara, Preparation of poly(lactic-acid)-particle stabilized liquid marble and the improvement of its stability by uniform shell formation through solvent vapor exposure, RSC Advances, 10.1039/c3ra40693h, 3, 21, 7862-7866, 2013.06, A liquid marble was prepared from bio-based poly(lactic acid) [PLA] microparticles and water droplets. Solvent vapor exposure to the liquid marble changed the morphology of the granular PLA microparticle shell layer to a film-like shell layer even though the spherical shape of the liquid marble is retained. The morphological changes suppressed the evaporation of the water within the liquid marble by a factor of six compared with a liquid marble without the solvent vapor treatment. The compression test revealed that the mechanical stability of the solvent-treated liquid marble was changed due to the increased rigidity of the shell structure. Solvent vapor exposure is a simple but effective way to fabricate a robust liquid marble with long-term stability..
259.	Kyunghwan Oh、Youngwook P. Seo、Soon Man Hong、Atsushi Takahara、Kyoung Hwan Lee、Yongsok Seo, Dispersion and reaggregation of nanoparticles in the polypropylene copolymer foamed by supercritical carbon dioxide, Physical Chemistry Chemical Physics, 15, 11061-11069, 2013.05.
260.	Hirohmi Watanabe、Aya Fujimoto、Atsushi Takahara, Concealing Surface Topography by Attachment of Nanometer-Thick Film, Langmuir, 29, 9, 2906-2911, 2013.05.
261.	Tatsuya Ishikawa, Moriya Kikuchi, Motoyasu Kobayashi, Noboru Ohta, Atsushi Takahara, Chain conformation of poly[2-(methacryloyloxy)ethyltrimethylammonium chloride] in aqueous sodium chloride solutions, Macromolecules, 10.1021/ma4001868, 46, 10, 4081-4088, 2013.05, A series of poly[2-(methacryloyloxy)ethyltrimethylammonium chloride] (PMTAC) in aqueous NaCl solutions with a weight-average molecular weight (M _w) of between 6.0 × 10³ and 1.5 × 10 ⁵ were characterized by synchrotron radiation small-angle X-ray scattering (SAXS) and dynamic light scattering (DLS) measurements at 298 K. The hydrodynamic radius (R_H) of PMTAC initially decreased with increasing salt concentration (C_s) and then leveled off at C_s = 0.5-1.0 M. The values of z-average root-mean-square radius of gyration (〈S²〉_z^1/2) simply increased with a decrease in C_s for M_w > 2 × 10⁴ g/mol. In contrast, the values of 〈S²〉_z^1/2 for M_w 4 g/mol increased with an increase in C_s probably because of a change in local conformation of PMTAC chain. To study local chain conformation of PMTAC, scattering functions and M_w dependences of 〈S²〉_z^1/2 and R_H for PMTAC were analyzed in terms of the helical wormlike chain (HW) model which is a simple continuous elastic wire model with bending and torsional energies. The characteristic helix of the HW model in potential energy minimum for PMTAC clearly indicates that the local conformation is strongly influenced by the ionic strength of the solution..
262.	Motoyasu Kobayashi、Yuki Terayama、Moriya Kikuchi、Atsushi Takahara, Chain dimensions and surface characterization of superhydrophilic polymer brushes with zwitterion side groups, Macromolecules, 46, 10, 4081-4088, 2013.04.
263.	Tatsuya Ishikawa、Moriya Kikuchi、Motoyasu Kobayashi、Noboru Ohta、Atsushi Takahara, Chain Conformation of Poly[2-(methacryloyloxy)ethyltrimethylammonium chloride] in Aqueous Sodium Chloride Solutions, Soft Matter, 5138-5145, 2013.04.
264.	Hui Wu、Yan Cao、Ryohei Ishige、Taiki Hoshino、Yuji Higaki、Noboru Ohta、Atsushi Takahara, Confinement-Induced Crystal Growth in One-Dimensional Isotactic Polystyrene Nanorod Arrays, ACS Macro Letters, 2, 5, 414-418, 2013.04.
265.	Hiroshi Jinnai、Toshihiko Tsuchiya、Sohei Motoki、Takeshi Kaneko、Takeshi Higuchi、Atsushi Takahara, Transmission Electron Microtomography in Soft Materials, Journal of Electron Microscopy, 62, 2, 243-258, 2013.04.
266.	Motoyasu Kobayashi、Yuki Terayama、Moriya Kikuchi、Atsushi Takahara, Chain dimensions and surface characterization of superhydrophilic polymer brushes with zwitterion side groups, Soft Matter, 9, 5138-5145, 2013.04.
267.	Yoshihiko Oniki、Ken Suzuki、Yuji Higaki、Ryohei Ishige、Noboru Ohta、Atsushi Takahara, Molecular Design of Environmentally Benign Segmented Polyurethane(urea)s: Effect of the Hard Segment Component on the Molecular Aggregation States and Biodegradation Behavior, Polymer Chemistry, 4, 13, 3735-3743, 2013.04.
268.	Masamichi Nishihara、Keiichi Imato、Atsushi Irie、Takwshi Kanehara、Arihiro Kano、 Atsushi Maruyama、Atsushi Takahara、Hideki Otsuka, Reversibly Crosslinked Polymeric Micelles Formed by Autonomously Exchangeable Dynamic Covalent Bonds, Chemistry Letters, 42, 4, 377-379, 2013.04.
269.	Hiroki Yamaguchi, Peter Gin, Hiroshi Arita, Motoyasu Kobayashi, Steve Bennett, Sushil K. Satija, Mitsunori Asada, Tadanori Koga, Atsushi Takahara, Effect of supercritical carbon dioxide on molecular aggregation states of side chains of semicrystalline poly{2-(perfluorooctyl)ethyl acrylate} brush thin films, RSC Advances, 10.1039/c3ra22692a, 3, 14, 4778-4785, 2013.04, We report a carbon dioxide-based approach to induce highly ordered molecular aggregation states of perfluoroalkyl (R_f) chains of densely-grafted poly{2-(perfluorooctyl)ethyl acrylate} (poly(FA-C₈)) brush in place of conventional thermal annealing. Poly(FA-C₈) brush films of 40 nm thickness were prepared by surface-initiated atom transfer radical polymerization. In-situ neutron reflectivity measurements for the poly(FA-C₈) brush films under the isothermal condition of T = 309 K, which is below the bulk melting temperature (T_m = 348 K), elucidated large expansion of polymer chains due to sorption of CO₂ molecules. Comparison of the swelling behavior with an amorphous poly{2-(perfluorobutyl) ethyl acrylate} brush thin film clarified that the sorption of CO₂ molecules results in the melting of the semicrystalline poly(FA-C₈) brush at P > 4.1 MPa. In addition, by using out-of-plane grazing incidence wide-angle X-ray diffraction, it was found that subsequent slow quench from P > 4.1 MPa induces rearrangement of the rigid rod-like R_f groups, forming highly ordered molecular aggregation structures similar to those via a conventional thermal process. The appropriate CO₂ process conditions for the effective induction of the highly ordered structures of the rigid R _f groups are discussed in detail..
270.	Hiroshi Jinnai, Toshihiko Tsuchiya, Sohei Motoki, Takeshi Kaneko, Takeshi Higuchi, Atsushi Takahara, Transmission electron microtomography in soft materials, Microscopy (Oxford, England), 10.1093/jmicro/dfs070, 62, 2, 243-258, 2013.04, This review summarizes the recent advances in three-dimensional (3D) imaging techniques and their application to polymer nanostructures, for example, microphase-separated structures of block copolymers. We place particular emphasis on the method of transmission electron microtomography (electron tomography for short; hereafter abbreviated as ET). As a result of recent developments in ET, truly quantitative 3D images of polymer nanostructures can now be obtained with subnanometer resolution. The introduction of scanning optics in ET has made it possible to obtain large amounts of 3D data from micrometer-thick polymer specimens by using conventional electron microscopes at a relatively low accelerating voltage, 200 kV. Thus, ET covers structures over a wide range of thicknesses, from a few nanometers to several hundred nanometers, which corresponds to quite an important spatial range for hierarchical polymer nanostructures. ET provides clear 3D images and a wide range of new structural information that cannot be obtained using other methods. Information traditionally derived from conventional microscopy or scattering methods can be directly acquired from 3D volume data. ET is a versatile technique that is not restricted to only polymer applications; it can also be used as a powerful characterization tool in energy applications such as fuel cells..
271.	Atsushi Takahara, Characterization of complexes formed by mixing aqueous solutions of poly(2-ethyl-2-oxazoline) and poly(methacrylic acid) with a wide range of concentrations, Polymer, 54, 7, 1896-1904, 2013.03.
272.	Atsushi Takahara, Gelation and Adhesion Behavior of Mussel Adhesive Protein Mimetic Polymer, Journal of Polymer Science Part A: Polymer Chemistry, 51, 5, 1058-1065, 2013.03.
273.	Atsushi Takahara, Preparation of poly(lactic-acid)-particle stabilized liquid marble and the improvement of its stability by uniform shell formation through solvent vapor exposure, RSC Advances, 2013.03.
274.	Yasuhiro Matsuda, Kazumasa Takatsuji, Yasunori Shiokawa, Moriya Kikuchi, Satoru Kidoaki, Atsushi Takahara, Shigeru Tasaka, Characterization of complexes formed by mixing aqueous solutions of poly(2-ethyl-2-oxazoline) and poly(methacrylic acid) with a wide range of concentrations, Polymer, 10.1016/j.polymer.2013.02.004, 54, 7, 1896-1904, 2013.03, Complexes were formed by mixing aqueous solutions of poly(2-ethyl-2- oxazoline) (PEOX) and poly(methacrylic acid) (PMAA) with a wide range of concentrations and were characterized with infrared and X-ray photoelectron spectroscopy, light scattering and intrinsic viscosity measurements. The infrared and X-ray photoelectron spectra indicated that PEOX and PMAA formed complexes by hydrogen bonds between the carbonyl groups in PEOX and the hydroxyl groups in PMAA but not between the nitrogen atoms in PEOX and the hydroxyl groups in PMAA. The results of light scattering and intrinsic viscosity measurements suggest that PEOX and PMAA first form complexes with high polymer chain density and that the complexes became large in size. The dependence of the precipitation concentration on the molecular weight of PEOX was also determined, and its unique dependence was discussed based on the experimental results..
275.	Hirohmi Watanabe, Aya Fujimoto, Atsushi Takahara, Concealing surface topography by attachment of nanometer-thick film, Langmuir, 10.1021/la304670c, 29, 9, 2906-2911, 2013.03, Concealing of surface topology of substrates by decal-like attachment of nanomembrane is demonstrated. The nanomembrane attachment provides a flat surface on various substrates, including porous substrates, and the surface property such as wettability was changed to that of the nanomembrane. The monitoring of drying process revealed that a nanomembrane with certain thickness tolerates their flexural deflection during the procedure. Moreover, the supporting position of nanomembranes as well as the physical properties of nanomembranes strongly affected the degree of deflection. The decal-like attachment of nanomembranes shown here is potentially a powerful method for creating a new functional surface that is independent of the topological and chemical properties of the original substrate..
276.	Jin Nishida, Motoyasu Kobayashi, Atsushi Takahara, Gelation and adhesion behavior of mussel adhesive protein mimetic polymer, Journal of Polymer Science, Part A: Polymer Chemistry, 10.1002/pola.26487, 51, 5, 1058-1065, 2013.03, An acrylamide-type copolymer containing catechol, amino, and hydroxyl groups was synthesized as a mimetic of the natural mussel adhesive protein (MAP). The obtained copolymer in a phosphate buffer solution (pH = 8.0) formed a hydrogel within 2 h under air, whereas gelation did not proceed under argon atmosphere. We confirmed that the cross-linking reaction of the synthesized MAP mimetic copolymer was triggered by aerobic oxidation of catechol moieties to form an adhesive hydrogel. Two aluminum plates were adhered by the gelation of the MAP mimetic copolymer solution under humid air at room temperature. The interfacial region between the two aluminum plates failed at a lap shear strength of 0.46 MPa due to cohesive failure of the hydrogel. The adhesion strength was dominated by mechanical strength of the hydrogel as well as the interface interaction of catechol groups with substrate surface. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013..
277.	Takamichi Shinohara, Tomoko Shirahase, Daiki Murakami, Taiki Hoshino, Moriya Kikuchi, Jun Ichiro Koike, Misao Horigome, Hiroyasu Masunaga, Hiroki Ogawa, Atsushi Takahara, Precise and nondestructive characterization of a 'buried' nanostructure in a polymer thin film using synchrotron radiation ultra-small angle X-ray scattering, Polymer Journal, 10.1038/pj.2012.133, 45, 3, 307-312, 2013.03, Nanoimprint lithography (NIL) is a simple and high-resolution patterning method. Nanoimprinted structures can be fabricated not only as surface structures but also as 'buried' structures for applications such as electro-optical devices. However, a precise and nondestructive evaluation method for nanoimprinted structures has not yet been established. Synchrotron radiation ultra-small angle X-ray scattering (SR-USAXS) is a nondestructive and high-resolution characterization method. In this study, we fabricated nanostructures on a poly(lactic acid) (PLA) film using NIL. In addition, the nanoimprinted PLA film was covered with a polystyrene thin film to fabricate a 'buried' structure. The fabricated surface and the 'buried' structure were evaluated using SR-USAXS. The scattering pattern was clearly obtained from the surface and the 'buried' structure. The size of the 'buried' structure, which was estimated from the diffraction pattern, was in good agreement with that of the surface structure. These results indicate that SR-USAXS is powerful tool for the nondestructive and precise characterization of surface and 'buried' structures..
278.	Atsushi Takahara, Structural effects of catechol-containing polystyrene gels based on a dual cross-linking approach, Soft Matter, 9, 1967-1974, 2013.02.
279.	Atsushi Takahara, Environmentally friendly repeatable adhesion using a sulfobetaine-type polyzwitterion brush, Polymer Chemistry, 2013.02.
280.	Atsushi Takahara, Effect of supercritical carbon dioxide on molecular aggregation states of side chains of semicrystalline poly{2-(perfluorooctyl)ethyl acrylate} brush thin films, RSC Advances, 3, 14, 4778-4785, 2013.02.
281.	Motoyasu Kobayashi, Tatsuya Ishikawa, Atsushi Takahara, Adhesion and Tribological Characteristics of Ion-Containing Polymer Brushes Prepared by Controlled Radical Polymerization, Polymer Adhesion, Friction, and Lubrication, 10.1002/9781118505175.ch2, 59-82, 2013.02.
282.	Yu Shoji, Ryohei Ishige, Tomoya Higashihara, Junko Morikawa, Toshimasa Hashimoto, Atsushi Takahara, Junji Watanabe, Mitsuru Ueda, Cross-linked liquid crystalline polyimides with siloxane units Their morphology and thermal diffusivity, Macromolecules, 10.1021/ma302486s, 46, 3, 747-755, 2013.02, Cross-linked liquid crystalline (LC) polyimides with siloxane units have been developed as high thermally conductive materials. The relationship between their thermal diffusivities and film morphologies was investigated. The cross-linking reaction of the LC polyimides was monitored by Fourier transform infrared spectroscopy and differential scanning calorimetry. It was found that the cross-linked LC polyimides successfully maintained their LC structures at room temperature as confirmed by polarized optical microscopy and wide-angle X-ray diffraction (WAXD). The thermal diffusivity of the films in the thickness direction measured by a temperature wave analysis method increased gradually from 0.116 to 0.185 mm² s^-1 with the increasing extent of the cross-linking. In the detailed WAXD study, the obtained cross-linked LC polyimide films showed that the polymer chains vertically aligned in the thickness direction of the films, and the increase in the extent of the cross-linking expanded the areas of chain alignment. Such a chain alignment plays an important role in the phonon conduction in the thickness direction of the films..
283.	Motoyasu Kobayashi, Tomoaki Matsugi, Junji Saito, Jun Ichi Imuta, Norio Kashiwa, Atsushi Takahara, Direct modification of polyolefin films by surface-initiated polymerization of a phosphobetaine monomer, Polymer Chemistry, 10.1039/c2py20712e, 4, 3, 731-739, 2013.02, The surfaces of polyethylene and polypropylene sheets were modified by grafting with polymeric brushes formed from a phosphobetaine monomer. Pressed sheets of bromo-functionalized polyethylene or polypropylene macroinitiators (PE-MIs and PP-MIs, respectively) were used to initiate the atom-transfer radical polymerization of 2-(methacryloyloxy)ethyl phosphorylcholine (MPC) under mild conditions to form a superhydrophilic grafted surface layer. The grafted polyolefin sheets showed excellent wettability and oil-detachment behaviour in water. Even three years after surface grafting had been performed, the PMPC-g-PP sheet retained a water contact angle of less than 10°. Furthermore, the water contact angle of the PMPC-g-PP sheet remained as low as 12° after it had been annealed at 373 K for 60 min under reduced pressure. Dynamic friction tests performed on the PMPC-g-PE sheet by sliding it against a glass ball revealed a marked reduction in the friction coefficient in water at sliding velocities in the range of 10^-5 to 10^-1 m s^-1, possibly as a result of lubrication by water..
284.	Hang Xu, Jin Nishida, Hui Wu, Yuji Higaki, Hideyuki Otsuka, Noboru Ohta, Atsushi Takahara, Structural effects of catechol-containing polystyrene gels based on a dual cross-linking approach, Soft Matter, 10.1039/c2sm26994e, 9, 6, 1967-1974, 2013.02, Based on efforts to develop synthetic materials with novel properties similar to the ingenious mussel adhesive, we present a structural study of gels with different cross-linking approaches, using a catechol-bearing polystyrene system. Prior studies have shown that catechol affords a dual cross-linking system based on Fe³⁺-catechol complexes and oxidative coupling. In this study, the structures of gels with different cross-linking ratios were investigated by field-emission scanning electron microscopy (FE-SEM), small angle X-ray scattering (SAXS), Raman spectroscopy, and dynamic viscoelastic measurements. These results revealed that Fe³⁺-catechol cross-linking leads to a more compact structure, which increased the gel rigidity. In addition, Fe³⁺-catechol cross-links could be removed from the hybrid cross-linking system by an acidifying process, yielding a catechol-catechol cross-linked gel with stable covalent bonds. A structure in which a continuous network of loosely folded poly(styrene-co-DOPMAm) chains is combined, with a cross-linking density varying from high (coordinative) to low (covalent), was achieved by balancing both oxidation and coordination. The work presented here will provide inspiration for those designing new classes of synthetic materials with advanced properties, biomimicking extensible byssal threads..
285.	Taiki Hoshino, Yoshihito Tanaka, Hiroshi Jinnai, Atsushi Takahara, Surface and interface analyses of polymer brushes by synchrotron radiation, Journal of the Physical Society of Japan, 10.7566/JPSJ.82.021014, 82, 2, 2013.02, In the present review, we focus on the characterization of polymer brushes by quantum beam, which is regarded as a promising probe of surface and interface analysis. The polymer brushes were prepared on various shapes of surface, and proved to be benefit to various applications. Among them, the polymer brushes grafted on sphere nanoparticles and flat substrates are investigated as representative cases. The static structure of polymer brushes, especially the chain dimension of polymer brushes grafted on nanoparticles and a flat substrate, have been studied by small angle X-ray scattering (SAXS) and neutron reflectivity (NR), respectively. The microscopic dynamical properties of polymer brushes are also expected to be revealed by quantum beam. X-ray photon correlation spectroscopy (XPCS), a technique using a coherent X-ray, is one of the promising methods for microscopically understanding of dynamical properties of polymer brushes. Some of our recent studies about dynamical behavior of polymer brush immobilized nanoparticle by XPCS are also presented..
286.	Atsushi Takahara, Surface and Interface Analysis of Polymer Brushes by Synchrotron Radiation, Journal of the Physical Society of Japan, 82, 0201014-1〜021014-12, 2013.01.
287.	Atsushi Takahara, Direct modification of polyolefin films by Surface-initiated polymerization of a phosphobetaine monomert, Polymer Chemistry, 4, 731-739, 2013.01.
288.	Atsushi Takahara, Thermal gradient effect on the dynamical behavior of nanoparticles observed using X-ray photon correlation spectroscopy, Polymer Journal, 45, 94-99, 2013.01.
289.	Atsushi Takahara, Novel Neutron Reflectometer SOFIA at J-PARC/MLF for In-Situ Soft-Interface Characterization, Polymer Journal, 45, 100-108, 2013.01.
290.	Atsushi Takahara, Experimental station for multiscale surface structural analyses of soft-material films at SPring-8 via a GISWAX/GIXD/XR-integrated system, Polymer Journal, 45, 109-116, 2013.01.
291.	Atsushi Takahara, Chain-Mixing Behavior at Interface between Polystyrene Brushes and Polystyrene Matrices, Polymer Journal, 45, 117-123, 2013.01.
292.	Atsushi Takahara, Mobility Gradient of Polystyrene in Films Supported on Solid Substrates, Advances in Polymer Science, 252, 1-27, 2013.01.
293.	Atsushi Takahara, Perfluoropolyether-infused nano-texture:a versatile approach to omniphobic coatings with low hysteresis and high transparency, Chemical Communications, 49, 597-599, 2013.01.
294.	Atsushi Takahara, Grazing-incidence wide-angle X-ray diffraction study on molecular aggregation state of imprinted polyimide film before and after hard baking, Polymer Bulletin, 70, 1, 105-115, 2013.01.
295.	Atsushi Takahara, Molecular simulation of 2-dimensional microphase separation of single-component homopolymers grafted onto a planar substrate, Europhysics Letters, 101, 16006-P1〜16006-P6, 2013.01.
296.	Atsushi Takahara, Internally Modified Halloysite Nanotubes as Inorganic Nanocontainers for a Flame Retardant, Chemistry Letters, 42, 2, 121-123, 2013.01.
297.	Atsushi Takahara, Influence of trace amount of well-dispersed carbon nanotubes on structural development and tensile properties of polypropylene, Macromolecules, 46, 2, 463-473, 2013.01.
298.	Atsushi Takahara, Precise and nondestructive characterization of a ‘buried’ nanostructure in a polymer thin film using synchrotron radiation ultra-small angle X-ray scattering, Polymer Journal, 45, 307-312, 2013.01.
299.	Atsushi Takahara, Spreading and structuring of water on　superhydrophilic polyelectrolyte brush surfaces, Langmuir, 29, 4, 1148-1151, 2013.01.
300.	Atsushi Takahara, Cross-Linked Liquid Crystalline Polyimides with Siloxane Units: Their Morphology and Thermal Diffusivity, Macromolecules, 46, 3, 463-473, 2013.01.
301.	Hiroshi Arita, Koji Mitamura, Motoyasu Kobayashi, Norifumi L. Yamada, Hiroshi Jinnai, Atsushi Takahara, Chain-mixing behavior at interface between polystyrene brushes and polystyrene matrices, Polymer Journal, 10.1038/pj.2012.198, 45, 1, 117-123, 2013.01, The effect of the molecular weight dispersity (MWD) on the interfacial width between an end-tethered polymer brush and a free polymer matrix has been experimentally investigated by neutron reflectivity (NR) measurements. We prepared high-density hydrogenous polystyrene (hPS) brushes with different MWDs by surface-initiated controlled radical polymerization. Unbound (free) deuterated polystyrene (dPS) with a similar molecular weight to the hPS was mounted on the hPS brush to form bilayer films and annealed at 398 K for 2-120 min. The interfacial width between the narrow-MWD hPS and dPS matrix was relatively unchanged after thermal annealing because of the high graft density and similar molecular architectures (dry-brush regime). However, the broad-MWD hPS brush showed a large interfacial width (wet-brush regime) due to the extension of the longer chains into the dPS matrix and intermixing. The interface width increased rapidly from 2 to 20 nm after annealing for 5 min and increased slowly to 30 nm after 120 min. The volume fraction profile of the broad-MWD hPS brush showed a characteristic gradient distribution as the distance from the substrate surface increased, consistent with the theoretical simulations by Laub and Koberstein. 7 Polydisperse brushes are expected to improve the adhesion and interfacial toughness at solid-polymer interfaces..
302.	Hiroki Ogawa, Hiroyasu Masunaga, Sono Sasaki, Shunji Goto, Takashi Tanaka, Takamitsu Seike, Sunao Takahashi, Kunikazu Takeshita, Nobuteru Nariyama, Haruhiko Ohashi, Toru Ohata, Yukito Furukawa, Tomohiro Matsushita, Yasuhide Ishizawa, Naoto Yagi, Masaki Takata, Hideo Kitamura, Atsushi Takahara, Kazuo Sakurai, Kohji Tashiro, Toshiji Kanaya, Yoshiyuki Amemiya, Kazuyuki Horie, Mikihito Takenaka, Hiroshi Jinnai, Hiroshi Okuda, Isamu Akiba, Isao Takahashi, Katsuhiro Yamamoto, Masamichi Hikosaka, Shinichi Sakurai, Yuya Shinohara, Yasunori Sugihara, Akihiko Okada, Experimental station for multiscale surface structural analyses of soft-material films at SPring-8 via a GISWAX/GIXD/XR-integrated system, Polymer Journal, 10.1038/pj.2012.194, 45, 1, 109-116, 2013.01, To gain a better understanding of the function of soft-material thin films, one should investigate the multiscale structural information from the surface roughness down to the atomically truncated structures at microarea. To achieve such an integrated investigation, a new experimental system has been launched by coupling with the measurement techniques, which include grazing incidence small/wide-angle X-ray scattering (GISWAXS) and grazing incidence X-ray diffraction (GIXD), as well as X-ray reflectivity (XR), at the BL03XU beamline of SPring-8. The high brilliance and low divergence beam allows the surface and interface structure measurements from the angstrom to the micrometer scale using a soller-slit system for proper optimization of measurement precision. A typical structural analysis of the soft-material film was performed to evaluate the practical performance and specifications of the experimental system..
303.	Sudu Siqing, Hui Wu, Hiroki Yamaguchi, Takamichi Shinohara, Osami Sakata, Atsushi Takahara, Grazing-incidence wide-angle X-ray diffraction study on molecular aggregation state of imprinted polyimide film before and after hard baking, Polymer Bulletin, 10.1007/s00289-012-0784-0, 70, 1, 105-115, 2013.01, Nanoimprint lithography (NIL) was carried out on precursor of polyimide (PI), poly(amic acid) film, and then hard baking to obtain imprinted PI film. The molecular aggregation states of imprinted PI films before and after hard baking were investigated by grazing-incidence wide-angle X-ray diffraction comparing with the one of flat PI film. It was found that NIL and hard baking can strongly affect the molecular aggregation states of PI film. Before hard baking, PI chain is aligned parallel to the line direction on the line. After hard baking, the alignment in ordered domain was changed to that the PI molecule of which chain axis is perpendicular to the line direction is significantly increased, while, PI molecule of which chain axis is parallel to the line direction is decreased after hard baking. Through comparing with the flat PI, crystallinity of imprinted PI film has been significantly enhanced..
304.	Peng Liu, Kevin L. White, Hiroaki Sugiyama, Jiang Xi, Takeshi Higuchi, Taiki Hoshino, Ryohei Ishige, Hiroshi Jinnai, Atsushi Takahara, Hung Jue Sue, Influence of trace amount of well-dispersed carbon nanotubes on structural development and tensile properties of polypropylene, Macromolecules, 10.1021/ma3020323, 46, 2, 463-473, 2013.01, Functionalized multiwalled carbon nanotubes (F-MWCNTs) were individually dispersed in a commercial polypropylene (PP) matrix using our well-established α-zirconium phosphate (ZrP) nanoplatelet-assisted dispersion approach. The F-MWCNTs remained uniformly dispersed in PP after melt mixing and injection-molding and were found to remarkably enhance modulus and strength at only 0.1 wt % loading. The individual F-MWCNTs were mostly oriented and extended in the flow direction and were shown to be integrated within the crystalline structure of the matrix. The change in mechanical properties is attributed to both the modification in crystal structure due to MWCNT-induced nucleation and the direct reinforcement of crystalline lamellae and amorphous regions by the MWCNTs. We propose that the compatibilized F-MWCNTs exhibit sufficient interfacial interaction with the PP matrix to anchor lamellae stacks and resist interlamellar slip. The F-MWCNTs also reinforce amorphous domains between crystallites and behave as "super"-tie chains, thereby achieving improvement in tensile properties at low MWCNT loading. This approach for nanocomposite preparation is scalable and easily adapted for other thermoplastics by proper MWCNT surface functionalization..
305.	Y. Norizoe, H. Jinnai, Atsushi Takahara, Molecular simulation of 2-dimensional microphase separation of single-component homopolymers grafted onto a planar substrate, Europhysics Letters, 10.1209/0295-5075/101/16006, 101, 1, 2013.01, The structural phase behavior of polymer brushes, single-component linear homopolymers grafted onto a planar substrate, is studied using the molecular Monte Carlo method in 3 dimensions. When simulation parameters of the system are set in regions of macrophase separation of solution for the corresponding non-grafted homopolymers, the grafted polymers also prefer segregation. However, macrophase separation is disallowed due to the spatially fixed grafting points of the polymers. Such constraints on the grafting are similar to connecting points between blocks of non-grafted diblock copolymers at the microphase separation in the melt state. This results in "microphase separation" of the homopolymer brush in the lateral direction of the substrate. Here we extensively search the parameter space and reveal various lateral domain patterns that are similar to those found in diblock copolymer melts at microphase separation..
306.	Koji Mitamura, Norifui L. Yamada, Hidenori Sagehashi, Naoya Torikai, Hiroshi Arita, Masami Terada, Motoyasu Kobayashi, Setsuo Sato, Hideki Seto, Shinji Goko, Michihiro Furusaka, Tatsuro Oda, Masahiro Hino, Hiroshi Jinnai, Atsushi Takahara, Novel neutron reflectometer SOFIA at J-PARC/MLF for in-situ soft-interface characterization, Polymer Journal, 10.1038/pj.2012.156, 45, 1, 100-108, 2013.01, Structural characterization of interfaces composed of soft materials (soft interfaces) helps in understanding their physical behavior. Neutron reflectometry is one of the most powerful tools to characterize interfacial structures with spatial resolution in nanometers. We have installed a novel horizontal-type time-of-flight neutron reflectometer SOFIA (SOFt Interface Analyzer) at the Japan Proton Accelerator Research Complex. The instrument is capable of accepting two downward neutron beams, at 2.2° and 5.7° to horizontal, which dedicate neutron reflectivity (NR) measurements over a wide range of neutron momentum transfer q (q=(4π/λ)sinθ, where λ and θ are wavelength and incident angle, respectively). The accuracy of NR up to q=6 nm^-1 was confirmed by measuring deuterated polystyrene (d-PS) thin films on a silicon (Si) wafer and multilayers of cadmium stearate prepared by the Langmuir-Blodgett method. NR at the deuterium oxide (D₂ O)/Si disk showed specular reflection down to 10 ^-6-10^-7 and q up to 2.0 nm^-1 along the perpendicular to the sample surface, which improved the precise analysis of swollen polyelectrolyte brush structure at the D₂ O interface. Then, time-resolved in-situ NR measurements were carried out at 1-min intervals to observe interfacial mixing of d-PS on the PS brush surface during 398 K annealing, demonstrating that nonequilibrium behavior at the interfaces can be analyzed on the order of minutes..
307.	Wei Ma, Yuji Higaki, Hideyuki Otsuka, Atsushi Takahara, Perfluoropolyether-infused nano-texture A versatile approach to omniphobic coatings with low hysteresis and high transparency, Chemical Communications, 10.1039/c2cc37576a, 49, 6, 597-599, 2013.01, By infusing a perfluoropolyether lubricating liquid into a nano-textured alumina gel film that was modified with perfluoroalkylphosphonic acid, an omniphobic coating with low hysteresis for both polar and non-polar liquids was prepared..
308.	Toshiji Kanaya, Kazuo Sakurai, Atsushi Takahara, Special issue Application of quantum beams to polymer science and engineering, Polymer Journal, 10.1038/pj.2012.208, 45, 1, 2, 2013.01.
309.	Daiki Murakami, Motoyasu Kobayashi, Taro Moriwaki, Yuka Ikemoto, Hiroshi Jinnai, Atsushi Takahara, Spreading and structuring of water on superhydrophilic polyelectrolyte brush surfaces, Langmuir, 10.1021/la304697q, 29, 4, 1148-1151, 2013.01, The wetting behavior of superhydrophilic polyelectrolyte brushes was investigated. Reflection interference contrast microscopy demonstrated that the contact angles of water on the polyelectrolyte brushes were extremely low but remained finite in the range of
310.	Taiki Hoshino, Daiki Murakami, Kiminori Ito, Yoshihito Tanaka, Sono Sasaki, Masaki Takata, Hiroshi Jinnai, Atsushi Takahara, Thermal gradient effect on the dynamical behavior of nanoparticles observed using X-ray photon correlation spectroscopy, Polymer Journal, 10.1038/pj.2012.193, 45, 1, 94-99, 2013.01, The effects of a thermal gradient on the dynamical behavior of nanoparticles dispersed in a polymer matrix were studied using X-ray photon correlation spectroscopy. Polystyrene (PS)-grafted silica nanoparticles (SiNPs-PS), which are nanoparticles dispersed in a PS matrix controlled at temperatures above the glass transition temperature, were used in this study. Anisotropic motions of the SiNPs-PS were observed when the sample was kept in a conventional capillary tube, whereas isotropic motion was observed when the sample was kept in a newly designed cell with a low thermal flow, demonstrating the importance of the thermal gradient on the dynamical behavior of the SiNPs-PS..
311.	Tatsuya Ishikawa, Motoyasu Kobayashi, Atsushi Takahara, Characterization and tribological behavior of polymer brush functionalized with ionic liquid moiety, Surfactants in Tribology, 10.1201/b13897, 3, 111-130, 2013.01, Since the use of room-temperature ionic liquids as novel lubricants was first reported by Liu and coworkers in 2001 [1-3], ionic liquids have attracted considerable attention as a new class of lubricants [4,5]. This is because of their unique properties such as negligible volatility, low flammability, high thermal stability [6], a low melting point, and a wide liquid range [7]. These characteristics are derived from ionic interactions between large organic cations and inorganic or organic noncoordinating anions, which together form salts with melting points below room temperature [8]. Ionic liquids are expected to be ideal candidates for new lubricants under severe conditions such as ultrahigh vacuum and extreme temperatures [9,10]. The tribological properties of some ionic liquids have been evaluated extensively. Ionic liquids exhibited excellent friction reduction, better wear resistance, and high load capacity than conventional lubricants such as synthetic hydrocarbons and fluoroether polymers [1]. The tribological properties of ionic liquids largely depend on the chemical structure of the organic cations and anions [11]. Liu and coworkers proposed that ionic liquids could be easily adsorbed on the sliding surfaces of frictional pairs because of their polar structure. These liquids can form an effective boundary film, which would reduce friction and wear [1-3]. Xiao and coworkers measured the film thicknesses of ionic liquids at high pressures up to 3 GPa in real time employing the relative optical interference intensity measurement method [12]. The film thicknesses of ionic liquids were greater than those of silicone oils of similar viscosities, indicating better film-forming ability of ionic liquids. Liu and coworkers further suggested that a tribochemical reaction between an ionic liquid and a friction surface under severe contact conditions forms surface-protective films, which was confirmed by Mori and his coworkers [13-15]. However, some tribochemical reactions involving the decomposition of the ionic liquid would cause corrosive wear. In the case of an N-alkyl imidazolium-derived ionic liquid, it has been reported that imidazolium with a short alkyl chain and a reactive anion, such as tetrafluoroborate (BF4-) or hexafluorophosphate (PF6-), increased wear through tribocorrosive attack on steel and aluminum surfaces [16]. One of the reasons for the increased wear is that BF4- and PF6- produce corrosive hydrogen fluoride upon hydrolysis, which can damage frictional systems [17]. Jiménez et al. reported that trifluoromethanesulfonate or 4-methylbenzenesulfonate anions can reduce tribocorrosion and, consequently, friction and wear, despite the presence of the short alkyl chains of the imidazolium cation [18]. In contrast, BF4- of imidazolium cations with longer chains results in lower friction and wear compared with the corresponding PF6- salt [18,19]. The pressure viscosity coefficient of ionic liquids is also an important factor in the formation of a lubrication film [20]. Therefore, the lubrication film for hydrodynamic lubrication and the boundary layer on the friction surface are important for reducing friction and wear using ionic liquids as well as conventional oil-based lubricants. In this study, we propose another type of boundary film prepared by grafting a polymer film consisting of an ionic liquid moiety on the friction surface to improve the tribological properties of ionic liquids. It is expected that the grafted polymer bearing ionic liquid moiety would assist the retention of ionic liquids between the sliding pairs and work as an effective lubrication layer in combination with an ionic liquid..
312.	Motoyasu Kobayashi, Masami Terada, Tatsuya Ishikawa, Atsushi Takahara, Tribological behavior of ionic polymer brushes in aqueous environment, Surfactants in Tribology, 10.1201/b13897, 3, 75-92, 2013.01, The surface-tethering of polymers has become a widely used method for improving the surface physicochemical properties, such as wettability, adhesion, and friction, of solid surfaces. An assembly of polymer chains end-grafted to a solid surface at a sufficiently high graft density in a good solvent is generally referred to as a “polymer brush” [1,2]. The graft density is the number of tethered chains at the surfaces per unit area, which largely depends on the preparation process, such as “grafting-to” or “grafting-from.” Over the last decade, various types of well-defined, high-density polymer brushes have been prepared via surface-initiated controlled radical polymerization (CRP). Such brushes are grown from surface initiating sites that are immobilized on solid surfaces or substrates through covalent bonding. As a result, the brush chains are strongly anchored and are hardly detached from the substrate, even in a good solvent as well as under large shear deformation. Therefore, the polymer brushes with nanometer-scale thickness can act as an efficient lubricant in friction..
313.	Hirohmi Watanabe, Aya Fujimoto, Atsushi Takahara, Characterization of catechol-containing natural thermosetting polymer "urushiol" thin film, Journal of Polymer Science, Part A: Polymer Chemistry, 10.1002/pola.26770, 51, 17, 3688-3692, 2013, Urushi (oriental lacquer) is made from the sap of Rhus vernicifera and consists mainly of the catechol derivative urushiol. Thermal curing of urushiol, unlike other catechol derivatives, is possible because of the unsaturated double bonds in the long hydrocarbon side chain. We described here a simple, efficient method to produce a thermally cross-linked urushi thin film using iron(II) acetate as the additive. The cured thin films showed robust, flexible feature as confirmed by strain-induced elastic buckling instability for mechanical measurements (SIEBIMM) and bulging experiments. In contrast, a thin film of poly(dopamine) that is a typical catechol derivative without long hydrocarbon side chain showed brittleness. The long hydrocarbon side chain of urushiol plays an important role for both thermal processability and superior mechanical properties of the material..
314.	Hui Wu, Yan Cao, Ryohei Ishige, Yuji Higaki, Taiki Hoshino, Noboru Ohta, Atsushi Takahara, Confinement-induced crystal growth in one-dimensional isotactic polystyrene nanorod arrays, ACS Macro Letters, 10.1021/mz400136d, 2, 5, 414-418, 2013, This work demonstrates the anomalous crystal growth of isotactic polystyrene (iPS) in nanorod arrays with different rod sizes. At the bottom of the nanorods, the crystals in bulk film grow into nanorods along either the [110] or [100] direction parallel to the rod axis. On the top side of the nanorods, the polymer exhibits different orientations corresponding to weak or strong confinement. In the weaker confinement (bigger nanorods of 300 nm diameter), the crystals grow with the [100] direction along the nanorod, which is similar to the crystals developed in the radial of spherulite. In the stronger confinement (smaller nanorods of 65 nm diameter), the splaying of crystals in the rod is significantly suppressed, and the preferred growth direction of iPS crystals is kept in either the [110] or [100] direction. The precise control of polymer crystal orientation and crystallinity at a local scale opens important perspectives for the design of one-dimensional nanomaterials whose performance depends on the anisotropic crystal properties..
315.	Peng Liu, Kevin Lee White, Hung Jue Sue, Hiroaki Sugiyama, Atsushi Takahara, Influence of exfoliated carbon nanotubes on crystal structure and tensile properties of polypropylene, 71st Annual Technical Conference of the Society of Plastics Engineers 2013, ANTEC 2013 71st Annual Technical Conference of the Society of Plastics Engineers 2013, ANTEC 2013, 3, 2484-2491, 2013, The objective of this work is to investigate the microstructural mechanisms responsible for the observed remarkable increase in modulus and strength of polypropylene (PP) containing only trace amounts of multi-walled carbon nanotubes (MWCNTs). The functionalized MWCNTs were individually dispersed in commercial polypropylene matrix by using our novel nanoplatelet-assistcd dispersion approach, followed by compatibilization of MWCNT in a small amount of stabilizing surfactant. We also report on the morphology and dynamic mechanical properties, and propose a novel mechanism for reinforcement of thermoplastic materials with individual MWCNTs..
316.	P. Liu, K. L. White, R. Ishige, H. Sugiyama, H. Higuchi, H. Jinnai, Atsushi Takahara, H. J. Sue, Influence of trace-amount of well-dispersed carbon nanotubes on structural development and tensile properties of polypropylene, 2013 SPE International Polyolefins Conference Society of Plastics Engineers - 2013 SPE International Polyolefins Conference, 2013, • PP/MWCNT Nanocomposites were successfully prepared:! - Individual dispersion of MWCNT in PP is achieved! - Structural development was characterized! - Tensile properties can be significantly improved by only a small amount of CNT! - Dramatic improvements in electrical conductivity, thermal degradation stability, and dimensional uniformity are observed! • The outlook for engineering application of polymer nanocomposites is bright!..
317.	Tomoyuki Ohishi, Yoko Iki, Keiichi Imato, Yuji Higaki, Atsushi Takahara, Hideyuki Otsuka, Insertion metathesis depolymerization of aromatic disulfide-containing dynamic covalent polymers under weak intensity photoirradiation, Chemistry Letters, 10.1246/cl.130639, 42, 11, 1346-1348, 2013, Aromatic disulfide bonds become dynamic in a radical process under weak intensity photoirradiation and can undergo metathesis. Aryl disulfide-containing dynamic covalent polyurethanes were prepared by the polyaddition of disulfidecontaining diol and diisocyanate compounds. To determine the dynamic nature of the aryl disulfide-containing polymers, insertion metathesis depolymerization was performed under weak intensity photoirradiation at room temperature. The molecular weights of the dynamic covalent polymers decreased as the irradiation time increased..
318.	Atsushi Takahara, Interfacial dynamics and surface mechanical properties of soft materials, Nihon Reoroji Gakkaishi, 41, 5, 271-281, 2013, Surface and interfacial dynamics and surface mechanical properties are important for both fundamental and practical aspects. In this paper, our recent researches on 1) surface molecular motion and frictional properties of organosilane monolayer immobilized on Si-substrate, 2) characterization of mechanical and thermal properties buried interface in multiphase polymer thin films by scanning force microscopy, 3) wettability, friction, and adhesion of polymer brushes, and 4) application of X-ray photon correlation spectroscopy for soft materials are summarized..
319.	Hui Jing, Yuji Higaki, Wei Ma, Hui Wu, Weng On Yah, Hideyuki Otsuka, Yuri M. Lvov, Atsushi Takahara, Internally modified halloysite nanotubes as inorganic nanocontainers for a flame retardant, Chemistry Letters, 10.1246/cl.2013.121, 42, 2, 121-123, 2013, We have selectively hydrophobized halloysite nanotube lumens for efficient loading with a flame retardant for controlled releasing composite materials. The inner lumen of octadecylphosphonic- acid-modified halloysite was loaded with hydrophobic bisphenol-A bis(diphenyl phosphate). This flame retardant was released from the clay nanotubes in linear fashion over 60 h demonstrating the system potential utility as effective nanocontainers for smart composite systems..
320.	Jin Nishida, Motoyasu Kobayashi, Atsushi Takahara, Light-triggered adhesion of water-soluble polymers with a caged catechol group, ACS Macro Letters, 10.1021/mz300524q, 2, 2, 112-115, 2013, An acrylamide-type copolymer containing hydroxyl, amino, and ortho-nitrobenzyl protected catechol groups was synthesized as a functional mussel adhesive protein (MAP) mimetic. The resulting copolymer was stable even in the oxidative condition. Light irradiation to aqueous solution of the copolymer induced deprotection of a caged compound to give a native catechol group and triggered an oxidative cross-linking reaction to afford the adhesive gel. Two glass plates were adhered through light-activated gelation of the polymer solution in a humid air atmosphere. A novel type of light-activated adhesive with excellent stability and light controllable activation properties was successfully fabricated by modification of the MAP mimetic copolymer..
321.	Yoshihisa Fujii, Hiroshi Morita, Atsushi Takahara, Keiji Tanaka, Mobility gradient of polystyrene in films supported on solid substrates, Glass Transition, Dynamics and Heterogeneity of Polymer Thin Films, 10.1007/12-2012-175, 252, 1-28, 2013, In this review, we show the distribution of glass transition temperature (T _g) in monodisperse polystyrene (PS) films coated on silicon oxide layers along the direction normal to the surface. Scanning force microscopy with a lateral force mode revealed that surface T _g () was lower than the corresponding bulk T _g (). Interestingly, the glass transition dynamics at the surface was better expressed by an Arrhenius equation than by a Vogel-Fulcher-Tamman equation. Interdiffusion experiments for PS bilayers at various temperatures, above and below, enabled us to gain direct access to the mobility gradient in the surface region. T _g at the solid substrate was examined by fluorescence lifetime measurements using evanescent wave excitation. The interfacial T _g was higher than the corresponding. The extent of the elevation was a function of the distance from the substrate and the interfacial energy. The T _g both at the surface and interface was also studied by the coarse-grained molecular dynamics simulation. The results were in good accordance with the experimental results. Finally, dynamic mechanical analysis for PS in thin and ultrathin films was made. The relaxation time for the segmental motion became broader towards the faster and slower sides, due probably to the surface and interfacial mobility. Graphical Abstract:.
322.	Masamichi Nishihara, Keiichi Imato, Atsushi Irie, Takeshi Kanehara, Arihiro Kano, Atsushi Maruyama, Atsushi Takahara, Hideyuki Otsuka, Reversibly crosslinked polymeric micelles formed by autonomously exchangeable dynamic covalent bonds, Chemistry Letters, 10.1246/cl.121289, 42, 4, 377-379, 2013, We report the preparation of amphiphilic block copolymer micelles with dynamic covalent bonds as autonomously exchangeable crosslinkers with high tolerance against oxygen. Diarylbibenzofuranone (DABBF) was employed as a crosslinker owing to its durability to oxygen and autonomous exchangeability at ambient temperature. It was confirmed that the amphiphilic block copolymer containing the DABBF unit has the capability to form micelles and can form a crosslinking with an exchangeable structure in the presence of oxygen..
323.	Yuji Higaki, Ryosuke Okazaki, Motoyasu Kobayashi, Atsushi Takahara, Tribological properties of polymer brushes from bio-based monomers, Society of Tribologists and Lubrication Engineers Annual Meeting and Exhibition 2013 Society of Tribologists and Lubrication Engineers Annual Meeting and Exhibition 2013, 242-243, 2013, Bio-based plastics can be designed with superior hardness and thermal properties comparable to conventional petroleum-based plastics. However, bio-based plastics often meet the processing challenges, and the brittleness limits the industrial application. A high density poly(α-methylene-γ-butyrolactone) (PMBL) brush film was prepared, and the molecular aggregation structure and tribological properties were studied. The PMBL and poly(methyl methacrylate) (PMMA) brushes exhibited a thickness larger than random coil dimension but lower than extended-chain conformation, indicating that a densely packed brush layer was formed and the chain conformation has been stretched almost perpendicular to the substrate. The PMBL brushes exhibited stable friction coefficient of ∼ 0.2 after 400 friction cycles, demonstrating a better wear resistance. Although the slight wear track was formed on the brush surface during the friction test, a decreased amount of wear debris and an overall smoother wear track were observed. This suggests that the PMBL brushes have a potential for practical scratch resistant applications. This is an abstract of a paper presented at the 2013 STLE Annual Meeting & Exhibition (Detroit, MI 5/5-9/2013)..
324.	Atsushi Takahara, Preparation of novel polyimide hybrid materials by multi-layered charge-transfer complex formation, Polymer Journal, 1-6, 2012.12.
325.	Atsushi Takahara, Dynamic Covalent Polymer Brushes: Reversible Surface Modification of Reactive Polymer Brushes with Alkoxyamine-based Dynamic Covalent Bonds, Polymer Chemistry, 3, 3077-3083, 2012.11.
326.	Tomoya Sato, Yoshifumi Amamoto, Hiroki Yamaguchi, Tomoyuki Ohishi, Atsushi Takahara, Hideyuki Otsuka, Dynamic covalent polymer brushes Reversible surface modification of reactive polymer brushes with alkoxyamine-based dynamic covalent bonds, Polymer Chemistry, 10.1039/c2py20294h, 3, 11, 3077-3083, 2012.11, Reactive poly(methacrylate)-based polymer brushes with radically exchangeable alkoxyamine units in the side chains were prepared on flat silicon substrates and their reactivity and surface properties were investigated. The reactive polymer brushes were prepared by surface-initiated atom transfer radical polymerization (ATRP) and the graft density of the brushes was estimated to be approximately 0.36 chains per nm ². Radical crossover reactions among the alkoxyamine units in the side chains of the polymer brushes and at the ends of the fluorinated polymer chains were carried out to produce polymer brushes with low surface free energies. Angular-dependent X-ray photoelectron spectroscopy (XPS) measurement suggested that the fluorinated polymer chains were predominantly attached to the outermost surface because of the size exclusion from the high graft density. In addition, the de-grafting reaction of the fluorinated polymer chains was also performed to confirm the reversibility of the radical crossover reactions. The surface properties of the polymer brushes after the grafting and de-grafting processes were characterized by XPS and contact angle measurements. The composition calculated from the XPS indicated that the reversible grafting of the fluorinated polymer chains proceeded successfully. The surface wettability of the polymer brushes also changed after the grafting of the fluorinated polymers. Furthermore, after the de-grafting of the fluorinated polymer chains, the peaks attributed to fluorine atoms completely disappeared from the XPS spectrum and the wettability of the surface after the de-grafting returned to that obtained before grafting..
327.	Taiki Hoshino, Moriya Kikuchi, Daiki Murakami, Yoshiko Harada, Koji Mitamura, Kiminori Ito, Yoshihito Tanaka, Sono Sasaki, Masaki Takata, Hiroshi Jinnai, Atsushi Takahara, X-ray photon correlation spectroscopy using a fast pixel array detector with a grid mask resolution enhancer, Journal of Synchrotron Radiation, 10.1107/S0909049512038769, 19, 6, 988-993, 2012.11, The performance of a fast pixel array detector with a grid mask resolution enhancer has been demonstrated for X-ray photon correlation spectroscopy (XPCS) measurements to investigate fast dynamics on a microscopic scale. A detecting system, in which each pixel of a single-photon-counting pixel array detector, PILATUS, is covered by grid mask apertures, was constructed for XPCS measurements of silica nanoparticles in polymer melts. The experimental results are confirmed to be consistent by comparison with other independent experiments. By applying this method, XPCS measurements can be carried out by customizing the hole size of the grid mask to suit the experimental conditions, such as beam size, detector size and sample-to-detector distance..
328.	Atsushi Takahara, Formation of Layered Perovskite Structure by Folding Monolayer during Compression, Journal of Nanoscience and Nanotechnology, 12, 10, 8094-8097, 2012.10.
329.	Hiroshi Arita, Kenji Hiramatsu, Takayuki Narita, Atsushi Takahara, Masanao Era, Yushi Oishi, Formation of layered perovskite structure by folding monolayer during compression, Journal of Nanoscience and Nanotechnology, 10.1166/jnn.2012.6607, 12, 10, 8094-8097, 2012.10, The morphology and layered structure of an alkyl ammonium bromide ultrathin film prepared on an aqueous solution of lead bromide were investigated on the basis of surface pressure-area curve measurements, reflection spectrum measurements, X-ray reflectivity measurements and atomic force microscopic observations. It became apparent that the layered structure sandwiched a twodimensional inorganic layer between two organic monolayers was formed by folding the monolayer by compression on an aqueous PbBr₂ solution..
330.	Sudu Siqing, Hui Wu, Atsushi Takahara, Morphology of nanoimprinted polyimide films fabricated via a controlled thermal history, Polymer Journal, 10.1038/pj.2012.53, 44, 10, 1036-1041, 2012.10, Fabricating nanopatterns on polyimide (PI) films directly by nanoimprint lithography (NIL) is difficult owing to the high glass transition temperature (T g). In this study, a nanopatterned PI film was successfully obtained by nanoimprinting poly(amic acid) (PAA) film and curing it afterward. Differential scanning calorimetry, thermogravimetry and dynamic mechanical analysis were carried out to study the state of thermal molecular motion in PAA thick films that have the same content of residual solvent as the PAA thin films used in NIL. The thermal and dynamic mechanical behaviors of PI thick films were studied for comparison. An appropriate nanoimprinting process was proposed based on an understanding of the thermal and dynamic mechanical properties of PAA and PI films. Atomic force microscopy showed that the line pattern was transferred without distortion from the PAA film to the PI film, even though a larger shrinkage took place during the hard baking..
331.	Taiki Hoshino, Moriya Kikuchi, Daiki Murakami, Yoshiko Harada, Koji Mitamura, Kiminori Ito, Yoshihito Tanaka, Sono Sasaki, Masaki Takata, Hiroshi Jinnai, Atsushi Takahara, X-ray photon correlation spectroscopy using a fast pixel array detector with a grid mask resolution enhancer, Journal of Synchrotron Radiation, 19, 6, 988-993, 2012.09.
332.	Motoyasu Kobayashi, Masami Terada, Atsushi Takahara, Tribological Behavior of Polymer Brushes Designed on the Basis of Biomimetic Water Lubrication, Proceedings of EcoDesign 2011: 7th International Symposium on Environmentally Conscious Design and Inverse Manufacturing（Springer）, 901-904, 2012.09.
333.	Hiroshi Arita, Koji Mitamura, Motoyasu Kobayashi, Norifumi. L. Yamada, Hiroshi Jinnai, Atsushi Takahara, Orientation of poly(vinyl alcohol) nanofiber and crystallites in non-woven electrospun nanofiber mats under uniaxial stretching, Polymer, 53, 4702-4708, 2012.09.
334.	M. Asada, N. Jiang, L. Sendogdular, P. Gin, Y. Wang, M. K. Endoh, T. Koga, M. Fukuto, D. Schultz, M. Lee, X. Li, J. Wang, M. Kikuchi, Atsushi Takahara, Heterogeneous lamellar structures near the polymer/substrate interface, Macromolecules, 10.1021/ma301000z, 45, 17, 7098-7106, 2012.09, We report the structural heterogeneity of recrystallized linear low-density polyethylene (LLDPE) films (25, 50, and 100 nm in thickness) in the direction normal to the surface, based on in situ grazing incidence small-angle X-ray scattering (GISAXS) and X-ray diffraction (GID) measurements. The GID results have clarified the presence of the edge-on lamellae at the surfaces and in the interior of the LLDPE films prepared on Si substrates as thin as 25 nm in thickness. However, the degree of the crystallinity for the 25 nm thick film was almost half of those for the 50 and 100 nm thick films, while the melting temperature (T _m) for all the films remained unchanged relative to the bulk (T _m = 117 °C). Moreover, the GISAXS results for the 25 nm thick film indicate the structural heterogeneity in the direction normal to the surface: (i) At the polymer/air interface, the presence of the disordered edge-on lamellae which lack well-defined long periods even at T ≪ T _m; (ii) At the polymer/substrate interface, the persistence of a substrate-bound edge-on lamellar layer even at T ≫ T _m; (iii) In between the two interfacial layers, the existence of the well-ordered edge-on lamellae with the long periods. These heterogeneous structures can be explained as a consequence of the nucleation initiated at the topmost surface of the substrate-bound lamellar layer..
335.	Takahiro Yano, Yuji Higaki, Di Tao, Daiki Murakami, Motoyasu Kobayashi, Noboru Ohta, Jun Ichiro Koike, Misao Horigome, Hiroyasu Masunaga, Hiroki Ogawa, Yuka Ikemoto, Taro Moriwaki, Atsushi Takahara, Orientation of poly(vinyl alcohol) nanofiber and crystallites in non-woven electrospun nanofiber mats under uniaxial stretching, Polymer, 10.1016/j.polymer.2012.07.067, 53, 21, 4702-4708, 2012.09, The development of macroscopic nanofiber orientation and microscopic crystallite and molecular chain orientation have been investigated during uniaxial stretching of electrospun poly(vinyl alcohol) (PVA) non-woven nanofiber mats. Scanning electron microscopy and stress-strain/small-angle X-ray scattering show that the macroscopic nanofiber orientation significantly increases during the initial stage of deformation, and approaches a plateau on the way of stretching. Detailed analyses of the stress-strain/wide-angle X-ray diffraction measurement and polarized Fourier transform infrared spectroscopy indicate that the microscopic crystallite and molecular chain orientation rapidly increase at the initial stage of stretching due to macroscopic nanofiber orientation. At higher deformation, the microscopic modes of orientation continuously develop as a result of the nanofiber stretching. The complicated deformation process of non-woven nanofiber mats is discussed in terms of macroscopic nanofiber orientation and the microscopic crystallite and molecular chain orientation..
336.	Yoshifumi Amamoto,Hideyuki Otsuka, Atsushi Takahara,Krzysztof Matyjaszewski, Self-Healing of Covalently Cross-Linked Polymers by Reshuffling Thiuram Disulfide Moieties in Air under Visible Light, Advanced Materials, 24, 29, 3975-3980, 2012.08.
337.	Hui Wu, Zhaohui Su, Atsushi Takahara, Characterization of an isotactic polystyrene/poly(2,6-dimethylphenylene oxide) nanorod blend with gradient composition and crystallinity, The Royal Society of Chemistry, 2, 8707-8712, 2012.08.
338.	Mitsunori Asada, Naisheng Jiang, Levent Sendogdular, Peter Gin, Yantian Wang, Maya K. Endoh, Tadanori Koga, Masafumi Fukuto, David Schultz, Myungae Lee, Xuefa Li, Jin Wang, Moriya Kikuchi, Atsushi Takahara, Heterogeneous lamellar structures near the polymer/substrate interface, Macromolecules, 45, 17, 7098-7106, 2012.08.
339.	Yoshifumi Amamoto, Hideyuki Otsuka, Atsushi Takahara, Krzysztof Matyjaszewski, Self-healing of covalently cross-linked polymers by reshuffling thiuram disulfide moieties in air under visible light, Advanced Materials, 10.1002/adma.201201928, 24, 29, 3975-3980, 2012.08, Self-healing of covalently cross-linked polymers under an ambient visible light in the bulk state, in air, at room temperature using radical exchange of thiuram disulfide units is reported. The successful attachment of surfaces of cut pieces proceeded under ambient conditions under exposure to visible light from a commercial tabletop lamp, as confirmed by bending and tensile tests..
340.	Wei Ma, Hui Wu, Yuji Higaki, Hideyuki Otsuka, Atsushi Takahara, A "non-sticky" superhydrophobic surface prepared by self-assembly of fluoroalkyl phosphonic acid on a hierarchically micro/nanostructured alumina gel film, Chemical Communications, 10.1039/c2cc32513f, 48, 54, 6824-6826, 2012.07, A hierarchically micro/nanostructured alumina gel film was prepared by using a simple sol-gel process; upon self-assembly of fluoroalkyl phosphonic acid, a "non-sticky" superhydrophobic surface was obtained..
341.	Naoyuki Morishige, Norihiro Yamada, Xu Zhang, Yukiko Morita, Naoyuki Yamada, Kazuhiro Kimura, Atsushi Takahara, Kohei Sonoda, Abnormalities of stromal structure in the bullous keratopathy cornea identified by second harmonic eneration imaging microscopy, Investigative Ophthalmology and Visual Science, 10.1167/iovs.12-10214, 53, 8, 4998-5003, 2012.07, PURPOSE. To identify structural alterations in collagen lamellae and the transdifferentiation of keratocytes into myofibroblasts in the corneal stroma of bullous keratopathy (BK) patients and to examine the relation of such changes to the duration of stromal edema or the underlying cause of BK. METHODS. Six normal human corneas and 16 BK corneas were subjected to second harmonic generation (SHG) imaging microscopy to allow three-dimensional (3-D) reconstruction of collagen lamellae. Expression of α-smooth muscle actin (αSMA) was examined by immunofluorescence analysis and conventional laser confocal microscopy. RESULTS. Collagen lamellae were interwoven at the anterior stroma and uniformly aligned at the posterior stroma, whereas aSMA was not detected throughout the entire stroma of the normal cornea. Nine (56%) and 7 (44%) of the 16 BK corneas showed abnormal collagen structure at the anterior and posterior stroma, respectively. Expression of αSMA was detected in the anterior or posterior stroma of 7 (44%) and 6 (38%) of the 16 BK corneas, respectively. Disorganization of collagen lamellae and myofibroblastic transdifferentiation were detected only in corneas with a duration of stromal edema of at least 12 months. Corneas with BK as a result of birth injury showed abnormal collagen structure at the posterior stroma, whereas those with BK resulting from laser iridotomy did not. CONCLUSIONS. Changes in the structure of the entire stroma were detected in BK corneas with a duration of stromal edema of at least 12 months, suggesting that such changes may be progressive. In addition, the underlying cause of BK may influence structural changes at the posterior stroma..
342.	Weng On Yah, Hang Xu, Hiroe Soejima, Wei Ma, Yuri Lvov, Atsushi Takahara, Biomimetic dopamine derivative for selective polymer modification of halloysite nanotube lumen, Journal of the American Chemical Society, 10.1021/ja303340f, 134, 29, 12134-12137, 2012.07, We demonstrate the use of a catecholic anchor (Dopa) for selective modification of the inner surface of an halloysite clay nanotube. Aqueous Dopa binds to alumina at the tube lumen and does not bind the silica surface under the same conditions. Selectivity of surface modification was evidenced using X-ray photoelectron spectroscopy (XPS) and ¹³C solid state NMR spectroscopy. Surface-initiated atom transfer radical polymerization (SI-ATRP) was performed through selectively adsorbed Dopa to graft a layer of polymer brush into the nanotube lumen..
343.	Naoyuki Morishige, Norihiro Yamada, Xu Zhang, Yukiko Morita, Naoyuki Yamada, Kazuhiro Kimura, Atsushi Takahara, Koh-Hei Sonoda, Abnormalities of Stromal Structure in the Bullous Keratopathy Cornes Indentified by Second Harmonic Generation Imaging Microscopy, Investigative Ophtalmology & Visual Science, 52, 8, 4998-5003, 2012.06.
344.	Wei Ma, Weng On Yah, Hideyuki Otsuka, Atsushi Takahara, Application of imogolite clay nanotubes in organic-inorganic nanohybrid materials, Journal of Materials Chemistry, 10.1039/c2jm31570j, 22, 24, 11887-11892, 2012.06, The unique one dimensional structure and the positively charged external surface are the driving forces for imogolite clay nanotubes emerging as one of the most promising nano building blocks for various hybrid materials. This paper reviews the utility of imogolite in organic-inorganic nanohybrids, including polymer-imogolite nanocomposites and imogolite based hybrid hydrogels. Several effective approaches for dispersing imogolite down to small-sized bundles or even individual nanotubes in polymer matrices, including both hydrophobic and hydrophilic polymers, are introduced. The application of imogolite for the direct gel formation of biomolecules is also introduced..
345.	Song Hong, Takeshi Higuchi, Hidekazu Sugimori, Takeshi Kaneko, Volker Abetz, Atsushi Takahara, Hiroshi Jinnai, Highly oriented and ordered double-helical morphology in ABC triblock terpolymer films up to micrometer thickness by solvent evaporation, Polymer Journal, 10.1038/pj.2012.69, 44, 6, 567-572, 2012.06, A triblock terpolymer, polystyrene-block-polybutadiene-block-poly(methyl methacrylate) (SBM), formed a double-helical nanoscale structure, composed of polybutadiene (PB) helical microdomains around hexagonally packed polystyrene (PS) cores in a poly(methyl methacrylate) matrix. The orientation of double-helical morphologies at various film thicknesses were studied using transmission electron microtomography, following solvent annealing and drying at a controlled solvent evaporation rate. The evaporation rate of the solvent and the film thickness were important factors in whether the double-helical microdomains were oriented parallel or perpendicular with respect to the substrate. In some cases, the perpendicularly aligned double-helical morphology extended several micrometers from the substrate to the air surface. A similar experiment using polystyrene-block-poly(methyl methacrylate) diblock copolymer proved that the presence of helical PB microdomains around PS cylinders is the key factor in achieving a uniform orientation over several micrometers throughout the film thickness..
346.	Motoyasu Kobayashi, Yuki Terayama, Hiroki Yamaguchi, Masami Terada, Daiki Murakami, Kazuhiko Ishihara, Atsushi Takahara, Wettability and Antifouling Behavior on the Surfaces of Superhydrophilic Polymer Brushes, Langumuir, 28, 7212-7222, 2012.05.
347.	Yongsok Seo, Sang Gil Youm, Ji Hun Kim, Youngwook P. Seo, Soon Man Hong, Dae Won Sohn, Atsushi Takahara, Hyoung Jin Choi, Aggregation behavior of a polystyrene-b-poly(phenylsilsesquioxane) H-type copolymer at the air/water interface, Polymer, 10.1016/j.polymer.2012.03.032, 53, 11, 2223-2232, 2012.05, A comprehensive Langmuir film balance/atomic force microscope study of the surface aggregation behavior of an H-type block copolymer having four branches of polystyrene (PS) blocks (number average molar mass (M _n) = 5000 Da per each branch) and poly(phenylsilsesquioxane) (PPSQ) (M _n = 40,000 Da) has been performed. Temperature dependent surface pressure isotherms and hysteresis experiments were combined with molecules aggregation number per surface micelle, leading to a self-consistent picture of the surface morphology and aggregation phenomena. In spite of the ladder structure of the PPSQ segment, the micelles mostly exist as spherical aggregates because of strong interaction between PS blocks..
348.	Hui Wu, Zhaohui Su, Yuki Terayama, Atsushi Takahara, Polystyrene-based blend nanorods with gradient composition distribution, Science China Chemistry, 10.1007/s11426-012-4501-5, 55, 5, 726-734, 2012.05, The polystyrene-based polymer blends, partially miscible poly(bisphenol A carbonate)/polystyrene (PC/PS) and completely miscible poly(2,6- dimethylphenylene oxide)/polystyrene (PPO/PS), in nanorods with gradient composition distribution were discussed. The polymer blend nanorods were prepared by infiltrating the polymer blends into nanopores of anodic aluminum oxide (AAO) templates via capillary action. Their morphology was investigated by micro-Fourier transform infrared spectroscopy (micro-FTIR) and nano-thermal analysis (nano-TA) with spatial resolution. The composition gradient of polymer blends in the nanopores is governed by the difference of viscosity and miscibility between the two polymers in the blends and the pore diameter. The capillary wetting of porous AAO templates by polymer blends offers a unique method to fabricate functional nanostructured materials with gradient composition distribution for the potential application to nanodevices..
349.	Motoyasu Kobayashi, Yuki Terayama, Hiroki Yamaguchi, Masami Terada, Daiki Murakami, Kazuhiko Ishihara, Atsushi Takahara, Wettability and antifouling behavior on the surfaces of superhydrophilic polymer brushes, Langmuir, 10.1021/la301033h, 28, 18, 7212-7222, 2012.05, The surface wettabilities of polymer brushes with hydrophobic and hydrophilic functional groups were discussed on the basis of conventional static and dynamic contact angle measurements of water and hexadecane in air and captive bubble measurements in water. Various types of high-density polymer brushes with nonionic and ionic functional groups were prepared on a silicon wafer by surface-initiated atom-transfer radical polymerization. The surface free energies of the brushes were estimated by Owens-Wendt equation using the contact angles of various probe liquids with different polarities. The decrease in the water contact angle corresponded to the polarity of fluoroalkyl, hydroxy, ethylene oxide, amino, carboxylic acid, ammonium salt, sulfonate, carboxybetaine, sulfobetaine, and phosphobetaine functional groups. The poly(2-perfluorooctylethyl acrylate) brush had a low surface free energy of approximately 8.7 mN/m, but the polyelectrolyte brushes revealed much higher surface free energies of 70-74 mN/m, close to the value for water. Polyelectrolyte brushes repelled both air bubbles and hexadecane in water. Even when the silicone oil was spread on the polyelectrolyte brush surfaces in air, once they were immersed in water, the oil quickly rolled up and detached from the brush surface. The oil detachment behavior observed on the superhydrophilic polyelectrolyte brush in water was explained by the low adhesion force between the brush and the oil, which could contribute to its excellent antifouling and self-cleaning properties..
350.	Wei Ma, Hui Wu, Yuji Higaki, Hideyuki Otsuka, Atsushi Takahara, A “non-sticky” superhydrophobic surface prepared by self-assembly of fluoroalkyl phosphonic acid on a hierarchically micro/nanostructured alumina gel film, Chemical Communications, 48, 6824, 2012.04.
351.	Weng On Yah, Hang Xu, Hiroe Soejima, Wei Ma, Yuri Lvov, Atsushi Takahara, Biomimetic Dopamine Derivative for Selective Polymer Modification of Halloysite Nanotube Lumen, Journal of American Chemcal Society, 139, 29, 12134-12137, 2012.04.
352.	Song Hong, Takeshi Higuchi, Hidekazu Sugimori, Takeshi Kaneko, Volker Abetz, Atsushi Takahara, Hiroshi Jinnai, Highly Oriented and Ordered Double-Helical Morphology in ABC Triblock Terpolymer Films up to Micrometer Thickness by Solvent Evaporation, Polymer Journal, 44, 567-572, 2012.04.
353.	Sudu Siqing, Hui Wu, Atsushi Takahara, Morphology of Nanoimprinted Polyimide Films Fabricated via a Controlled Thermal History, Polymer Journal, 44, 1036-1041, 2012.04.
354.	Motoyasu Kobayashi, Masami Terada, Yuki Terayama, Moriya Kikuchi, Atsushi Takahara, Direct controlled polymerization of ionic monomers by surface-initiated ATRP using a fluoroalcohol and ionic liquids, Israel Journal of Chemistry, 10.1002/ijch.201100136, 52, 3-4, 364-374, 2012.04, Surface-initiated atom transfer radical polymerization (ATRP) of (2-methacryloyloxyethyl)trimethylammonium chloride (MTAC), 3-(N-2- methacryloyloxyethyl-N,N-dimethyl) ammonatopropanesulfonate) (MAPS), and 2-methacryloyloxyethyl phosphorylcholine (MPC) was carried out in 2,2,2-trifluoroethanol (TFE) containing a small amount of 1-hexyl-3- methylimidazolium chloride at 60 °C to produce well-defined ionic polymer brushes and the corresponding free polymers with predictable number-average molecular weight (M _n, 1×10 ⁴-3×10 ⁵ g mol ^-1) and narrow molecular weight dispersity (M _w/M _n0/[M])) and polymerization time. Reduction in polymerization rates was observed with an increase in ionic liquid concentration. The M _n of both poly(MTAC) and poly(MAPS) increased in proportion to the conversion. The sequential polymerization of MAPS initiated with the chain ends of poly(MAPS) produced the postpolymer with quantitative efficiency. The thickness of the polymer brush was controllable from 5 to 100 nm based on the M _n of the polymer. These results suggest the successful control of the polymerization of sulfobetaine-type methacrylates owing to the TFE and ionic liquids. In particular, the high affinity of TFE for the sulfobetaine monomers and polymers yielded a homogeneous polymerization media to improve surface-initiated polymerization generating the polymer brushes on the substrate surface as well as the free polymers formed in the solution. The effect on ATRP of the chemical structure of ionic liquids and ligands for copper catalyst was also investigated..
355.	Wei Ma, Weng On Yah, Hideyuki Otsuka, Atsushi Takahara, Surface functionalization of aluminosilicate nanotubes with organic molecules, Beilstein J. Nanotechnol, 10.3762/bjnano.3.10, 2012.3, 82-100, 2012.03.
356.	Hui Wu, Zhaohui Su, Atsushi Takahara, Isotactic polystyrene nanorods with gradient crystallite states, Soft Matter, 10.1039/c2sm06896f, 8, 11, 3180-3184, 2012.03, In this paper, isotactic polystyrene (iPS) nanorods with gradient crystallite distribution were demonstrated. The polymer nanorods with a diameter of 65 nm were prepared by melt-wetting the nanoporous alumina template with fractionated iPS melts. Spatial distribution of crystallinity and orientation of the polymer in the nanorods from top to bottom were analyzed by Fourier transform infrared spectroscopy. The crystallites with perpendicular orientation (c-axis perpendicular to the long axis of rod) increased from the top to the bottom of the nanorods due to crystallization initiated by nuclei formed in the bulk and subsequent crystallite growth constrained by the nanopores. This result offers a unique approach to design polymeric nanomaterials with gradient crystallite distribution for functional nanodevice applications..
357.	Moriya Kikuchi, Yuki Terayama, Tatsuya Ishikawa, Taiki Hoshino, Motoyasu Kobayashi, Hiroki Ogawa, Hiroyasu Masunaga, Jun-ichiro Koike, Misao Horigome, Kazuhiko Ishihara, Atsushi Takahara, Chain dimension of polyampholytes in solution and immobilized brush states, Polym J, 10.1038/pj.2011.116, 44, 121-130, 2012.02.
358.	Tetsuro Soejima, Ren-Hua Jin, Yuki Terayama, Atsushi Takahara, Takamasa Shiraishi, Seishiro Ito, Nobuo Kimizuka, Synthesis of TiO2 Nanocoral Structures in Ever-Changing Aqueous Reaction Systems, Langmuir, 10.1021/la203943j, 28, 5, 2637-2642, 2012.02.
359.	Weng On Yah, Atsushi Takahara,Yuri M. Lvov, Selective Modification of Halloysite Lumen with Octadecylphosphonic Acid: New Inorganic Tubular Micelle, J. Am. Chem. Soc., 10.1021/ja210258y, 134, 3, 1853-1859, 2012.02.
360.	Hiroki Yamaguchi, Moriya Kikuchi, Motoyasu Kobayash, Hiroki Ogawa, Hiroyasu Masunaga, Osami Sakata, Atsushi Takahara, Influence of Molecular Weight Dispersity of Poly{2-(perfluorooctyl)ethyl acrylate} Brushes on Their Molecular Aggregation States and Wetting Behavior, Macromolecules, 10.1021/ma202300r, 45, 3, 1509-1516, 2012.02.
361.	Motoyasu Kobayashi, Atsushi Takahara, Tribological properties in aqueous media of polyelectrolyte brushes prepared by controlled polymerization surface design for novel type of environment friendly lubrication, Toraibarojisuto/Journal of Japanese Society of Tribologists, 57, 2, 91-96, 2012.02.
362.	H. Wu, Z.H. Su, A. Takahara, Isotactic Polystyrene Nanorods with Gradient Crystallie States, Soft Matter, 10.1039/C2SM06896F, 8, 3180-3184, 2012.01.
363.	N. Jiravanichanun, K. Yamamoto, K. Kato, J. Kim, Jungeun, S. Horiuchi, W.-O. Yah, H. Otsuka, A. Takahara, Preparation and Characterization of Imogolite/DNA Hybrid Hydrogels, Biomacromolecules, 10.1021/bm201616m, 13, 276?281, 2012.01.
364.	Hang Xu, Jin Nishida, Wei Ma, Hui Wu, Motoyasu Kobayashi, Hideyuki Otsuka, Atsushi Takahara, Competition between Oxidation and Coordination in Cross-Linking of Polystyrene Copolymer Containing Catechol Groups, ACS Macro Lett., 10.1021/mz200217d, 1, 4, 457-460, 2012.01.
365.	Yoshifumi Amamoto, Hideyuki Otsuka, Atsushi Takahara, Krzysztof Matyjaszewski, Changes in Network Structure of Chemical Gels Controlled by Solvent Quality through Photoinduced Radical Reshuffling Reactions of Trithiocarbonate Units, ACS Macro Lett., 10.1021/mz300070t, 1, 4, 478?481, 2012.01.
366.	Keiichi Imato,Masamichi Nishihara,Takeshi Kanehara,Yoshifumi Amamoto,Atsushi Takahara, Hideyuki Otsuka, Self-Healing of Chemical Gels Cross-Linked by Diarylbibenzofuranone-Based Trigger-Free Dynamic Covalent Bonds at Room Temperature, Angewandte Chemie, 10.1002/anie.201104069, 50, 5, 1138-1142, 2012.01.
367.	Motoyasu Kobayashi, Koji Mitamura, Masami Terada, Moriya Kikuchi, Daiki Murakami, Hiroki Yamaguchi, Hiroshi Arita, Tatsuya Ishikawa, Yuki Terayama, Hiroe Soejima, Atsushi Takahara, Applications of Polymer Brushes to Structural Nano-Coatings, Proceeding of IEEE NMDC 2011, in press., 2012.01.
368.	K.Imato,. M. Nishihara, T. Kanehara, Y. Amamoto, A. Takahara, H. Otsuka, Self-Healing of Chemical Gels Cross-Linked by Diarylbibenzofuranone-Based Trigger-Free Dynamic Covalent Bonds at Room Temperature, Angew. Chemie in press., 10.1002/anie.201104069, 51, 5, 1138-1142, 2012.01.
369.	Moyotasu Kobayashi, Yuki Terayama, Tatsuya Ishikawa, Masami Terada, Hiroe Soejima, Daiki Murakami, Atsushi Takahara, Applications of surface initiated ATRP to the preparation of polyelectrolyte brushes for antifouling, adhesion control, friction control, Progress in Controlled Radical Polymerization: Materials and Applications, 10.1021/bk-2012-1101.ch012, 1101, 183-195, 2012, Polyelectrolytes show unique characteristics at aqueous interfaces. High-density hydrophilic polyelectrolyte brushes were prepared on Si-wafer and various substrates by surface-initiated controlled radical polymerization. Chain dimension at liquid/solid interface was characterized by neutron reflectivity. Applications of polymer brushes to super hydrophilic surface, antifouling surface, water lubrication layer and adhesion control layer are presented..
370.	Hui Wu, Zhaohui Su, Atsushi Takahara, Characterization of an isotactic polystyrene/poly(2,6-dimethylphenylene oxide) nanorod blend with gradient composition and crystallinity, RSC Advances, 10.1039/c2ra21570e, 2, 23, 8707-8712, 2012, Using a nanoporous alumina template, we prepared an isotactic polystyrene/poly(2,6-dimethylphenylene oxide) (iPS/PPO) nanorod blend with gradient composition and gradient crystallinity. The crystallinity, orientation and composition of the polymer in the nanorods were investigated by micro-FTIR spectroscopy. Although iPS and PPO are compatible at the molecular level, due to the viscosity difference between the two components, the polymer blend underwent phase separation during the capillary flow into the nanopores to form a gradient distributed composition in the nanorods. Along the growth direction (from the bottom to the top) of the nanorods, the iPS content increased, but the iPS crystallinity decreased due to crystallization initiated by the nuclei formed in the bulk and the constrained crystal growth. This finding provides a unique approach to the design and fabrication of novel nanomaterials with gradient properties in nanoscale engineering. This journal is.
371.	Motoyasu Kobayashi, Masami Terada, Atsushi Takahara, Friction control utilizing biomimetic polymer brush technology, Society of Tribologists and Lubrication Engineers Annual Meeting and Exhibition 2012 Society of Tribologists and Lubrication Engineers Annual Meeting and Exhibition 2012, 254-256, 2012, The environmentally friendly biomimetic lubrication system was designed by tethering poly electrolytes on the substrates with sufficiently high grafting density, so-called 'polymer brushes'. The hydrated brushes in aqueous media formed water lubrication layer to reduce friction coefficient, which is useful not only for artificial joints and bio-devices but also for various mechanical devices. Macroscopic tribological properties of polyelectrolyte brushes bearing ammonium salt, sulfonic acid, or phosphorylcholine unit were characterized by ball-on-plate type tribotester in the air, water, and salt solution through sliding a glass ball on the surface under a normal pressure of ca. 140MPa. The low friction coefficient below 0.02 was observed in polyelectrolyte brushes in water..
372.	Motoyasu Kobayashi, Masami Terada, Atsushi Takahara, Polyelectrolyte brushes A novel stable lubrication system in aqueous conditions, Faraday Discussions, 10.1039/c2fd00123c, 156, 403-412, 2012, Surface-initiated controlled radical copolymerizations of 2-dimethylaminoethyl methacrylate (DMAEMA), 2-(methacryloyloxy)ethyl phosphorylcholine (MPC), 2-(methacryloyloxy)ethyltrimethylammonium chloride) (MTAC), and 3-sulfopropyl methacrylate potassium salt (SPMK) were carried out on a silicon wafer and glass ball to prepare polyelectrolyte brushes with excellent water wettability. The frictional coefficient of the polymer brushes was recorded on a ball-on-plate type tribometer by linear reciprocating motion of the brush specimen at a selected velocity of 1.5 × 10^-3 m s^-1 under a normal load of 0.49 N applied to the stationary glass ball (d = 10 mm) at 298 K. The poly(DMAEMA-co-MPC) brush partially cross-linked by bis(2-iodoethoxy)ethane maintained a relatively low friction coefficient around 0.13 under humid air (RH > 75%) even after 200 friction cycles. The poly(SPMK) brush revealed an extremely low friction coefficient around 0.01 even after 450 friction cycles. We supposed that the abrasion of the brush was prevented owing to the good affinity of the poly(SPMK) brush for water forming a water lubrication layer, and electrostatic repulsive interactions among the brushes bearing sulfonic acid groups. Furthermore, the poly(SPMK-co-MTAC) brush with a chemically cross-linked structure showed a stable low friction coefficient in water even after 1400 friction cycles under a normal load of 139 MPa, indicating that the cross-linking structure improved the wear resistance of the brush layer..
373.	Yuji Higaki, Ryosuke Okazaki, Atsushi Takahara, Semirigid biobased polymer brush Poly(α-methylene-γ- butyrolactone) brushes, ACS Macro Letters, 10.1021/mz3002148, 1, 9, 1124-1127, 2012, High-density poly(α-methylene-γ-butyrolactone) (PMBL) brushes were produced by surface-initiated atom transfer radical polymerization of α-methylene-γ-butyrolactone (MBL), a biomass derived from tulips, on a silicon substrate. The relative elastic modulus was evaluated through force-curve measurements using a scanning force microscopy. The friction coefficient was measured using a macroscopic friction test. The PMBL brushes exhibit larger elastic modulus and better friction resistance than PMMA brushes as a result of the highly stretched conformation and polar interaction between PMBL chains..
374.	R. Li, S. Liu , J. Zhao H. Otsuka, A. Takahara, Preparation of superparamagnetic beta-cyclodextrin-functionalized composite nanoparticles with core-shell structures, Polym. Bull, 10.1007/s00289-010-0410-y, 66, 8, 1125-1136, 2011.11.
375.	Wei Ma, Hideyuki Otsuka, Atsushi Takahara, Preparation and properties of PVC/PMMA-g-imogolite nanohybrid via surface-initiated radical polymerization, Polymer, 10.1016/j.polymer.2011.09.054, 52, 24, 5543-5550, 2011.11.
376.	N. L. Yamada, N. Torikai, K. Mitamura, H. Sagehashi, S. Sato, H. Seto, T. Sugita, S. Goko, M. Furusaka, T. Oda, M. Hino, T. Fujiwara, H. Takahashi, A. Takahara, Design and Performance of Horizontal Type Neutron Reflectometer SOFIA at J-PARC/MLF, submitted to Euro. Phys. J. Plus., 10.1140/epjp/i2011-11108-7, 126, 11, 2011.11.
377.	M.Kobayashi, K. Mitamura, M. Terada, M. Kikuchi, D.Murakami,?Hiroki?Yamaguchi, H. Arita, T. Ishikawa, Y. Terayama, H. Soejima, and?A. Takahara, Applications of Polymer Brushes to?Structural Nano-Coatings, Proceeding of IEEE NMDC, 2011, 69-74, 2011.10.
378.	M, Kikuchi, Y. Terayama, T. Ishikawa, T. Hoshino,　M. Kobayashi, H. Ogawa, H. Masunaga,　J.-I. Koike, M. Horigome, K.Ishihara ,A. Takahara, Chain Dimension of Polyampholytes in Solution and Immobilized Brush States, Polym. J. in press., 10.1038/pj.2011.116, 44, 121-130, 2011.09.
379.	Takamichi Shinohara, Tomoko Shirahase, Daiki Murakami, Taiki Hoshino, Moriya Kikuchi, Jun-ichiro Koike, Misao Horigome, Hiroyasu Masunaga, Hiroki Ogawa, Atsushi Takahara, Characterization of Surface Microstructures on Bio-based Polymer Film Fabricated with Nano-imprint Lithography by Synchrotron Radiation Small Angle X-ray Scattering, Materials Science and Engineering, 10.1088/1757-899X/24/1/012004, 24, 12004, 2011.09.
380.	W.- O. Yah, A. Irie, N. Jiravanichanun, H.Otsuka, A. Takahara, Molecular Aggregation States of Terthiophene Derivatives on Aluminosilicate Nanofiber Imogolite: Novel Optical and Electrical Properties, Bull. Chem. Soc. Japan, 10.1246/bcsj.20110080, 84, 9, 893-902, 2011.09.
381.	Jing Su, Yoshifumi Amamoto, Masamichi Nishihara, Atsushi Takahara, Hideyuki Otsuka, Reversible cross-linking of hydrophilic dynamic covalent polymers with radically exchangeable alkoxyamines in aqueous media, Polymer Chemistry, 10.1039/c1py00176k, 2, 9, 2021-2026, 2011.09, Reversible cross-linking of alkoxyamine-containing hydrophilic dynamic covalent polymers in aqueous media has been accomplished. Water-soluble polymers with alkoxyamine units in the side chains were synthesized by radical copolymerization of 2-(dimethylamino)ethyl methacrylate and methacrylic esters with alkoxyamine units, and subsequent protonation of dimethylaminoethyl groups by hydrochloric acid. By heating the polymers in water at 100 °C in a closed system, hydrogels were formed by radical exchange reactions. Because the radical reactions are tolerant of water, the exchange reactions of alkoxyamine units in the side chain caused the cross-linking reaction even in aqueous media. Cross-linking behaviors depended on the amounts of alkoxyamine units in the polymers and the reaction concentrations. A de-cross-linking reaction was also accomplished by radical exchange reaction between the cross-linked polymer and added hydrophilic alkoxyamine compound. This dynamic cross-linking nature in aqueous media provides a foundation for a wide range of polymer reactions, and it can be applied to environmentally benign dynamic materials..
382.	H. Wu, Z. Su, A. Takahara, Molecular composition distribution of polycarbonate/polystyrene blends in cylindrical nanopores, Polymer Journal, 10.1038/pj.2011.25, 43, 600-605, 2011.07.
383.	Sehyun Kim, Jiseok Lee, Hoyun Kim, Youngwook P. Seo, Soon Man Hong, Atsushi Takahara, Hyoung Jin Choi, Yongsok Seo, Enhanced Interfacial Adhesion between an Amorphous Polymer (Polystyrene) and a Semicrystalline Polymer [a Polyamide (Nylon 6)], ACS Appl. Mater. Interfaces, 10.1021/am200435w, 3, 7, 2622-2629, 2011.07.
384.	H. Watanabe, A. Fujimoto, A. Takahara, Manipulation of surface properties: the use of nanomembrane as a nanometer-thick decal, Soft Matter, 10.1039/C0SM01105C, 7, 471-477, 2011.07.
385.	H. Wu, Z.-H. Su, A. Takahara, 'Gradient Composition Distribution in Poly(2,6-dimethylphenylene oxide)/Polystyrene Blend Nanorods, Soft Matter, 10.1039/C0SM00968G, 7, 5, 1868-1873, 2011.07.
386.	Takahiro Yano, Weng-on Yah, Hiroki Yamaguchi, Yuki Terayama, Masamichi Nishihara, Motoyasu Kobayashi, Atsushi Takahara, Precise Control of Surface Physicochemical Properties for Electrospun Fiber Mats by Surface-Initiated Radical Polymerization, Polymer Journal, 10.1038/pj.2011.80, 43, 838-848, 2011.06.
387.	T.Koga, P. Gin, H. Yamaguchi, M. K. Endoh, M. Asada, L. Sendogdular, M. Kobayashi, A. Takahara, B. Akgun, S. K. Satija, T. Sumi, Generality of Anomalous Expansion of Polymer Chains in Supercritical Fluids, Polymer, 10.1016/j.polymer.2011.07.039, 52, 4331-4336, 2011.06.
388.	Motoyasu Kobayashi, Masami Terada, Atsushi Takahara, Reversible adhesive-free nanoscale adhesion utilizing oppositely charged polyelectrolyte brushes, Soft Matter, 10.1039/c1sm05132f, 7, 12, 5717-5722, 2011.06, Two prepared silicon wafers bearing cationic and anionic polyelectrolyte brushes were joined with 2 μL of water under 0.098 MPa of pressure at room temperature. The bonded area was fixed at 5 × 10 mm². A lap shear strength of 1.52 MPa was achieved through the adhesion of poly[2-(methacryloyloxy)ethyl trimethylammonium chloride] and poly(3-sulfopropyl methacrylate potassium salt) brush substrates due to electrostatic attractive interactions between the positively and negatively charged polymers. In contrast, the lap shear strength of bonded polymer brushes with like charges was only 0.027-0.072 MPa. The polyelectrolyte brushes remained on the substrates even after their separation in the lap shear test; and the brush substrates readhered in the presence of a small amount of water. Furthermore, the adhering substrates were smoothly debonded in aqueous NaCl solution due to the electrostatic interaction of the hydrated salt ions. However, the substrates did not separate in deionized water. In summary, reversible nanoscale adhesion was achieved using oppositely charged polyelectrolyte brushes combined with aqueous solution..
389.	Jing Su, Yoshifumi Amamoto, Masamichi Nishihara, Atsushi Takahara, Hideyuki Otsuka, Reversible cross-linking of hydrophilic dynamic covalent polymers with radically exchangeable alkoxyamines in aqueous media, Polym. Chem., 10.1039/C1PY00176K, 2, 2021-2026, 2011.05.
390.	Hiroyasu masunaga, Hiroki Ogawa, Takumi Takano, Sono Sasaki, Shunji Goto, Takashi Tanaka, Takamitsu Seike, Sunao Takahashi, Kunikazu Takeshita, Nobuteru Nariyama, Haruhiko Ohashi, Toru Ohata, Yukito Furukawa, Tomohiro Matsushita, Yasuhide Ishizawa, Naoto Yagi, Masaki Takata, Hideo Kitamura, Kazuo Sakurai, Kohji Tashiro, Atsushi Takahara, Yoshiyuki Amamiya, Kazuyuki Horie, Mikihito Takenaka, Toshiji Kanaya, Hiroshi Jinnnai, Hiroshi Okuda, Isamu Akiba, Isao Takahashi, Katsuhiro Yamamoto, Masamichi Hikosaka, Shinichi Sakurai, Yuya Shinohara, Akihiko Okada, Yasunori Sugihara, Multipurpose soft-material SAXS/WAXS/GISAXS beamline at Spring-8, Polymer Jounal, 10.1038/pj.2011.18, 43, 471-477, 2011.05.
391.	Calleja Gerard, Houdayer Axel, Etienne-calas Sylvie, Bourgogne David, Flaud Valerie, Silly Gilles, Shibahara Sota, Takahara Atsushi, Jourdan Alex, Hamwi Andre, Conversion of poly (ethylene-alt-tetrafluoroethylene) copolymers into polytetrafluoroethylene by direct fluorination: A convenient approach to access new properties at the ETFE surface, Journal of Polymer Science, Part A: Polymer Chemistry, 10.1002/pola.24588, 49, 7, 1517-1527, 2011.04.
392.	Y. Terayama, M. Kikuchi, K. Mitamura, N.-L. Yamada, M. Kobayashi,A. Takahara, Salt Concentration Dependence of Swelling States for Poly(sulfobetaine) Brush at Aqueous Solution Interface, ACS Symposium Series, 10.1021/bk-2011-1070.ch009, 1070 "Amphiphiles: Molecular Assembly and Applications, Chapter 9, 5543-5550, 2011.04.
393.	M. Kobayashi, M. Terada, A. Takahara, Reversible Adhesive-free Nanoscale Adhesion Utilizing Oppositely Charged Polyelectrolyte Brushes, Soft Matter, 10.1039/C1SM05132F, 7, 230-236, 2011.03.
394.	W. Ma, H. Otsuka, A. Takahara, Poly(methyl methacrylate) Grafted Imogolite Nanotubes Prepared through Surface-Initiated ARGET ATRP, Chem. Comm., 10.1039/C1CC10661A, 47, 20, 5813-5815, 2011.03.
395.	Hui Wu, Zhaohui Su, Atsushi Takahara, Gradient composition distribution in poly(2,6-dimethylphenylene oxide)/polystyrene blend nanorods, Soft Matter, 10.1039/c0sm00968g, 7, 5, 1868-1873, 2011.03, We report formation of nanorods that exhibit a gradient distribution of poly(2,6-dimethylphenylene oxide) and polystyrene (PPO and PS), i.e., the PPO weight fractions in the nanorods increase from top to bottom along the long axis of the nanorods. PPO/PS nanorods with various diameters were prepared by infiltrating porous anodic aluminium oxide (AAO) templates with polymer blend melts. Their morphology was investigated by Fourier transform infrared spectroscopy (FTIR). The gradient distribution of polymer blends in the nanopores is governed by (1) the viscosity difference between the two polymers and (2) the pore diameter. This remains true although PPO/PS blends are compatible in the segmental level. For various diameter nanorods made of PPO/PS blends, the PPO content decreased as the rod diameter became smaller owing to the increased confinement imposed by the nanopores. This leads to a higher rate of capillary rise in smaller nanopores..
396.	Hirohmi Watanabe, Aya Fujimoto, Atsushi Takahara, Manipulation of surface properties The use of nanomembrane as a nanometre-thick decal, Soft Matter, 10.1039/c0sm01105c, 7, 5, 1856-1860, 2011.03, Precise control of surfaces and interfaces is essential for the fabrication of various functional materials. Although various methods have been applied to the functionalization of surfaces, these methods are specialized for the fabrication of specific surfaces for specific purpose. In this context, a versatile, yet efficient tool for the surface manipulation is strongly desired. Here, we demonstrate a simple method of functionalizing various surfaces through a decal-like transfer of a giant nanomembrane. Control of wettability was chosen as an example, and a hydrophobic nanomembrane was transferred to various other substrates, including Si, polymer film, and metal. A drastic change in contact angle clearly indicated that the wettability of the processed material was identical to that of the surface-functionalized nanomembrane. In contrast, other physical properties such as the mechanical properties of the processed material remain unchanged. The decal-like transfer of nanomembrane will become a powerful means for the fabrication of unique functional surfaces..
397.	Yoshifumi Amamoto, Jun Kamada, Hideyuki Otsuka, Atsushi Takahara, Krzysztof Matyjaszewski, Repeatable Photoinduced Self-Healing of Covalently Cross-Linked Polymers through Reshuffling of Trithiocarbonate Units, Angwandte Chemie, Int. Ed., 10.1002/anie.201003888, 50, 838-848, 2011.02.
398.	Yoshifumi Amamoto, Moriya Kikuchi, Hiroyasu Masunaga, Hiroki Ogawa, Sono Sasaki, Hideyuki Otsuka，Atsushi Takahara, Mesh-Size Control and Functionalization of Reorganizable Chemical Gels by Monomer Insertion into Their Cross-Linking Points, Polymer Chemistry, 10.1039/C0PY00304B, 2, 4331-4336, 2011.02.
399.	N. Morishige, Y.Takagi, T. Chikama, A. Takahara, T. Nishida, Three-Dimensional Analysis of　Collagen Lamellae in the Anterior Stroma of the Human Cornea Visualized by Second Harmonic Generation Imaging Microscopy", Investigative Ophthalmology and Visual Science, 10.1167/iovs.10-5657, 52, 911-915, 2011.02.
400.	Motoyasu Kobayashi, Koji Mitamura, Masami Terada, Norifumi L. Yamada, Atsushi Takahara, Characterization of Swollen States of Polyelectrolyte Brushes in Salt Solution by Neutron Reflectivity, Jounal of Physics ：Conference series, 10.1088/1742-6596/272/1/012019, 272, 12019, 2011.02.
401.	Koji Mitamura, Norifumi L. Yamada, Hidenori Sagehashi, Hideki Seto, Naoya Torikai, Tsukasa Sugita, Michihiro Furusaka, Atsushi Takahara, Advanced Neutron Reflectometer for Investigation on Dynamic/Static Structure of Soft-Interface in J-PARC, Jounal of Physics ：Conference series, 10.1088/1742-6596/272/1/012017, 272, 12017, 2011.02.
402.	Moriya Kikuchi, Yuki Terayama, Taiki Hoshino, Motoyasu Kobayashi, Hiroki Ogawa, Hiroyasu Masunaga, Atsushi Takahara, Static and Dynamic Scattering from Polysulfobetaine Immobilized on Silica Nanoparticle in Ionic Liquid, Jounal of Physics ：Conference series, 10.1088/1742-6596/272/1/012016, 272, 12016, 2011.02.
403.	Weng On Yah, Atsushi Irie, Hideyuki Otsuka, Sono Sasaki, Naoto Yagi, Masugu Sato, Tomoyuki Koganezawa, Atsushi Takahara, Molecular Aggregation States of Imogolite/P3HT Nanofiber Hybrid, Journal of Physics: Conference Series, 10.1088/1742-6596/272/1/012021, 272, 12021, 2011.02.
404.	Taiki Hoshino, Moriya Kikuchi, Daiki Murakami, Koji Mitamura, Yoshiko Harada, Kiminori Ito, Yoshihito Tanaka, Sono Sasaki, Masaki Tanaka, Atsushi Takahara, X-ray Photon Correlation Spectroscopy of Silica Particles Grafted with Polymer Brush in Polystyrene Matrix, Journal of Physics: Conference Series, 10.1088/1742-6596/272/1/012020, 272, 12020, 2011.02.
405.	Daisuke Matsukuma, Hirohmi Watanabe, Hiroki Yamaguchi, Atsushi Takahara, Preparation of Low-Surface-Energy Poly(2-(perfluorooctyl)ethyl acrylate) Microparticles and Its Application to Liquid Marble Formation, Langmuir, 10.1021/la.1040689, 27, 4, 1269-1274, 2011.02.
406.	Y Terayama, H Arita, T Ishikawa, M Kikuchi, K Mitamura, M Kobayashi, N L Yamada and A Takahara, Chain dimensions in free and immobilized brush states of polysulfobetaine in aqueous solution at various salt concentrations, Journal of Physics: Conference Series 272, 10.1088/1742-6596/272/1/012010, 272, 1, 2011.02.
407.	Yoshifumi Amamoto, Moriya Kikuchi, Hiroyasu Masunaga, Hiroki Ogawa, Sono Sasaki, Hideyuki Otsuka, Atsushi Takahara, Mesh-size control and functionalization of reorganizable chemical gels by monomer insertion into their cross-linking points, Polymer Chemistry, 10.1039/c0py00304b, 2, 4, 957-962, 2011.02.
408.	Daisuke Matsukuma, Hirohmi Watanabe, Hiroki Yamaguchi, Atsushi Takahara, Preparation of low-surface-energy poly[2-(perfluorooctyl)ethyl acrylate] microparticles and its application to liquid marble formation†, Langmuir, 10.1021/la1040689, 27, 4, 1269-1274, 2011.02, We demonstrate the successful preparation of stable liquid marbles from various liquids. This is accomplished by using low-surface-energy poly[2-(perfluorooctyl)ethyl acrylate] (PFA-C₈) as microparticles. The PFA-C₈ microparticles were prepared by the spontaneous self-organized microparticulation of PFA-C₈. The physical properties remained intact in the polymer morphologyas confirmed bywide-angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC) measurements. The extremely low surface energyof PFA-C₈ providesahigh solid-liquid spreading coefficient (S_S/L) value for various combinations of liquids. As a result, liquid marbles were obtained from various liquids, unlike the case with other fluorine polymer particles such as poly(tetrafluoroethylene) (PTFE) and poly(vinilydene fluoride) (PVDF). These results suggest that the technique is widely applicable for preparing novel functional materials..
409.	W. Ma, H.Otsuka, A. Takahara, Fabrication of poly(methyl methacrylate) grafted imogolite clay nanotubes and their application to poly(vinyl chloride)-based nanohybrid　Polymer, Polymer in press, 2011.01.
410.	Y Terayama, H Arita, T Ishikawa, M Kikuchi, K Mitamura, M Kobayashi, N L Yamada and A Takahara, Chain dimensions in free and immobilized brush states of polysulfobetaine in aqueous solution at various salt concentrations, J. Phys. Conf. Ser., 10.1088/1742-6596/272/1/012010, 272, 5717-5722, 2011.01.
411.	Y. Terayama, M. Kikuchi, M. Kobayashi, A. Takahara, Well-Defined Poly(sulfobetaine) Brushes Prepared by Surface-Initiated ATRP Using a Fluoroalcohol and Ionic Liquids as the Solvents, Macromolecule, 10.1021/ma102223y, 44, 135-143, 2011.01.
412.	Yuki Terayama, Moriya Kikuchi, Motoyasu Kobayashi, and Atsushi Takahara, Well-Defined Poly(sulfobetaine) Brushes Prepared by Surface-Initiated ATRP Using a Fluoroalcohol and Ionic Liquids as the Solvent, Macromolecules, 10.1021/ma102223y, 44, 1, 104-111, 2011.01.
413.	Motoyasu Kobayashi, Koji Mitamura, Masami Terada, Moriya Kikuchi, Daiki Murakami, Hiroki Yamaguchi, Hiroshi Arita, Tatsuya Ishikawa, Yuki Terayama, Hiroe Soejima, Atsushi Takahara, Applications of polymer brushes to structural nano-coatings, 2011 IEEE Nanotechnology Materials and Devices Conference, NMDC 2011 2011 IEEE Nanotechnology Materials and Devices Conference, NMDC 2011, 10.1109/NMDC.2011.6155315, 69-74, 2011, Hydrophilic polymers show unique characteristics at various interfaces. High-density hydrophilic polymer brushes nano-coatings were prepared on Si-wafer and various substrates by surface-initiated controlled radical polymerization. Chain conformation at liquid/solid liquid/solid interface was characterized by neutron reflectivity. Applications of polymer brushes as structural nano-coatings such as super hydrophilicity, antifouling behavior, low friction behavior, and intelligent adhesion are presented..
414.	Kazuo Sakurai, Atsushi Takahara, Journal of Physics Conference Series: Preface, Journal of Physics: Conference Series, 10.1088/1742-6596/272/1/011001, 272, 1, 2011.
415.	Jihun Kim, Soonjong Kwak, Soon Man Hong, Jae Rock Lee, Atsushi Takahara, Yongsok Seo, Nonisothermal crystallization behaviors of nanocomposites prepared by in situ polymerization of high-density polyethylene on multiwalled carbon nanotubes, Macromolecules, 10.1021/ma102036h, 43, 24, 10545-10553, 2010.12, Thermal properties and nonisothermal crystallization kinetics of polyolefin nanocomposites (high-density polyethylene/multiwalled carbon nanotubes) were characterized by differential scanning calorimetry and thermogravimetric analysis. In situ metallocence polymerization was used to prepare nanocomposites of multiwalled carbon nanotubes (MWCNTs) and high-density polyethylene (HDPE). This polymerization method consists of attaching a metallocene catalyst complex onto the surface of the MWCNTs followed by surface-initiated polymerization to generate polymer brushes on the surface. A kinetic equation for the nonisothermal crystallization was employed to analyze the crystallization characteristics of the nanocomposites. The Avramic exponent, n, can be reasonably well determined from the nonisothermal crystallization exotherm. The polarized optical microscopy showed that neat polyethylene possessed a well-developed spherulite morphology, whereas the nanocomposites displayed elongated entities that subsequently developed as bundlelike entities. Nonisothermal analysis implicitly provides clues about the morphological development history and HDPE molecular ordering around the carbon nanotubes..
416.	Yoshifumi Amamoto,Moriya Kikuchi,Hideyuki Otsuka and Atsushi Takahara, Arm-replaceable star-like nanogels: arm detachment and arm exchange reaction by dynamic covalent exchanges of alkoxyamine units, Polymer Journal, 10.1038/pj.2010.83, 42, 11, 860-867, 2010.11.
417.	Tomoya Sato,Yoshifumi Amamoto,Hiroki Yamaguchi,Hideyuki Otsuka,and Atsushi Takahara, "Substitutable" Polymer Brushes:Reactive Poly(methacrylate)Brushies with Exchangeable Alkoxyamine Units in the Side Chain, Chemistry Letters, 10.1246/cl.2010.1209, 39, 11, 1209-1211, 2010.11.
418.	Reddy Thatiparti Thimma,Kano Arihiro,Maruyama Atsushi,Takahara Atsushi, Synthesis, Characterization and Drug Release of Biocompatible/Biodegradable Non-toxic Poly(urethane urea)s Based on Poly(ε-caprolactone)s and Lysine-Based Diisocyanate, Journal of Biomaterials Science, Polymer Edition, 10.1163/092050609X12518804794785, 21, 11, 1483-1502, 2010.11.
419.	Takahiro Yano, Weng On Yah, Hiroki Yamaguchi, Yuki Terayama, Masamichi Nishihara, Motoyasu Kobayashi, Atsushi Takahara, Preparation anda Surface characterization of Surface-Modified Electrospun Poly(methylmethacrylate) Copolymer Nanofibers, Chemistry Letters, 10.1246/cl.2010.1110, 39, 10, 1110-1111, 2010.10.
420.	Motoyasu Kobayashi, Masami Terada, Yuki Terayama, Moriya Kikuchi, Atsushi Takahara, Direct synthesis of well-defined poly[{2-(methacryloyloxy)ethyl} trimethylammonium chloride] brush via surface-initiated atom transfer radical polymerization in fluoroalcohol, Macromolecules, 10.1021/ma1014897, 43, 20, 8409-8415, 2010.10, A well-defined cationic polymer and polymer brush were simultaneously prepared by copper-catalyzed atom transfer radical polymerization (ATRP) of 2-(methacryloxy)ethyltrimethylammonium chloride (MTAC) in 2,2,2-trifluoroethanol (TFE) at 60 °C initiated with ethyl 2-bromoisobutylate and the corresponding alkylbromide immobilized on silicon wafer. ATRP of MTAC in TFE as well as aqueous solution proceeded quickly but in a poorly controlled manner, leading to a relatively higher molecular weight distribution (MWD) than M _w/M_n = 1.3, where M_w and M_n are weight-average and number-average molecular weights, respectively. Addition of a small amount of isopropyl alcohol to the TFE-based reaction mixture reduced the polymerization rate and produced a poly(MTAC) with predictable molecular weight and narrower MWD than 1.19. The M_n of poly(MTAC) was controllable in the range 10⁴-10⁵ g mol^-1 based on the molar ratio of monomer and initiator in the feed. The M_n of the brush on a flat silicon wafer matched that of the free poly(MTAC). The graft density of poly(MTAC) was 0.20 chains nm^-2. The ATRP of MTAC in TFE/1-ethyl-3-methylimidazolium chloride (EMImCl) also proceeded in a controlled manner at 60 °C, yielding polymers with narrow MWDs (M_w/M _n = 1.12-1.13). Analysis of the ¹³C NMR spectra of the carbonyl region of the resulting poly(MTAC)s revealed that syndiotactic-rich configurations were produced by ATRP of MTAC in aqueous solution, TFE/isopropyl alcohol, and TFE/EMImCl. The solvent effect of TFE and ionic liquid on the tacticity of polymer was negligible..
421.	Motoyasu Kobayashi,Masami Terada,Yuki Terayama,Moriya Kikuchi,and Atsushi Takahara, Direct Synthesis of Well-Defined Poly[{2-(methacryloyloxy)ethyl}trimethylammonium chloride]Brush via Surface-Initiated Atom Transfer Radical Polymerization in Fluoroalcohol, Macromolecules, 10.1016/j.apsusc.2010.07.093, 257, 13, 1145-1148, 2010.09.
422.	Ifu Narayama,Daisuke Baba,Atsushi Takahara,Keiji Tanaka, Direct observation of surface and internal phase-separated structure of the active layer buried in organic photovoltaic cells, Applied Surface Science, 1900年9月, 1900年1月, 1145-1148, 2010.08.
423.	Motoyasu Kobayashi,?Atsushi Takahara, Tribological properties of hydrophilic polymer brushes under wet conditions, THE CHEMICAL RECORD, 10.1002/tcr.201000001, 10, 4, 208-216, 2010.08.
424.	Y. Amamoto, M. Kikuchi, H. Otsuka and A. Takahara, Solvent-Controlled Formation of Star-like Nanogels via Dynamic Covalent Exchange of PSt-b-PMMA Diblock Copolymers with Alkoxyamine Units in the Side Chain, Macromolecules, 10.1021/ma100276n, 43, 12, 5470-5473, 2010.06.
425.	Takashi Iwamoto, Yuki Komorida, Masaki Mito, Atsushi Takahara, Chemical and physical characterizations of spinel ferrite nanoparticles containing Nd and B elements, Journal of Colloid and Interface Science, 10.1016/j.jcis.2010.01.077, 345, 2, 143-148, 2010.05.
426.	Thimma Reddy Thatiparti, Arihiro Kano, Atsushi Maruyama, Atsushi Takahara, Novel Silver-Loaded Semi-Interpenetrating Polymer Network Gel Films with Antibacterial Activity, Polymer Chemistry, 10.1002/pola.23546, 47, 19, 4950-4962, 2010.05.
427.	Hideyuki Otsuka, Takatoshi Muta, Masahide Sakada, Takeshi Maeda, Atsushi Takahara, Scrambling reaction between polymers prepared by step-growth and chain-growth polymerizations: macromolecular cross-metathesis between 1,4-polybutadiene and olefin-containing polyester, Chem.Commun., 10.1039/b818014h, 9, 1073-1075, 2010.05.
428.	Tatsuya Ishikawa, Motoyasu Kobayashi, Atsushi Takahara, Macroscopic Frictional Properties of Poly(1-(2-methacryloyloxy)ethyl-3-butyl Imidazolium Bis(trifluoromethanesulfonyl)-imide) Brush Surfaces in an Ionic Liquid, ACS Appl. Mater. Interfaces, 10.1021/am9009082, 2, 4, 1120-1128, 2010.04.
429.	Ruixue Li, Shumei Liu, Jianqing Zhao, Otsuka Hideyuki, Atsushi Takahara, Application of polymerizable surfactant in the preparation of polystyrene/nano-Fe₃O₄ composite, Journal Wuhan University of Technology, Materials Science Edition, 10.1007/s11595-010-2184-3, 25, 2, 184-187, 2010.04, Monooctadecyl maleate, as a polymerizable surfactant, was synthesized by the mono-esterification of maleic anhydride and octadecanol, and was utilized to surface-modify nano- Fe₃O₄ particles. A polymerizable magnetic fluid was obtained by directly dispersing modified nano-Fe3O4 particles into styrene monomer, and the polystyrene/nano- Fe₃O₄ composite was prepared through free radical polymerization of polymerizable magnetic fluid. The structure and dispersion status in different dispersion phases of modified nano- Fe₃O₄ particles were studied by Fourier transform infrared (FTIR) spectrometry, X-ray diffraction (XRD) and transmission electron microscopy (TEM), respectively. The experimental results show that the nano- Fe₃O₄ particles modified by monooctadecyl maleate with the size of about 7-10 nm can be uniformly dispersed into styrene and fixed in the composite during the procedure of polymerization. Thermogravimetric analysis (TGA) and vibrating sample magnetometry (VSM) indicate that the thermal stability of polystyrene/nano- Fe₃O ₄ composite is improved compared to that of pure polystyrene, and the composite is a sort of superparamagnetic materials..
430.	Weng On Yah,Kazuya Yamamoto,Nattha Jiravanichanun,Hideyuki Otsuka,Atsushi Takahara, Imogolite Reinforced Nanocomposites: Multifaceted Green Materials, Materials, 10.3390/ma3031709, 3, 3, 1746-1767, 2010.03.
431.	T. Miyayama,N. Sanada,M. Suzuki,J. S. Hammond,S.-Q. D. Si,A. Takahara, X-ray photoelectron spectroscopy study of polyimide thin films with Ar cluster ion depth profiling, Journal of Vacuum Science & Technology, 10.1116/1.3336242, 28, 2, L1-L4, 2010.03.
432.	Hideyuki Otsuka, Shinsuke Nagano, Yasuharu Kobashi, Takeshi Maeda, Atsushi Takahara, A dynamic covalent polymer driven by disulfide metathesis under photoirradiation, Chemical Communications, 10.1039/B916128G, 46, 7, 1150-1152, 2010.03.
433.	Hideaki Yukutake, Motoyasu Kobayashi, Hideyuki Otsuka, Atsushi Takahara, Influence of magadiite dispersion states on the flammability of polystyrene and polyphenylene ether-polystyrene alloy nanocomposites, Polymer Journal, 10.1038/pj.2009.336, 42, 3, 223-231, 2010.03.
434.	Koji Honda, Masamichi Morita, Hiroyasu Masunaga, Sono Sasaki, Masaki Tanaka, Atsushi Takahara, Room-temperature nanoimprint lithography for crystalline poly(fluoroalkylacrylate) thin films, Soft Matter, 10.1039/B918316G, 6, 5, 870-875, 2010.03.
435.	Y. Amamoto, M. Kikuchi, H. Masunaga, S. Sasaki, H. Otsuka and A. Takahara, Intelligent Build-Up of Complementarily Reactive Diblock Copolymers via Dynamic Covalent Exchange toward Symmetrical and Miktoarm Star-like Nanogels, Macromolecules, 10.1021/ma902413f, 43, 4, 1785-1791, 2010.02.
436.	K. Honda, M. Morita, O. Sakata, S. Sasaki and A. Takahara, Effect of Surface Molecular Aggregation State and Surface Molecular Motion on Wetting Behavior of Water on Poly(fluoroalkyl methacrylate) Thin Films, Macromolecules, 10.1021/ma901973t, 43, 1, 454-460, 2010.01.
437.	Hideyuki Otsuka, Shinsuke Nagano, Yasuharu Kobashi, Takeshi Maeda, Atsushi Takahara, A dynamic covalent polymer driven by disulfide metathesis under photoirradiation, Chemical Communications, 10.1039/b916128g, 46, 7, 1150-1152, 2010, A disulfide-containing polyester indicates a dynamic nature in a bulk state based on a disulfide metathesis reaction driven by photoirradiation..
438.	Koji Honda, Masamichi Morita, Hiroyasu Masunaga, Sono Sasaki, Masaki Takata, Atsushi Takahara, Room-temperature nanoimprint lithography for crystalline poly(fluoroalkyl acrylate) thin films, Soft Matter, 10.1039/b918316g, 6, 5, 870-875, 2010, A mold with a line pattern was imprinted onto a thin film of poly{2-(perfluorooctyl)ethyl acrylate} with long crystalline fluoroalkyl groups (PFA-C₈), and the nanoimprinting characteristics of PFA-C₈ thin films were investigated. It was revealed that nanostructures could be imprinted on PFA-C₈ at room temperature because of the weak interaction among the fluoroalkyl groups in crystallites. The nanotextured PFA-C₈ film with a line pattern exhibited anisotropic wetting behavior. The anisotropic wetting behavior was attributed to the difference between the energy barriers of wetting in the direction parallel and orthogonal to the lines. Fabricated nanostructures were stable for annealing below its melting point and were stable at room temperature (RT) for several months..
439.	Hideyuki Otsuka, Atsushi Takahara, Structure and Properties of Imogolite Nanotubes and Their Application to Polymer Nanocomposites, Inorganic and Metallic Nanotubular Materials: Recent Technologies and Applicatons, 10.1007/978-3-642-03622-4_13, 117, 169-190, 2010, Imogolite is a hydrous aluminosilicate nanofiber with the general formula of [SiO₂ · Al₂O₃ · 2H₂O]. It forms a hollow nanotube with an external diameter of ca. 2.5 nm, an internal diameter of less than 1 nm, and lengths ranging from several hundred nanometers to several micrometers. This chapter describes the synthesis and properties of imogolite, along with its application to nanohybrids with polymers..
440.	Takeshi Maeda, Hideyuki Otsuka, Atsushi Takahara, Dynamic Combinatorial Methods in Materials Science, Dynamic Combinatorial Chemistry: In Drug Discovery, Bioorganic Chemistry, and Materials Science, 10.1002/9780470551554.ch8, 229-260, 2009.12.
441.	Atsushi Takahara, Dynamic viscoelastic properties-from bulk to surface of polymeric solods, Sen'i Gakkaishi, 65, 12, 2009.12.
442.	Jinwoo Kim, Junmo Koo, Tomoko Shirahase, Atsushi Takahara, Daewon Sohn, Preparation of Organic/Inorganic Hybrid Gel after γ-Ray Radiation, Chemistry Letters, 10.1246/cl.2009.1112, 38, 11, 1112-1113, 2009.10.
443.	Yoshifumi Amamoto, Moriya Kikuchi, Hiroyasu Masunaga, Sono Sasaki, Hideyuki Otsuka, Atsushi Takahara, Reorganizable Chemical Polymer Gels Based on Dynamic Covalent Exchange and Controlled Monomer Insertion, Macromolecules, 10.1021/ma901746n, 42, 22, 87338738, 2009.10.
444.	K. Honda, H. Yamaguchi, O. Sasaki, M Takata, M. Morita, A. Takahara, Influence of -methyl group on molecular aggregation structure and surface physicochemical properties of fluoroalkyl side chain polymers, Journal of Physics:Conference Series, 10.1088/1742-6596/184/1/012007, 184, 12007, 2009.08.
445.	Motoyasu Kobayashi, Yuki Terayama, Masahiro Hino, Kazuhiko Ishihara, Atsushi Takahara, Characterization of Swollen Structure of High-density Polyelectrolyte Brushes in Salt Solution by Neutron Reflectivity, Journal of Physics:Conference Series, 10.1088/1742-6596/184/1/012010, 184, 12010, 2009.08.
446.	H. Yamaguchi, K. Honda, M. Kobayashi, M. Morita, H. Masunaga, O.Sakata, S. Sasaki, M. Takata, A. Takahara, Molecular Aggregation States of Poly {2-(perfluorooctyl)ethyl acrylate} Polymer Brush Thin Film Analyzed by Grazing Incidence X-ray Diffraction, Journal of Physics:Conference Series, 10.1088/1742-6596/184/1/012009, 184, 12009, 2009.08.
447.	Yuki Terayama, Moriya Kikuchi, Motoyasu Kobayashi, Masahiro Hino, Atsushi Takahara, Influence of Salt Concentration on Swelling States of Poly(sulfobetaine) Brush at Aqueous Solution Interface, Journal of Physics:Conference Series, 10.1088/1742-6596/184/1/012011, 184, 12011, 2009.08.
448.	S. Sasaki, H. Masunaga, K. Itou, K .Tashiro, H. Okuda, A. Takahara, M. Takata, Crystallization Behavior of Polyethylene on Silicon Wafers in Solution Casting Processes Traced by Time-resolved Measurements of Synchrotron Grazing-Incidence Small-angle and Wide-angle X-ray Scattering, Journal of Physics:Conference Series, 10.1088/1742-6596/184/1/012015, 184, 12015, 2009.08.
449.	Y Amamoto, H Otsuka, A Takahara, Formation of Polystyrene/Poly(methyl methacrylate) Heteroarm Star-Like Nanogels from Complementarily Reactive Well-Defined Diblock Copolymers, Journal of Physics:Conference Series, 10.1088/1742-6596/184/1/012019, 184, 12019, 2009.08, [URL].
450.	Moriya Kikuchi, Motoyasu Kobayashi, Akihiro Tanaka, Atsushi Takahara, Chain dimension of polystyrene-like hyperbranched polymers with various chain end groups in THF, Journal of Physics:Conference Series, 10.1088/1742-6596/184/1/012033, 184, 12033, 2009.08.
451.	Hideyuki Otsuka, Yoshifumi Amamoto, Yasuhiro Matsuda, Takeshi Maeda, Atsushi Takahara, Synthesis and reaction of well-defined copolymers with thermally exchangeable dynamic covalent bonds in the side chains, ACS Symposium Series, 10.1021/bk-2009-1024.ch021, 1024, 319-329, 2009.08, Synthesis of well-defined linear copolymers with thermally exchangeable dynamic covalent bonds in their side chains and their structural interconversion system were demonstrated. The well-defined linear polymers with alkoxyamine moieties in their side chains were successfully prepared by the atom transfer radical polymerization (ATRP) method by tuning the reaction conditions. Random copolymer was successfully converted into macroscopic gel due to the cross-linking reaction between complementarily-reactive alkoxyamine units. From the results of gel permeation chromatography - multi-angle laser light scattering (GPC-MALLS) and small angle X-ray scattering (SAXS) measurements, it was made clear that the star-like nanogels are formed as the most stable structure in the diblock copolymer system. The molecular weights of the nanogels at equilibrium are clearly controlled by initial concentrations as well as the composition and molecular weights of the diblock copolymers. The structures of the nanogels were observed by scanning force microscopy (SFM) observation, which revealed that nanogels consisted of both a gel part and branching molecular chains. By controlling the stoichiometric ratio of added alkoxyamine, structural conversion from nanogels to diblock copolymer also proceeded, as the structures of the compounds depend on the equilibrium state..
452.	Zhe Wang,Xinhong Yu,Rubo Xing,Yanchun,Atsushi Takahara, Micropatterning of polymeric semiconductor by selective lift-off method using epoxy mold, J. Vac. Sci. Technol. B, 10.1116/1.3167372, 27, 4, 1958-1962, 2009.07.
453.	Weng On Yah, Zhe Wang, Hideyuki Otsuka, Kenichi Kato, Jungeun Kim, Masaki Takata, Atsushi Takahara, Molecular Aggregation State and Photovoltaic Properties of Chlorophyll-Doped Conducting Poly(3-hexylthiophene)/MCM-41 Nanocomposites, APPLIED MATERIALS&INTERFACES, 10.1021/am9002099, 1, 7, 15441552, 2009.07.
454.	T. Thimma Reddy, Atsushi Takahara, Simultaneous and sequential micro-porous semi-interpenetrating polymer network hydrogel films for drug delivery and wound dressing applications, Polymer, 10.1016/j.polymer.2009.05.062, 50, 15, 3537-3546, 2009.07.
455.	Takeshi Maeda, Hideyuki Otsuka, Atsushi Takahara, Dynamic covalent polymers Reorganizable polymers with dynamic covalent bonds, Progress in Polymer Science, 10.1016/j.progpolymsci.2009.03.001, 34, 7, 581-604, 2009.07, The recent research on dynamic covalent polymers is reviewed. These polymers exhibit dynamic features originating in the reversibility of dynamic covalent bonds. The main body of the review is presented in four sections: (i) utilization of dynamic covalent bonds in reactive polymer blends, (ii) ring-chain equilibrium based on dynamic covalent bonds, (iii) reorganizable polymers and polymeric systems with dynamic covalent bonds, and (iv) dynamic smart polymer materials. Unlike conventional polymers that are irreversibly formed, dynamic covalent polymers can reform their structures and constitutions under appropriate conditions, even after polymerization. Utilization of dynamic covalent bonds is seen in research concerning polymerization controls and polymer blends. In addition, reorganizable macromolecules specially programmed to exhibit dynamic features have recently been highlighted in line with increased understanding of dynamic phenomena through reversible formation of non-covalent bonds. They include various dynamic covalent bonds typified by C{double bond, long}N bonds in imine derivatives and C{single bond}O bonds in alkoxyamine moieties, and are not only converted into macromolecules with different constitutions or gels, but also exhibit discriminating properties attributed to the reversibility of dynamic covalent bonds by adequate external stimuli, such as heating and the addition of a catalyst. The trend of dynamic covalent polymers is directed to intelligent systems using equilibrium under reorganization processes and stimulus-responsive polymeric materials based on bond-reformation..
456.	Motoyasu Kobayashi, Hiroki Yamaguchi, Yuki Terayama, Zhe Wang, Kazuhiko Ishihara, Masahiro Hino, Atsushi Takahara, Structure and Surface Properties of High-density Polyelectrolyte Brushes at the Interface of Aqueous Solution, Macromolecular Symposia, 10.1002/masy.200950513, 279, 1, 79-87, 2009.05.
457.	Nattha Jiravanichanun, Kazuya Yamamoto, Atsushi Irie, Hideyuki Otsuka, Atsushi Takahara, Preparation of hybrid films aluminosilicate nanofiber and conjugated polymer, Synthetic Metals, 10.1016/j.synthmet.2009.01.047, 159, 9月10日, 885-888, 2009.05.
458.	Koji Honda, Hiroki Yamaguchi, Taichi Kimura, Yuki Terayama, Motoyasu Kobayashi, Masamichi Morita, Sono Sasaki, Osami Sakata, Naoya Torikai Kazuhiro Ishihara, Atsushi Takahara, Precise Design of Surface nano-texture and Surface Chemistry of Polymeric Solids, Composite Interfaces, 10.1163/156855409X450963, 16, 4, 519-533, 2009.05.
459.	Hideaki YUKUTAKE, Motoyasu KOBAYASHI, Hideyuki OTSUKA, Atsushi TAKAHARA, Thermal Degradation Behavior of Polystyrene/Magadiite Nanocomposites Prepared by Surface-initiated Nitroxide-Mediated Radical Polymerization, Polymer Journal, 10.1295/polymj.PJ2009044, 41, 7, 555-561, 2009.05.
460.	Tomoaki MATSUGI, Junji SAITO, Nobuo KAWAHARA, Shingo MATSUO, Hideyuki KANEKO, Norio KASHIWA, Motoyasu KOBAYASHI, Atsushi TAKAHARA, Surface Modification of Polypropylene Molded Sheets by Means of Surface-Initiated ATRP of Methacrylates, Polymer Journal, 10.1295/polymj.PJ2009034, 41, 7, 547-554, 2009.05.
461.	Taichi Kimura, Motoyasu Kobayashi, Masamichi Morita, Atsushi Takahara, Preparation og Poly(vinylidene fluoride-co-trifluoroethylene) Film with a Hydrophilic Surface by Direct Surface-initiated Atom Transfer Radical Polymerization without Pretreatment, Chemistry Letters, 10.1246/cl.2009.446, 38, 5, 446-447, 2009.05.
462.	T. Thimma Reddy, A. Kano, A. Maruyama, M. Hadano, A. Takahara, Synthesis and characterization of semi-interpenetrating polymer networks based on polyurethane and N-isopropylacrylamide for wound dressing, J. Biomed. Mater. Res., 88B,32-40, 2009.05.
463.	Shin Horiuchi, Takeshi Hanada, Masaharu Ebisawa, Yasuhiro Matsuda Motoyasu Kobayashi, Atsushi Takahara, Contamination-Free Transmission Electron Microscopy for High-Resolution Carbon Elemental Mapping of Polymers, ACS NANO, 10.1021/nn9001598, 3, 5, 1297-1304, 2009.04.
464.	Kosuke Sugawa, Tomoaki Kawahara, Tsuyoshi Akiyama, Motoyasu Kobayashi, Atsushi Takahara, Sunao Yamada, Enhaanced Absorption and Emission in a Copper Phthalocyanine-Gold Nanoparticle System Assisted by Localized Surface Plasmon, Chemistry Letters, 10.1246/cl.2009.326, 38, 4, 326-327, 2009.04.
465.	Naoyuki Morishige, Naoyuki Yamada, Shinichiro Teranishi, Tai-ichiro Chikama, Teruo Nishida, and Atsushi Takahara, Detection of Subepithelial Fibrosis Associated with Corneal Stromal Edema by Second Harmonic Generation Imaging Microscopy, Investigative Ophthalmology & Visual Science, 10.1167/iovs.08-3309, 50, 7, 3145-3150, 2009.02.
466.	Yoshifumi Amamoto, Takeshi Maeda, Moriya Kikuchi, Hideyuki Otsuka, Atsushi Takahara, Rational approach to star-like nanogels with defferent arm lengths: formation by dynamic covalent exchange and their imaging, Chem.Commun., 10.1039/b818049k, 6, 689-691, 2009.02.
467.	Thatiparti Thimma Reddy, Arihiro Kano, Atsushi Maruyama, Michiko Hadano, Atsushi Takahara, Synthesis and characterization of semi-interpenetrating polymer networks based on polyurethane and N-isopropylacrylamide for wound dressing, Journal of Biomedical Materials Research - Part A, 10.1002/jbm.b.31185, 88, 1, 32-40, 2009.01, Thermosensitive semi-interpenetrating polymer networks (semi-IPNs) composed of crosslinked poly(N-isopropylacrylamide) (PNiPAAm) and linear segmented polyurethane urea (SPUU) were synthesized via thermal initiated free radical polymerization. Synthesized semi-IPNs of various compositions were characterized by Fourier transform infrared spectroscopy, water equilibrium swelling at different temperatures, drug lading, drug release, cell adhesion, and detachment. The semi-IPN films of all the compositions were transparent in dry state and negative thermosensitivity in their swelling ratio, that is, lower swelling levels with increasing temperature. The drug release study revealed that the rate of drug release is fast in case of pure SPUU compared to PNiPAAm and semi-IPN film. Drug release depended mainly on solubility of the drugs and physical networks between SPUU and PNiPAAm. Finally NIH3T3 cells were seeded on the semi-IPN films and found that cells were securely attached and proliferated to confluence. Upon cooling, cells were detached from the semi-IPN films. Therefore, the semi-IPN films may be good candidate materials for wound dressing applications..
468.	Motoyasu Kobayashi, Zhe Wang, Yasuhiro Matsuda, Masataka Kaido, Atsushi Suzuki, Atsushi Takahara, Tribological behaviour of polymer brush prepared by the “grafting-from” method, Polymer Tribology, 10.1142/9781848162044_0018, 582-602, 2009.01, This article describes the tribological properties of well-defined highdensity polymer brushes prepared by the “grafting-from” method based on surface-initiated living radical polymerization. The authors have demonstrated here a water-lubrication system using hydrophilic polymer brushes consisting of 2,3-dihydroxypropyl methacrylate and 2-methacryloyloxyethyl phosphorylcholine (MPC). Macro- and microscopic frictional properties were carried out by a ball-on-plate type tribotester and an AFM cantilever attached with a colloidal sphere, respectively. Friction coefficients and adhesion forces of brush surfaces depend on the solvent quality. For example, the friction coefficient of poly(MPC) brush was reduced to be 0.02 under the highly humid atmosphere because water molecules adsorbed into the brush surfaces acted as a lubricant. Furthermore, high-density polymer brushes showed the low friction coefficient even after 100 reciprocating friction test, which clearly indicates an excellent wear resistance of brush film..
469.	Atsushi Takahara, Keiji Tanaka, IUMRS-ICA 2008 symposium, sessions X. applications of synchrotron radiation and neutron beam to soft matter science and Y. frontier of polymeric nano-soft-materials - Precision polymer synthesis, self-assembling and their functionalization, Journal of Physics: Conference Series, 10.1088/1742-6596/184/1/011001, 184, 2009, Applications of Synchrotron Radiation and Neutron Beam to Soft Matter Science (Symposium X of IUMRS-ICA2008) Toshiji Kanaya, Kohji Tashiro, Kazuo Sakura Keiji Tanaka, Sono Sasaki, Naoya Torikai, Moonhor Ree, Kookheon Char, Charles C Han, Atsushi Takahara This volume contains peer-reviewed invited and contributed papers that were presented in Symposium X Applications of Synchrotron Radiation and Neutron Beam to Soft Matter Science at the IUMRS International Conference in Asia 2008 (IUMRS-ICA 2008), which was held on 9-13 December 2008, at Nagoya Congress Center, Nagoya, Japan. Structure analyses of soft materials based on synchrotron radiation (SR) and neutron beam have been developed steadily. Small-angle scattering and wide-angle diffraction techniques clarified the higher-order structure as well as time dependence of structure development such as crystallization and microphase-separation. On the other hand, reflectivity, grazing-incidence scattering and diffraction techniques revealed the surface and interface structural features of soft materials. From the viewpoint of strong interests on the development of SR and neutron beam techniques for soft materials, the objective of this symposium is to provide an interdisciplinary forum for the discussion of recent advances in research, development, and applications of SR and neutron beams to soft matter science. In this symposium, 21 oral papers containing 16 invited papers and 14 poster papers from China, India, Korea, Taiwan, and Japan were presented during the three-day symposium. As a result of the review of poster and oral presentations of young scientists by symposium chairs, Dr Kummetha Raghunatha Reddy (Toyota Technological Institute) received the IUMRS-ICA 2008 Young Researcher Award. We are grateful to all invited speakers and many participants for valuable contributions and active discussions. Organizing committee of Symposium (IUMRS-ICA 2008) Professor Toshiji Kanaya (Kyoto University) Professor Kohji Tashiro (Toyota Technological Institute) Professor Kazuo Sakurai(Kitakyushu University) Professor Keiji Tanaka (Kyushu University) Dr Sono Sasaki (JASRI/Spring-8) Professor Naoya Torikai (KENS) Professor Moonhor Ree (POSTECH) Professor Kookheon Char (Seoul National University) Professor Charles C Han (CAS) Professor Atsushi Takahara(Kyushu University) Frontier of Polymeric Nano-Soft-Materials, Precision Polymer Synthesis, Self-assembling and Their Functionalization (Symposium Y of IUMRS-ICA2008) Seiichi Kawahara, Rong-Ming Ho, Hiroshi Jinnai, Masami Kamigaito, Takashi Miyata, Hiroshi Morita, Hideyuki Otsuka, Daewon Sohn, Keiji Tanaka It is our great pleasure and honor to publish peer-reviewed papers, presented in Symposium Y Frontier of Polymeric Nano-Soft-Materials Precision Polymer Synthesis, Self-assembling and Their Functionalization at the International Union of Materials Research Societies International Conference in Asia 2008 (IUMRS-ICA2008), which was held on 9-13 December 2008, at Nagoya Congress Center, Nagoya, Japan. Polymeric nano-soft-materials are novel outcomes based on a recent innovative evolution in polymer science, i.e. precision polymer synthesis, self-assembling and functionalization of multi-component systems. The materials are expected to exhibit specific functions and unique properties due to their hierarchic morphologies brought either by naturally-generated ordering or by artificial manipulation of the systems, e.g., crystallization and phase-separation. The emerging precision synthesis has brought out new types of polymers with well-controlled primary structures. Furthermore, the surface and interface of the material are recognized to play an important role in the outstanding mechanical, electrical and optical properties, which are required for medical and engineering applications. In order to understand structure-property relationships in the nano-soft-materials, it is indispensable to develop novel characterization techniques. Symposium Y aimed to provide recent advances in polymer synthesis, self-assembling processes and morphologies, and functionalization of nano-soft-materials in order to initiate mutual and collaborative research interest that is essential to develop revolutionarily new nano-soft-materials in the decades ahead. Four Keynote lectures, 15 invited talks and 30 posters presented important new discoveries in polymeric nano-soft-materials, precision polymer synthesis, self-assembling and their functionalization. As for the precision polymer synthesis, the latest results were provided for studies on synthesis of polyrotaxane with movable graft chains, organic-inorganic hybridization of polymers, supra-molecular coordination assembly of conjugated polymers, precision polymerization of adamantane-containing monomers, production of high density polymer brush and synthesis of rod coil type polymer. The state-of-the-art results were introduced for the formation of nano-helical-structure of block copolymer containing asymmetric carbon atoms, self-assembling of block copolymers under the electric field, self-assembling of liquid crystalline elastomers, preparation of nano cylinder template films and mesoscopic simulation of phase transition of polymers and so forth. Moreover, recent advantages of three-dimensional electron microtomography and scanning force microscopy were proposed for analyses of nano-structures and properties of polymeric multi-component systems. Syntheses, properties and functions of slide-ring-gel, organic-inorganic hybrid hydrogels, hydrogel nano-particles, liquid-crystalline gels, the self-oscillating gels, and double network gels attracted participants' attention. Modifications of naturally occurring polymeric materials with supercritical carbon dioxide were introduced as a novel technology. Some of the attractive topics are presented in this issue. We are grateful to all the speakers and participants for valuable contributions and active discussions. Organizing committee of Symposium Y (IUMRS-ICA 2008) Chair Seiichi Kawahara (Nagaoka University of Technology, Japan) Vice Chairs Rong-Ming Ho (National Tsing Hua University, Taiwan) Hiroshi Jinnai (Kyoto Institute of Technology, Japan) Masami Kamigaito (Nagoya University, Japan) Takashi Miyata (Kansai University, Japan) Hiroshi Morita (National Institute of Advanced Industrial Science and Technology, Japan) Hideyuki Otsuka (Kyushu University, Japan) Daewon Sohn (Hanyang University, Korea) Keiji Tanaka (Kyushu University, Japan).
470.	Motoyasu Kobayashi, Masataka Kaido, Atsushi Suzuki, Kazuhiko Ishihara, Atsushi Takahara, Lubrication properties of surfaces with superhydrophilic polymer brushes, Japanese Journal of Tribology, 53, 3, 259-266, 2008.11.
471.	Hiroki Yamaguchi, Koji Honda, Motoyasu Kobayashi, Masamichi Morita, Hiroyasu Masunaga, Osami Sakata, Sono Sasaki, Atsushi Takahara, Molecular aggregation state of surface-grafted poly{2-(perfluorooctyl)ethyl acrylate} thin film analyzed by grazing incidence X-ray diffraction, Polymer Journal, 10.1295/polymj.PJ2008107, 40, 9, 854-860, 2008.11, Surface-initiated atom transfer radical polymerization of 2-(perfluorooctyl)ethyl acrylate on a flat silicon wafer was carried out to give poly{2-(perfluorooctyl)ethyl acrylate} (PFA-C₈) brush thin film with three different thicknesses of 4, 11, and 43 nm, respectively. The water contact angle of the PFA-C₈ brush surface was 120°. The molecular aggregation state of the perfluoroalkyl (R_f) group of PFA-C ₈ brush was analyzed by X-ray reflectivity (XR), wide-angle X-ray diffraction, and grazing incidence X-ray diffraction (GIXD) measurements. XR analysis revealed that R_f groups at the air/brush interface formed a densely packed structure, while a relatively low-density region was generated at the brush/substrate interface. The peaks of in-plane GIXD for brush films with thicknesses of 11 and 43 nm were observed at q_xy = 12.5 nm ^-1, which indicated that R_f groups at the outermost surface oriented perpendicular to the surface of silicon substrate. In an out-of-plane diffraction profile of the 43 nm-thick PFA-C₈ brush film, peaks corresponding to a periodic length of the bilayer lamellae were observed. Therefore, R_f groups of the thicker brush film were crystallized and formed ordered bilayer lamellar structure at the outermost surface. In contrast, no diffraction pattern was observed from the PFA-C ₈ at a thickness of 4 nm by WAXD and GIXD. These results indicate that an amorphous layer was formed at the interface of the brush/substrate. The R_f groups at the anchoring region of the brush could not form a sufficiently ordered structure due to immobilization of brush chain ends on the substrate. It was suggested that the R_f groups in a PFA-C₈ brush thin film at the outermost surface aggregated in a different manner from those in the anchoring region..
472.	Y. Matsuda, M. Kobayashi, M. Annaka, K. Ishihara, A. Takahara, Dimensions of Free Linear Polymer and Polymer Immobilized on Silica Nano Particles of a Zwitter Ionic Polymer in Aqueous Solutions with Various Ionic Strengths, Langmuir, 2008.10.
473.	Toshimi Takajo, Atsushi Takahara, Takefumi Kichikawa, Surface modification of engineering plastics through swelling in supercritical carbon dioxide, Polymer Journal, 10.1295/polymj.PJ2007212, 40, 8, 716-724, 2008.10, In order to improve the tribological characteristics of polymer materials, the authors tried to impregnate the surface of engineering plastics with the lubricating oil by using supercritical carbon dioxide. The oil impregnation ratio on crystalline polymer was influenced by both the glass transition temperature (T_g) and the degree of crystallinity. In case of using the polymer possessing lower T_g with large difference between the T_g and treatment temperature, the higher impregnation ratio was obtained, and the crystallite in crystalline polymer prevented the impregnation of lubricating oil. The results of polarized optical microscopic observations and FT-IR spectroscopy studies indicated that the lubricating oil was preferentially impregnated to the amorphous region in crystalline polymer, and the high-concentration layer of lubricating oil having the thickness of ca. 30 um was formed at the vicinity of surface area. The result obtained in this study, which reports the preferential lubricating oil impregnation to the surface of crystalline polymer under supercritical carbon dioxide, suggests that the tribological characteristics of crystalline polymer would be improved by applying this oil impregnation method without sacrificing the bulk mechanical strength..
474.	Thatiparti Thimma Reddy, Arihiro Kano, Atsushi Maruyama, Michiko Hadano, Atsushi Takahara, Synthesis and Characterization of Semi-Interpenetrating Polymer Networks based on Polyurethane and N-isopropylacrylamide for Wound Dressing, Journal of Biomedical Materials Research Part B, 32-40, 2008.09.
475.	H. Yamaguchi, K. Honda, M. Kobayashi, M. Morita, H. Masunaga, O. Sakata, S. Sasaki, A. Takahara, Molecular Aggregation States of Surface-grafted Poly{2-(perfluorooctyl)ethyl acrylate} Thin Film Analyzed by Grazing Incidence X-ray Diffraction, Polym. J., 2008.09.
476.	Yasuhiro Matsuda, Motoya Kobayashi, Annaka Masahiko, Kazuhiko Ishihara, Atsushi Takahara, Dimensions of a free linear polymer and polymer immobilized on silica nanoparticles of a zwitterionic polymer in aqueous solutions with various ionic strengths, Langmuir, 10.1021/la8005647, 24, 16, 8772-8778, 2008.08, The dimensions and intermolecular interactions of a surface-grafted and unbound free polyampholyte, poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC), were estimated in aqueous solutions with various ionic strengths. Free linear PMPC was synthesized by atom-transfer radical polymerization (ATRP), and static light scattering (SLS) and dynamic light scattering (DLS) were carried out for the PMPC solutions with various concentrations of NaCl, c_s. The hydrodynamic radius RH and the second virial coefficient A₂ of PMPC were independent of c_s (0-0.5 M), though both R_H and A₂ of polyampholytes usually strongly depend on the ionic strength. PMPC-immobilized silica nanoparticles (PMPC-SiNP) were also synthesized by surface-initiated ATRP, and DLS was carried out as for the solutions of linear PMPC to investigate the dependence of the dimensions of PMPC immobilized on a solid surface on the ionic strength. The molecular weight and surface density of PMPC immobilized on SiNP were estimated from the results obtained by GPC, NMR, and thermogravimetric analysis. The independence of RH of PMPC-SiNP was also observed, but its magnitude was larger than that of linear PMPC, although the molecular weight of PMPC immobilized on SiNP was smaller than that of linear PMPC. The larger dimension of PMPC immobilized on SiNP was explained by the excluded volume effect between the immobilized polymer chains..
477.	Motoyasu Kobayashi, Masataka Kaido, Atsushi Suzuki, Kazuhiko Ishihara, Atsushi Takahara, Lubrication properties of surfaces with super-hydrophilic polymer brushes, Toraibarojisuto/Journal of Japanese Society of Tribologists, 53, 6, 357-362, 2008.08.
478.	Motoyasu Kobayashi, Hiroki Yamaguchi, Yuki Terayama, Zhe Wang, Masataka Kaido, Atsushi Suzuki, Atsushi Takahara, Surface and interface structure and tribological properties of hydrophilic polymer brushes, Nihon Reoroji Gakkaishi, 10.1678/rheology.36.107, 36, 2, 107-112, 2008.07, The hydrophilic polymer brushes with 25-35 nm thick were prepared by surface-initiated atom transfer radical polymerization of (2,2-dimethyl-1,3- dioxolan-4-yl)methyl methacrylate (DMM), 2-methacryloyloxyethyl phosphorylcholine (MPC), 2-dimethylaminoethyl methacrylate (DMAEMA), and vinyl acetate (VAc) on the initiator-immobilized silicon wafer. PDMM, PDMAEMA, and PVAc were converted to poly(2,3-dihyroxypropyl methacrylate) (PDHMA), poly(2-methacryloxyethyltrimethylammonium iodide) (PMETA), and polyvinyl alcohol) (PVA), respectively. Macroscopic frictional properties of the hydrophilic polymer brushes were characterized by sliding a glass ball probe in air, water, and toluene under the load of 0.49 N at a sliding velocity of 90 mm/min. The dynamic frictional coefficient of the surfaces immobilized with PDHMA, PMPC, PMETA and PVA brushes were lowered in water (good solvent) compared with in dry air condition, while they increased in toluene (poor solvent). Extremely low friction coefficient of PMPC brush was observed in humid atmosphere because water molecules adsorbed into brush surface acted as a lubricant. Adhesion force measurement of high-density PMPC brush was also carried out by AFM using a colloidal probe. Larger adhesion force was observed in a poor solvent (ethanol/water = 75/25, v/v) compared with good solvent (pure water), because of strong interaction between a brush and a probe in a poor solvent. These results indicate that the frictional properties largely depend on the solvent quality and the adhesion force between the substrate and the sliding probe..
479.	Yasuhiro Matsuda, Motoyasu Kobayashi, Annaka Masahiko, Kazuhiko Ishihara, Atsushi Takahara, UCST-type cononsolvency behavior of poly(2-methacryloxyethyl phosphorylcholine) in the mixture of water and ethanol, Polymer Journal, 10.1295/polymj.PJ2008009, 40, 5, 479-483, 2008.07, A study was conducted for turbimetry and dynamic light scattering (DLS) measurements of poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) in the mixture of water and ethanol. PMPC has positive and negative charge in its phosphorylcholine group. PMPC never shrinks in aqueous solution with low ionic strength and network of water molecular formed by hydrogen bonds remain unchanged. PMPC is used for medical materials for its high hydrophilic properties and high biocompatibility. PMPC was synthesized by atom transfer radial polymerization from the corresponding monomer. The size exclusion chromatography (SEC) was used to determine the molecular weight of PMPC samples. The study found that with phase separation, water and alcohols can form hydrogen bonds, which decreased the enthalpy of the system and entropy of PMPC decreased by the precipitation..
480.	Nao Hosaka, Hideyuki Otsuka, Masahiro Hino, Atsushi Takahara, Control of dispersion state of silsesquioxane nanofillers for stabilization of polystyrene thin films, Langmuir, 10.1021/la704062n, 24, 11, 5766-5772, 2008.06, The influence of the dispersion states of the nanofillers on the dewetting behavior of the polymer thin film was investigated. Polyhedral oligomeric silsesquioxanes (POSS) with various substituents were added into polystyrene (PS) thin films as the nanofillers. The dewetting rate of the films drastically changed with the surface substituents of POSS additives. Neutron reflectivity measurements indicated that the difference of the dewetting rate was associated with the dispersion state of POSS additives in the films. POSS with phenethyl groups (PhPOSS), which homogeneously dispersed into the films, resulted in the decrease of the glass transition temperature of PS and the enhancement of the dewetting of the films. POSS with a fluoroalkyl group (CpPOSS-Rf) segregated to the film surface and showed the retardation of the dewetting by the decrease of the surface energy of the film. POSS with hydroxyl groups (CpPOSS-2OH) segregated to the film surface and film-substrate interface and led to the elimination of the dewetting, suggesting the importance of the interfacial segregation for the inhibition of dewetting. These results revealed the strong relationship between the dispersion state of the nanofillers and the dewetting of the nanofilled films..
481.	Yasuhiro Matsuda, Motoyasu Kobayashi, Atsushi Takahara, Akihiro Tanaka, Hisato Hayashi, Annaka Masahiko, Takahiro Sato, On the dimension of a hyperbranched polymer synthesized from a styrene derivative, Polymer Journal, 10.1295/polymj.PJ2007211, 40, 4, 375-378, 2008.06, A study was conducted to find out the dimension of a hyperbranched polymer (HBP) synthesized from a N,N-diethylamino dithiocarbamoylmethylstyrene (DCS) derivatives by one-pot reaction and photopolymerization. Dynamic light scattering (DLS) measurement was used for HBP to obtain the hydrodynamic radius, which was larger than linear PS with the same degree of polymerization. The study compared the chain dimension of the HBP, in tetrahydrofuran (THF) and methyl ethyl ketone (MEK)with linear PS. The study found that phenyl ring attached the polymer chain as the side group for PS and for the HBP the phenylene ring was attached into the main chain. The study stated that solvent qualities of MEK and cyclohexane were worse for the HBP than for PS. HBP formed a tiny amount of aggregates at concentrations of 10^-2 g/cm ³ for THF and MEK..
482.	Keiji Tanaka, Noriaki Sanada, Masaya Hikita, Tetsuya Nakamura, Tisato Kajiyama, Atsushi Takahara, Surface depth analysis for fluorinated block copolymer films by X-ray photoelectron spectroscopy using C60 cluster ion beam, Applied Surface Science, 10.1016/j.apsusc.2008.02.089, 254, 17, 5435-5438, 2008.06, X-ray photoelectron spectroscopy (XPS) using fullerene (C₆₀) cluster ion bombardment was applied to films of a fluorinated block copolymer. Spectra so obtained were essentially different from those using Ar ion beam. Structure in the surface region with the depth down to 60 nm drawn on the basis of XPS with C₆₀ beam was essentially the same as the one drawn by the result using dynamic secondary ion mass spectrometry, which is a well-established method for the depth analysis of polymers. This implies that XPS using C₆₀ beam enables one to gain access to the depth analysis of structure in polymer films with the depth range over the analytical depth of conventional XPS, that is, three times inelastic mean-free path of photoelectrons..
483.	Koji Honda, Masamichi Morita, Atsushi Takahara, Room-temperature fabrication of nanotexture in crystalline poly(fluoroalkyl acrylate) thin film, Soft Matter, 10.1039/b803076f, 4, 7, 1400-1402, 2008.06, A mold with a several hundreds of nanometres line pattern was successfully imprinted onto poly(fluoroalkyl acrylate) film with long crystalline fluoroalkyl groups (PFA-C₈) at room-temperature..
484.	Y. Matsuda, M. Kobayashi, A. Takahara, A. Tanaka, H. Hayashi, M. Annaka, and T. Sato, On the Dimension of a Hyperbranched Polymer Synthesized from a Styrene Derivative, Polym. J., 2008, 40(4), 375-378., 2008.04.
485.	T. Thimma Reddy, Arihiro Kano, Atsushi Maruyama, Michiko Hadano, Atsushi Takahara, Thermosensitive transparent semi-interpenetrating polymer networks for wound dressing and cell adhesion control, Biomacromolecules, 10.1021/bm701390f, 9, 4, 1313-1321, 2008.04, Thermosensitive, transparent, and flexible semi-interpenetrating polymer networks (semi-IPNs) composed of segmented polyurethane urea/ poly(N-isopropylacrylamide) (SPUU/ PNiPAAm) were new class of materials, which holds promise for its potential use as wound dressings. A series of semi-IPNs, obtained via thermal initiated polymerization of NiPAAm, were characterized by infrared spectroscopy (IR), nuclear magnetic resonance (NMR), dynamic viscoelastic measurements, wide-angle X-ray diffraction (WAXD), and mechanical properties. The resulting semi-IPNs were also investigated for their dynamic water contact angles, thermodynamic interaction parameters, in vitro drug release, and cell adhesion and detachment. The semi-IPNs with differing compositions possess good mechanical properties in both dry and hydrated states. In addition, NIH3T3 fibroblasts can attach to and detach from these semi-IPN films with varying temperature. In addition, these film extracts do not show significant cytotoxicity. Therefore, these materials have great potential for the construction of a new generation of dressings and cell transplantation for wound healing..
486.	Hideki Sugihara, Kazuyuki Oya, Hiroki Murase, Keiichi Akabori, Keiji Tanaka, Tisato Kajiyama, Atsushi Takahara, Simultaneous imaging for surface and internal structure of polymer blend thin films, Applied Surface Science, 10.1016/j.apsusc.2007.10.080, 254, 10, 3180-3183, 2008.03, A novel experimental technique for three-dimensional (3D) visualization of phase-separated structure of polymer blend thin film was proposed. Polystyrene/poly(methyl methacrylate) (PS/PMMA) blend thin films with the thickness of approximately 100 nm were cut at extremely low angle by utilizing surface and interface cutting analysis system (SAICAS), and the cross-section was exposed as gradient surface with the width of approximately 2.5 μm. SFM investigation for the grazing cross-section imaged the detailed internal and surface phase separated structure of the (PS/PMMA) blend thin films on one image..
487.	K. Honda, H. Yamaguchi, M. Kobayashi, M. Morita, Atsushi Takahara, Surface molecular aggregation structure and surface physicochemical properties of poly(fluoroalkyl acrylate) thin films, Journal of Physics: Conference Series, 10.1088/1742-6596/100/1/012035, 100, 1, 2008.03, Effect of side chain length on the molecular aggregation states and surface properties of poly(fluoroalkyl acrylate)s [PFA-C_y, where y is fluoromethylene number in R_f group] thin films were systematically investigated. Spin-coated PFA-C_y thin films were characterized by static and dynamic contact angle measurements, X-ray photoelectron spectroscopy (XPS), and grazing- incidence X-ray diffraction (GIXD). The receding contact angles showed small values for PFA-C_y with short side chain (y≤6) and increased above y≥8. GIXD revealed that fluoroalkyl side chain of PFA-C_y with y≥8 was crystallized and formed ordered structures at the surface region as well as bulk one. These results suggest that water repellent mechanism of PFA-C_y can be attributed to the presence of highly ordered fluoroalkyl side chains at the outermost surfaces. The results of XPS in the dry and hydrated states and contact angle measurement in water support the mechanism of lowering contact angle for water by exposure of carbonyl group to the water interface through reorientation of short fluoroalkyl chains. The surface nanotextured PFA-C₈ through imprinting of anodic aluminum oxide mold showed extremely high hydrophobicity as well as high oleophobicity..
488.	T. Thimma Reddy, Arihiro Kano, Atsushi Maruyama, Michiko Hadano, Atsushi Takahara, Cell adhesion and detachment on novel semi-interpenetrating polymer network films, Quaternary International, 49, 1, 826-827, 2008.
489.	Nattha Jiravaniehanun, Kazuya Yamamoto, Hiroaki Yonemura, Sunao Yamada, Hideyuki Otsuka, Atsushi Takahara, Fabrication of conjugated polymer hybrid thin films with radially oriented aluminosilicate nanoflbers by spin-assembly, Bulletin of the Chemical Society of Japan, 10.1246/bcsj.81.1663, 81, 12, 1663-1668, 2008, Multilayer hybrid films of imogolite nanofibers and water-soluble poly(p-phenylene) (WS-PPP) were prepared by two assembly methods. Layer-by-layer (LBL) assembly and spin-assembly were applied to fabricate the hybrid films. The deposited amount of WS-PPP per thickness was not significantly different between the two methods. However, the spin-assembly method gave significant orientation of imogolite nanofibers aligned in the radial direction, while imogolite nanofibers were randomly networked in the LBL film. The results suggested that lyotropic mesophase of imogolite and centrifugal and shear forces influenced a self-assembly of imogolite fibers oriented in a force-inducing direction..
490.	Teruo Murakami, Shunichiro Doi, Atsushi Takahara, Kazuya Yamamoto, Influence of surface films on wear in sliding pairs of ceramic-on-ceramic for total hip prostheses, 8th World Biomaterials Congress 2008, WBC 2008 8th World Biomaterials Congress 2008, 2, 595, 2008.
491.	Kei Ichi Akabori, Keiji Tanaka, Hiroki Murase, Atsushi Takahara, Tisato Kajiyama, Model analysis of scanning viscoelasticity microscopy and its applications to polymer surfaces, Nihon Reoroji Gakkaishi, 10.1678/rheology.36.87, 36, 2, 87-92, 2008, Scanning viscoelasticity microscopy (SVM) with a mechanical model analysis was applied to polystyrene (PS) surfaces. When the surface was in a glassy state, that is, in an elastic regime, the SVM vibrational system can be simply expressed by a series model composed of two springs such as a cantilever and the sample surface. Once the surface reaches in a viscoelastic regime, a damping factor must be incorporated into the model surface. The spring constants for the PS surfaces being in glassy and transition states were successfully extracted by the analysis. The surface value even for the glassy state was lower than the corresponding bulk value by a few decades..
492.	K. Miyamoto, N. Hosaka, M. Kobayashi, H. Otsuka, N. Yamada, N. Torikai, A. Takahara,, Dewetting Inhibition and Interfacial Structures of Silsesquioxane-terminated Polystyrene Thin Films, Polymer Journal, 39, 1247-1252, 2007.12.
493.	T. Koga, Atsushi Takahara, Chapter 8 Structure and Physicochemical Properties of Polyalkylsiloxane Monolayers Prepared onto the Solid Substrate, Advanced Chemistry of Monolayers at Interfaces Trends in Methodology and Technology, 10.1016/S1573-4285(06)14008-9, 193-217, 2007.12.
494.	Kyota Miyamoto, Nao Hosaka, Motoyasu Kobayashi, Hideyuki Otsuka, Norifumi Yamada, Naoya Torikai, Atsushi Takahara, Dewetting inhibition and interfacial structures of silsesquioxane- terminated polystyrene thin films, Polymer Journal, 10.1295/polymj.PJ2007067, 39, 12, 1247-1252, 2007.12, Polyhedral oligomeric silsesquioxane (POSS)-terminated polystyrene (PS-POSS) was prepared by nitroxide-mediated radical polymerization of styrene with POSS-containing initiator, and the thermal stability of PS-POSS thin films was investigated. Rheological measurement of PS-POSS revealed that the rheological properties were profoundly affected by the presence of POSS end groups in low molecular weight region (M_n ≈ 2000), while those were nearly unaffected in high molecular weight region (M_n ≈ 40000). However, the introduction of POSS as a PS end group can actually stabilize PS thin films against de wetting in a range of the molecular weight used in this study. Neutron reflectivity measurement of deuterated PS-POSS thin film revealed that the POSS moieties Of PS-POSS formed enrichment layer at the interfaces of the film. The segregation of the POSS end group at the film-substrate interface, which can modify the interface by tethering the PS chains at the interface, seems to be an important factor in the dewetting inhibition effect..
495.	Y. Amamoto, Y. Higaki, Y.. Matsuda, H. Otsuka, A. Takahara,, Programmed Thermodynamic Formation and Structure Analysis of Star-like Nanogels with Core Cross-linked by Thermally Exchangeable Dynamic Covalent Bonds, J. Am. Chem. Soc., 129(43); 13298-13304, 2007.10.
496.	Yuki Terayama, Motoyasu Kobayashi, Atsushi Takahara, Preparation and surface properties of polyvinyl alcohol brush, Chemistry Letters, 10.1246/cl.2007.1280, 36, 10, 1280-1281, 2007.10, Poly(vinyl alcohol) (PVA) brush was prepared by surface-initiated iodine-transfer polymerization of vinyl acetate (VAc) from a silicon wafer and successive hydrolysis of acetyl groups. The adhesion forces of PVA and PVAc brush surfaces were measured by atomic force microscopy..
497.	Yoshifumi Amamoto, Yuji Higaki, Yasuhiro Matsuda, Hideyuki Otsuka, Atsushi Takahara, Programmed thermodynamic formation and structure analysis of star-like nanogels with core cross-linked by thermally exchangeable dynamic covalent bonds, Journal of the American Chemical Society, 10.1021/ja075447n, 129, 43, 13298-13304, 2007.10, Programmed thermodynamic formation of star-like nanogels from designed diblock copolymers with thermally exchangeable dynamic covalent bonds in their side chains and structure analysis of the nanogels were performed. Linear diblock copolymers that consist of poly(methyl methacrylate) block and random copolymer block of methyl methacrylate (MMA) and methacrylic esters with alkoxyamine moiety were prepared by atom transfer radical polymerization (ATRP). By heating the diblock copolymers in anisole, a cross-linking reaction occurred as a result of the radical crossover reaction of alkoxyamine moieties to afford star-like nanogels. Kinetic studies have revealed that the cross-linking behavior reaches equilibrium at a given reaction time, with characteristic reaction behaviors for thermodynamic reactions being observed. The equilibrium structures of the star-like nanogels were controlled by the initial concentrations of diblock copolymers as well as their compositions and molecular weights. Furthermore, by heating the star-like nanogels with excess alkoxyamine, linear polymers were successfully regenerated. The molecular weights and sizes of the nanogels were evaluated by gel permeation chromatography-multiangle laser light scattering (GPC-MALLS) and small-angle X-ray scattering (SAXS) measurements, respectively, and the morphologies of the nanogels were directly observed by scanning force microscopy (SFM)..
498.	Masayuki Kaneda, Yuu Takao, Hirotaka Ishizuka, Jun Fukai, Shigekazu Yasutake, Atsushi Takahara, Effect of a binary solvent on film formation in ink-jet printing, kagaku kogaku ronbunshu, 10.1252/kakoronbunshu.33.396, 33, 5, 396-401, 2007.10, The effect of a binary solvent with high and low boiling points on the film formation in ink-jet printing of a polymer solution was studied experimentally. The principal reason that the binary solvent prevents the formation of a ring-stain is that the low boiling solvent evaporates quickly, resulting in an increase in the solution viscosity at the pinning of the contact line. The experimental results revealed that this increase in viscosity is caused by Marangoni convection due to the concentration profile of the solvents on the free surface. Based on this finding, experiments with a single-solvent droplet showed that ring-stain formation can be suppressed by increasing the initial solute concentration. With the binary solvent, it becomes possible to impact fluids of even higher viscosity on the surface by increasing the evaporation of the low boiling solvent. Furthermore, the atmospheric temperature and the gap between the nozzle and the surface affect the viscosity at impact at which the ring stain is eliminated..
499.	Kei Ichi Akabori, Keiji Tanaka, Noriaki Satomi, Toshihiko Nagamura, Atsushi Takahara, Tisato Kajiyama, Effects of static and dynamic forces on surface viscoelastic response of polymer films in scanning viscoelasticity microscopy, Polymer Journal, 10.1295/polymj.PJ2006230, 39, 7, 684-689, 2007.09, Scanning force microscopy with force-modulation mode enables one to gain direct insights into local viscoelastic properties at polymer surfaces. Changing modulation condition such as dynamic amplitude and frequency in addition to static normal force, surface viscoelastic response of polystyrene (PS) film was studied. If dynamic and/or static forces were/was ill-chosen, non-linearity of viscoelastic response became dominant, resulting in hole formation at the surface. On the contrary, if they were appropriately adjusted, linear viscoelastic measurement could be realized in the frequency range from 10 Hz to 4 kHz. This leads to traditional rheological analysis even at the surface..
500.	S.-G. Park, Y,-H. Lee, B.-J. Kim, J.-S. Lee, Y.-D. Jeong, J.-Ｇ． Noh, A. Takahara,　D. Ｗ．-Sohn, Two dimensional alignment of the alumino-silicate nanofiber, imogolite, on a solid surface, Chem. Commun., 2917-2919, 2007.08.
501.	T.　Koga, K. Honda, S. Sasaki, O. Sakata, A. Takahara,, Phase Transition of Alkylsilane Monolayers Studied by Temperature Dependent Grazing Incidence X-ray Diffraction, Langmuir, 23(17); 8861-8865, 2007.08.
502.	Tomoyuki Koga, Koji Honda, Sono Sasaki, Osami Sakata, Atsushi Takahara, Phase transition of alkylsilane monolayers studied by temperature-dependent grazing incidence X-ray diffraction, Langmuir, 10.1021/la7006588, 23, 17, 8861-8865, 2007.08, The phase transition of organosilane monolayers on Si-wafer substrate surfaces prepared from octadecyltrichlorosilane (OTS) or docosyltrichlorosilane (DOTS) was investigated on the basis of grazing incidence X-ray diffraction (GIXD) at various temperatures. The OTS monolayer was prepared by a chemisorption method. The DOTS monolayer was prepared by a water-cast method (DOTS). The GIXD measurement clarified that the OTS monolayer also changed from hexagonal phase to amorphous state above a melting point of otadecyl groups. The GIXD measurements also clarified that the molecular aggregation state of the DOTS monolayer changes from an anisotropic phase to an isotropic phase with an increase in temperature. An estimated linear thermal expansion coefficient of the lattice lengths of a and b of the DOTS monolayer in the rectangular crystalline state assigned a similar value to those of bulk polyethylene with an orthorhornbic crystalline lattice. The setting angle of the ab plane of the rectangular DOTS monolayer also showed similar behavior to that of the ab plane of bulk polyethylene..
503.	D. Kawaguchi, K. Tanaka, N. Torikai, A.Takahara, and T.Kajiyama, Surface and Interfacial Segregation in Blends of Polystyrene with Functional End Groups and Deuterated Polystyrene, Langmuir, 23 , 7269-7275, 2007.07.
504.	K. Akabori, K. Tanaka, N. Satomi, T. Nagamura, A. Takahara, and T. Kajiyama, Effects of Static and Dynamic Forces on Surface Viscoelastic Response of Polymer Films in Scanning Viscoelasticity Microscopy, Polymer J.,, Polymer Journal, 39(7), 684-689(2007)., 2007.07.
505.	Sungjin Park, Yunha Lee, Bumjung Kim, Jisun Lee, Youngdo Jeong, Jaegeun Noh, Atsushi Takahara, Daewon Sohn, Two-dimensional alignment of imogolite on a solid surface, Chemical Communications, 10.1039/b706505a, 28, 2917-2919, 2007.07, Surface modified imogolite fiber, hydrated aluminium silicate that has the shape of a rigid hollow cylinder, was aligned with consistent nano spacing and was visualized by scanning tunneling microscopy..
506.	S. Sasaki, H. Masunaga, H. Tajiri,a K.i Inoue, H. Okuda, H. Noma, K. Honda, A. Takahara, M. Takata,, In situ investigation of annealing effect on lamellar stacking structure of polyethylene thin films by synchrotron grazing-incidence small-angle and wide-angle X-ray scattering, J. Appl. Cryst., 40, S643-644, 2007.06.
507.	Yoshifumi Amamoto, Yuji Higaki, Yasuhiro Matsuda, Hideyuki Otsuka, Atsushi Takahara, Programmed formation of nanogels via a radical crossover reaction of complementarily reactive diblock copolymers, Chemistry Letters, 10.1246/cl.2007.774, 36, 6, 774-775, 2007.06, By heating two types of diblock copolymers with complementarity reactive alkoxyamine units in the side chains, nanogels were formed as a result of a radical crossover reaction of the alkoxyamine units. The transformation from the diblock copolymers to nanogels and their absolute molecular weight were obviously dependent on reaction concentrations and the mixing ratio of two types of diblock copolymers..
508.	Daisuke Kawaguchi, Keiji Tanaka, Naoya Torikai, Atsushi Takahara, Tisato Kajiyama, Surface and interfacial segregation in blends of polystyrene with functional end groups and deuterated polystyrene, Langmuir, 10.1021/la700418j, 23, 13, 7269-7275, 2007.06, The effect of chain-end chemistry on surface and interfacial segregation in symmetric blends of polystyrene (hPS)/ deuterated polystyrene (dPS) has been investigated by X-ray photoelectron and secondary ion mass spectroscopy in conjunction with neutron reflectivity measurements. α,ω-Fluoroalkyl- and α,ω-carboxy-terminated polystyrenes (α,ω-hPS(R _f)₂ and α,ω-hPS(COOH)₂) were used as end-functionalized polymers; the former possesses chain ends with lower surface energies, and the latter possesses higher surface energies compared with that of the main chain. In the case of an α,ω-hPS(R _f)₂/dPS blend film, α,ω-hPS(R _f)₂ was enriched at the surface owing to the surface localization of the R_f groups, although the surface energy of the hPS segments was slightly higher than that of the dPS ones. On the contrary, in the case of an α,ω-hPS(COOH)₂/dPS blend film, dPS was preferentially segregated at the surface. This may be due to a surface depletion of COOH ends and an apparent molecular weight increase of α,ω- hPS(COOH)₂ produced by a hydrogen-bonded intermolecular association of COOH ends in addition to the surface energy difference between hPS and dPS segments. Interestingly, both R_f and COOH chain ends were partitioned to the substrate interface for the α,ω-hPS(R_f) ₂/dPS and α,ω-hPS(COOH)₂/dPS blend films, resulting in the segregation of the hPS component at the substrate interface for both blends. The results presented imply that surface and interfacial segregation in polymer blends could be regulated by incorporating functional groups into the end portions of one component..
509.	M. Kaneda, H. Ishizuka, Y. Sakai, J. Fukai, S. Yasutake, A. Takahara, Film Formation from Polymer Solution Using Inkjet Printing Method, AIChE. J., 53, 1100-1108, 2007.05.
510.	M. Kobayashi, Y. Terayama, M. Kaido, A. Suzuki, K. Ishihara, A. Takahara, Friction Behavior of High-density Poly(2-methacryloyloxyethyl phosphorylcholine) Brush in Aqueous Media, Soft Matter, 3, 740-746, 2007.05.
511.	Masayuki Kaneda, Hirotaka Ishizuka, Yousuke Sakai, Jun Fukai, Shigekazu Yasutake, Atsushi Takahara, Film formation from polymer solution using inkjet printing method, AIChE Journal, 10.1002/aic.11154, 53, 5, 1100-1108, 2007.05, The factors determining the thin-film shape from an evaporating polymer solution droplet are experimentally studied. The polystyrenelxylene droplets, whose diameter is controlled in the range of 30-100 μm with the mass fraction of 0.5-3.0 wt % are ejected onto a lyophobic substrate. The droplet on the substrate results in an axisymmetric or nonaxisymmetric ring-like/dot-like film. The film configuration is dominated by the evaporation rate and the film symmetry is governed by the local pinning time at the periphery. Various relationships are also found among the evaporation rate, pinning time, wetting diameter, and average solute concentration of which the nondimensionalization pronounces explicit relationships and similarity..
512.	Motoyasu Kobayashi, Yuki Terayama, Nao Hosaka, Masataka Kaido, Atsushi Suzuki, Norifumi Yamada, Naoya Torikai, Kazuhiko Ishihara, Atsushi Takahara, Friction behavior of high-density poly(2-methacryloyloxyethyl phosphorylcholine) brush in aqueous media, Soft Matter, 10.1039/b615780g, 3, 6, 740-746, 2007.05, Super-hydrophilic polymer brushes were prepared by surface-initiated atom transfer radical polymerization of 2-methacryloyloxyethyl phosphorylcholine (MPC) on initiator-immobilized silicon wafers. The graft density was estimated to be ca. 0.22 chains nm^-2 based on the linear relationship between M_n and the layer thickness. The contact angle against water was very low, and air bubbles in water hardly attached onto the brush surface, indicating a super-hydrophilic surface. Neutron reflectivity measurements of the poly(MPC) brush showed that the grafting polymer chains extended a fair amount in the vertical direction from the substrate in a good solvent such as water, while they shrunk in a poor solvent. Frictional properties of the poly(MPC) brushes were characterized by sliding a glass ball probe in air and various solvents under a load of 0.49 N at a sliding velocity of 90 mm min^-1. An extremely low friction coefficient of the poly(MPC) brush was observed in humid atmosphere because water molecules adsorbed into the brush layer acted as a lubricant..
513.	Tomoyuki Koga, Koji Honda, Sono Sasaki, Osami Sakata, Atsushi Takahara, Two-dimensional molecular aggregation structure and thermal molecular motion of polyalkylsiloxane ultrathin films, KOBUNSHI RONBUNSHU, 10.1295/koron.64.269, 64, 5, 269-279, 2007.05, Two-dimensional molecular aggregation states of polyalkylsiloxane ultrathin films on silicon wafer substrates surface were investigated by various techniques. The in-plane grazing incidence X-ray diffraction, Fourier transform infrared spectroscopy, field emission scanning electron microscopy, and scanning force microscopy revealed that the alkyl chains in the octadecyltrimethoxysilane (OTMS) ultrathin films prepared by the CVA method (OTMS-CVA) are in an amorphous state at room temperature. On the other hand, octadecyltrichlorosilane (OTS) ultrathin films prepared by the solution chemisorption method and water-cast method are in a hexagonal crystalline state. According to lateral force microscopic measurements, the transition temperature from the hexagonal crystalline phase to the amorphous phase was found to be ca 333 K for the OTS ultrathin film prepared by the chemisorption method. However, the phase transition was not clearly observed in the OTMS-CVA ultrathin film. These results indicated that organosilane compounds in the ultrathin film prepared by the CVA method were immobilized on the silicon wafer substrate surface in an amorphous state, which was quite different from the hexagonal crystalline state obtained by the solution chemisorption and water-cast methods..
514.	Jun Fukai, H. Ishizuka, Y. Sakai, M. Kaneda, M. Morita, Atsushi Takahara, Drying process of micro-scale polymer solution droplets deposited on lyophobic surfaces, Experimental Heat Transfer, 10.1080/08916150601091449, 20, 2, 137-146, 2007.04, A micro-scale polymer solution droplet is deposited on a lyophobic surface using an inkjet printing method, and then dried to form a thin polymer film. The shapes of the films formed from xylene-polystyrene (PS) droplets are changed from ring-like to dot-like as the initial PS concentration decreases. Detailed investigations of the drying processes reveal that the pinning time of the contact line dominates the shape and dimension of the polymer film. For ethyl acetate/acetophenone-PS solutions, ethyl acetate rapidly evaporates at the initial stage, but it plays an important role in delaying the pinning time. As a result, this binary solvent forms a dot-like polymer film..
515.	Sono Sasaki, Hiroyasu Masunaga, Hiroo Tajiri, Katsuaki Inoue, Hiroshi Okuda, Hiromichi Noma, Kohji Honda, Atsushi Takahara, Masaki Takata, In situ investigation of annealing effect on lamellar stacking structure of polyethylene thin films by synchrotron grazing-incidence small-angle and wide-angle X-ray scattering, Journal of Applied Crystallography, 10.1107/S002188980700578X, 40, SUPPL. 1, s642-s644, 2007.04, We have investigated lamellar stacking structure of melt-crystallized and annealed high-density polyethylene (HDPE) thin films, with a thickness of ca 400 nm prepared on silicon wafers, using synchrotron grazing-incidence small-angle and wide-angle X-ray scattering (GISWAXS) measurements at the BL40B2 beamline in SPring-8. In-situ measurements of GISWAXS were carried out for the films in a stepwise annealing process under vacuum. Scattering peaks relating to the long period, the average distance between stacked crystalline lamellae, were measured only in the in-plane direction near the Yoneda peak of the grazing-incidence small-angle X-ray scattering patterns. On the other hand, the orthorhombic (110) and (200) reflections of oriented HDPE crystals were measured in the out-of-plane direction of the grazing-incidence wide-angle X-ray scattering patterns. It was revealed that crystalline lamellae were stacked in a parallel direction to the film surface and the long period increased from ca 25 nm to ca 32 nm in a stepwise annealing process. Within a lamella, molecular chains were found to be packed regularly and the chain axis (the c axis) was relatively oriented parallel to the film surface..
516.	Koji Honda, Masamichi Morita, Atsushi Takahara, Surface molecular aggregation structure and surface properties of poly (fluoroalkyl acrylate) thin films, KOBUNSHI RONBUNSHU, 10.1295/koron.64.181, 64, 4, 181-190, 2007.04, Effects of side chain length on the molecular aggregation states and surface properties of poly (fluoroalkyl acrylate) s [PFA-C_y, where y is the fluoromethylene number in R_f group] thin films were systematically investigated. Spin-coated PFA-Cy thin films were characterized by static and dynamic contact angle measurements, X-ray photoelectron spectroscopy (XPS), differential scanning calorimetry and wide-angle X-ray diffraction. The receding contact angles showed small values for PFA-C_y with short side chain (y≤6) and increased above y≥ 8. Results revealed that the fluoroalkyl side chain of PFA-C_y with y≥8 was crystallized and formed ordered structures. These results suggest that the water-repellent mechanism of PFA-C, can be attributed to the presence of highly ordered fluoroalkyl side chains at the outermost surfaces. The results of XPS in the dry and hydrated states and contact angle measurement in water support the mechanism of lowering contact angle for water by exposure of carbonyl group to the water interface through reorientation of short fluoroalkyl chains. The surface nanotexture was formed on PFA-C₈ through imprinting of anodic aluminum oxide films with a pore diameter of 200 nm. This nanoimprinted surface showed extremely high hydrophobicity as well as high oleophobicity..
517.	Kazuya Yamamoto, Hideyuki Otsuka, Atsushi Takahara, Preparation of novel polymer hybrids from imogolite nanofiber, Polymer Journal, 10.1295/polymj.PJ2006128, 39, 1, 1-15, 2007.03, Polymer hybrids designed on a nanometer scale were prepared by several methods with an alumino-silicate nanofiber, "imogolite." This review paper introduces the preparation of polymer hybrid materials from imogolite nanofiber by two different approaches. In order to realize the fine dispersion of imogolite in polymer matrix, poly-(vinyl alcohol)/imogolite hybrids were prepared by in situ synthesis method of imogolite in polymer solution. In addition, through utilizing the strong interaction between phosphoric acid group and Al-OH on the surface of imogolite, poly(methyl methacrylate)/imogolite hybrid, and enzyme/imogolite hybrid gel were prepared and characterized..
518.	Hideyuki Otsuka, Koichiro Aotani, Yuji Higaki, Yoshifumi Amamoto, Atsushi Takahara, Thermal reorganization and molecular weight control of dynamic covalent polymers containing alkoxyamines in their main chains, Macromolecules, 10.1021/ma061667u, 40, 5, 1429-1434, 2007.03, Dynamic covalent polymers incorporating thermally reversible alkoxyamine units in the main chain were synthesized, and their thermal structural reorganization behavior was systematically investigated. The model reaction using alkoxyamine derivatives clearly revealed that the exchange reaction between the derivatives occurred upon heating over 60 °C, and the degree of exchange strongly depended on the reaction temperature, time, and concentration. Polycondensation from alkoxyamine-based diol and adipoyl chloride at room temperature successfully afforded the corresponding poly(alkoxyamine ester) without any decomposition of the alkoxyamine units. Their molecular weight can be readily estimated by conventional gel permeation chromatography (GPC). In contrast, their thermal reorganization behavior was completely different from common polymers; for instance, the peak in the GPC profiles of the fractionated polymer with a narrow molecular weight distribution broadened to 1.6-2.0 upon heating. Furthermore, the mixture of poly(alkoxyamine)s with different molecular weights reorganized to form the poly(alkoxyamine) with an average molecular weight that showed as a unimodal peak in the GPC profile. However, NMR spectroscopy measured after heating did not reveal any change in the primary chemical structure of the repeating unit. The thermal reorganization in the presence of excess N-O stable free radical resulted in the scission of the main chain due to the chain transfer reaction..
519.	H. Otsuka, K. Aotani,Y. Higaki, Y. Amamoto, A. Takahara, Thermal Reorganization and Molecular Weight Control of Dynamic Covalent Polymers Containing Alkoxyamines in Their Main Chains, Macromolecules, 40, 1429-1434, 2007.02.
520.	H. Otsuka, K. Aotani,Y. Higaki, Y. Amamoto, A. Takahara, Thermal Reorganization and Molecular Weight Control of Dynamic Covalent Polymers Containing Alkoxyamines in Their Main Chains, Macromolecules, 40, 1429-1434, 2007.02.
521.	K. I. Akabori, Keiji Tanaka, Atsushi Takahara, T. Kajiyama, T. Nagamura, Substrate effect on mechanical relaxation of polystyrene in ultrathin films, European Physical Journal: Special Topics, 10.1140/epjst/e2007-00036-8, 141, 1, 173-180, 2007.02, Mechanical relaxation behavior in ultrathin polystyrene(PS) films supported on silicon oxide (SiO_x) and gold (Au) substrates has been studied by dynamic viscoelastic measurement. Based on the method, effects of free surface and substrate interface on the segmental dynamics were discussed. In the case of thin PS films with a thickness of approximately 200 nm, α_a-relaxation process corresponding to the segmental motion did not show any deviation from the bulk behavior. Incontrast, for the films thinner than about 50 nm, the relaxation time distribution for the α_a-process became broader, probably due toa mobility gradient in the surface and interfacial regions. When we sandwiched an ultrathin PS film between SiO_x layers, another relaxation process, in addition to the original α_a-process, appeared at ahigher temperature side that we assigned to the interfacial α_a-relaxation process. However, this was never seen for an ultrathin PS film between Au layers, implying that restriction from the substrate interface might be weak in this case..
522.	Kei Ichi Akabori, Keiji Tanaka, Toshihiko Nagamura, Atsushi Takahara, Tisato Kajiyama, Thermal molecular motion in polystyrene thin and ultrathin films by dynamic viscoelastic measurement, Journal of Central South University of Technology (English Edition), 10.1007/s11771-007-0279-6, 14, 1 SUPPL., 346-349, 2007.02, Segmental motion in polystyrene (PS) thin and ultrathin films supported on substrates was studied by dynamic viscoelastic measurement. A polymer film, which has the thickness comparable to or less than twice of radius of gyration of an unperturbed chain (2R _g), is defined as an ultrathin film. In the case of PS, α _a-relaxation process corresponding to the segmental motion was generally observed at approximately 380 K. Even for both the PS thin and ultrathin films, the α _a-absorption peak was clearly observed. A rheological analysis reveals that the α _a-relaxation behavior for the thin films with the thickness of about 200 nm is the same as that of the bulk sample. On the contrary, in the case of the PS ultrathin films, the α _a-absorption peak on temperature-loss modulus (E) curve is broadened toward both lower and higher temperature sides. This can be interpreted by taking into account that the segmental motion in the vicinity of surface and interface is detectable for such ultrathin films, which should be faster and slower than that in the bulk, respectively. And, it is found that the apparent activation energy (ΔH) for the α _a-relaxation in the ultrathin films becomes smaller than the bulk value probably due to the surface effect. Finally, an interfacial effect on the ΔH was studied by using different substrates. When the interaction between PS and substrate becomes stronger, the ΔH value for the α _a-relaxation in the ultrathin films increases. The results imply that the segmental motion in the polymer ultrathin films is strongly influenced by surface and interfacial effects..
523.	K. Yamamoto, H. Otsulka, A. Takahara,, Preparation of Novel Polymer Hybrids from Imogolite Nanofiber, Polymer J., 39(1), 1-15, 2007.01.
524.	N. Hosaka, H.Otsuka, N. Torikai, A. Takahara, Structure and Dewetting Behavior of Polyhedral Oligomeric Silsesquioxane-Filled Polystyrene Thin Films, Langmuir, 23(2),902-907, 2007.01.
525.	Nao Hosaka, Naoya Torikai, Hideyuki Otsuka, Atsushi Takahara, Structure and dewetting behavior of polyhedral oligomeric silsesquioxane-filled polystyrene thin films, Langmuir, 10.1021/la062255h, 23, 2, 902-907, 2007.01, Polyhedral oligomeric silsesquioxane (POSS) meets increasing interest as a building unit for inorganic-organic hybrid materials. The incorporation of cyclopentyl-substituted POSS (CpPOSS) into polystyrene (PS) thin films led to an inhibition of dewetting. In this paper, the dispersion state of CpPOSS in the CpPOSS/PS hybrid films and, furthermore, the relationships between the structure and dewetting inhibition effect are discussed. Structural analysis of the hybrid films revealed that CpPOSS segregated to the film surface and crystallized. The segregation of CpPOSS to the surface changes the surface free energy and spreading coefficient of the film. Interfacial structure was also roughened by the segregation of CpPOSS, which can contribute to the inhibition of dewetting by pinning the contact line of the PS film with the substrate. The inhibition of dewetting can be attributed to the modification of the film surface and interface by the segregation of CpPOSS..
526.	K. Kuroiwa, T. Shibata, S. Sasaki, A. Takahara, T Kunitake, N. Kimizuka, Supramolecular Control of Spin-Crossover Phenomena in Lipophilic Fe(ll)-1,2,4-triazole Complexes, J. of Polymer Science、Polym. Chem. Ed., Vol.44 pp.5192-5202, 2006.12.
527.	M. Ohnishi, Y. Kozuk, Q.-L. Ye, H. Yoshikawa, K. Awaga, R. Matsuno, M. Kobayashi, A. Takahara, T. Yokoyama, S. Bandow and S. Iijima, Phase selective preparations and surface modifications of spherical hollow nanomagnets, J. Mater. Chem., 16 pp.3215-3220, 2006.12.
528.	M. Kobayashi, R. Matsuno, H. Otsuka, A. Takahara, Precise surface structure control of inorganic solid and metal oxide nanoparticles through surface-initiated radical polymerzation, Sci. Tech. .Adv. Mater., 7 pp.617-628, 2006.12.
529.	Thatiparti Thimma Ready, Michiko Hadano, Atsushi Takahara, Controlled release of model drug from biodegradable segmented polyurethane ureas Morphological and structural features, Macromolecular Symposia, 10.1002/masy.200651033, 242, 241-249, 2006.12, Segmented polyurethane ureas (SPUUs), which are being used in implant devices, were evaluated as drug delivery matrices using theophylline as a model drug without much sacrificing the mechanical properties of films after drug doping. SPUUs were synthesized from aliphatic diisocyanate (lysine methyl ester diisocyante (LDI)), poly(caprolactone) diol with molecular weights 530, 1250 and 2000 and 1,4-butanediamine. Three series of segmented SPUUs were prepared with various soft segment lengths and were characterized by Fourier transform infrared spectroscopy, dynamic viscoelastic measurements and tensile testing. A single tanδ peak was observed in dynamic viscoelastic measurements, which revealed phase mixing of hard and soft segments. Low elongation at break was observed in case of PCL 2000 based SPUUs, may be due to partial cystallization of PCL segment. The degradation of SPUUs in alkaline solution and In vitro drug release of theophylline in pH 7.4 buffer were also investigated. The drug release behavior from these films were analyzed by the exponent relation M _t/M_∞ = ktⁿ, where k and n are constants and M_t/M_∞ is the fraction of drug released until time, t. The constant n was found to be close to 0.5 in all samples, which suggests the release of drug from these polymers can be explained by the Fickian diffusion model..
530.	Y. Lee, B. Kim, W.. Yi, A. Takahara, D.-W. Sohn, Conducting Properties of Polypyrrole Coated Imogolite, Bull.Korean Chem. Soc., Vol.27 No.11 pp.1817−1824, 2006.11.
531.	Y. Matsuda, M. Kobayashi, M. Annaka, K. Ishihara, A. Takahara, Dimension of Poly(2-methacryloyloxyethyl phosphorylcholine) in Aqueous Solutions with Various Ionic Strength, Chemistry Letters, Vol.35 No.11 pp.1310-1311, 2006.11.
532.	Yunha Lee, Bumjoong Kim, Whikun Yi, Atsushi Takahara, Daewon Sohn, Conducting properties of polypyrrole coated imogolite, Bulletin of the Korean Chemical Society, 10.5012/bkcs.2006.27.11.1815, 27, 11, 1815-1818, 2006.11, Imogolite which has chemical composition, (HO)₃Al ₂O₃SiOH, was synthesized with orthosilicate acid and aluminium chloride at low pH solution. It has extremely large aspect ratio with an external diameter of 2nm and the length of a few micrometers. The high aspect ratio of the imogolite could make the material as the filler for the high strength fiber and as the wire for the electronic applications. Here, Imogolite that derives considerable microporosity from a nanometer-sized tubular structure has been modified with a conducting polymer, polypyrrole. Its bonding and wiring structure were confirmed by IR and TEM. The measured conductivity after modification with polypyrrole increased with polypyrrole thickness at various voltage conditions..
533.	Yasuhiro Matsuda, Motoyasu Kobayashi, Annaka Masahiko, Kazuhiko Ishihara, Atsushi Takahara, Dimension of poly(2-methacryloyloxyethyl phosphorylcholine) in aqueous solutions with various ionic strength, Chemistry Letters, 10.1246/cl.2006.1310, 35, 11, 1310-1311, 2006.11, The dimension and intermolecular interaction of poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) in aqueous solutions with various ionic strength was investigated with static and dynamic light scattering. Although PMPC is a polyelectrolyte, its dimension and intermolecular interaction did not change in the aqueous solution of NaCl at 0-0.5 M..
534.	T.T. Reddy, M. Hadano, A. Takahara, Controlled Release of Model Drug from Biodegradable Segmented Polyurethane Ureas: Morphological and Structural Features, Macromol.Symp., p241-249, 2006.10.
535.	K. Miyamoto, N. Hosaka, H. Otsuka, and A. Takahara, Stabilization of Polystyrene Thin Films against Dewetting by Silsesquioxane-terminated Polystyrene Additives, Chemistry Letters, Vol.35 No.l10 pp.1098-1099, 2006.10.
536.	T. Akinaga, S. Yasutake, S. Sasaki, O. Sakata, H. Otsuka, A. Takahara, Analysis of Molecular Aggregation States in Pentacene Thin Films Prepred from Soluble Precursor, Chemistry Letters, Vol.35 No.10 pp.1162-1163, 2006.10.
537.	Takahiro Akinaga, Shigekazu Yasutake, Sono Sasaki, Osami Sakata, Hideyuki Otsuka, Atsushi Takahara, Analysis of molecular aggregation states in pentacene thin films prepared from soluble precursor, Chemistry Letters, 10.1246/cl.2006.1162, 35, 10, 1162-1163, 2006.10, Molecular packing structure in pentacene films prepared from the Afzali's precursor soluble in general organic solvents was characterized by in-plane grazing-incidence X-ray diffraction (GIXD) measurements. The crystallographic ab plane of pentacene was parallel to the surface of a Si substrate. Crystal structure of pentacene near the substrate was identified as the thin-film phase..
538.	Motoyasu Kobayashi, Ryosuke Matsuno, Hideyuki Otsuka, Atsushi Takahara, Precise surface structure control of inorganic solid and metal oxide nanoparticles through surface-initiated radical polymerization, Science and Technology of Advanced Materials, 10.1016/j.stam.2006.07.008, 7, 7, 617-628, 2006.10, Surface-initiated radical polymerization was carried out in order to modify the surface of inorganic solid and metal oxide nanoparticles. Novel (inorganic nanoparticles/polymer) nanocomposites were prepared through a direct polymer grafting reaction from the surfaces of magnetite (Fe₃O₄) (d=10 and 25 nm) and titanium oxide (TiO₂) (d=15 nm) nanoparticles. The initiator for nitroxide-mediated radical polymerization with a phosphoric acid group was chemisorbed onto the nanoparticles and gave controlled polystyrene (PS) and poly(3-vinylpyridine) (P3VP) graft layers on their surfaces. The PS- and P3VP-modified nanoparticles were finely dispersed in organic solvents, whereas protonated P3VP-modified magnetite nanoparticles were dispersed in aqueous phase. The fine dispersion of nanoparticles in the polymer matrix was confirmed by microscopic observation. In order to realize tribological control, atom transfer radical polymerization of (2,2-dimethyl-1,3-dioxolan-4-yl)methyl methacrylate was also carried out from an immobilized initiator on a flat silicon wafer, resulting in a high-density polymer brush that was subsequently converted to a hydrophilic polymer brush consisting of 2,3-dihyroxypropyl methacrylate units. The poly(2,3-dihydroxypropyl methacrylate) brush-immobilized surface showed a low dynamic friction coefficient in water due to the highly stable hydrophilicity..
539.	Kyota Miyamoto, Nao Hosaka, Hideyuki Otsuka, Atsushi Takahara, Stabilization of polystyrene thin films against dewetting by silsesquioxane-terminated polystyrene additives, Chemistry Letters, 10.1246/cl.2006.1098, 35, 10, 1098-1099, 2006.10, A polyhedral oligomeric silsesquioxane (POSS)-containing initiator for nitroxide-mediated radical polymerization was synthesized to prepare organic-inorganic hybrid polymers (PS-POSS), which are polystyrene (PS) with a POSS end group. PS-POSS were well dispersed in PS thin films and provided thermal stability to films against dewetting..
540.	Jun Fukai, Hirotaka Ishizuka, Yosuke Sakai, Masayuki Kaneda, Masamichi Morita, Atsushi Takahara, Effects of droplet size and solute concentration on drying process of polymer solution droplets deposited on homogeneous surfaces, International Journal of Heat and Mass Transfer, 10.1016/j.ijheatmasstransfer.2006.02.049, 49, 19-20, 3561-3567, 2006.09, An experimental setup is constructed to investigate the drying process of a micro-scale polymer solution droplet deposited on homogeneous surfaces. The contact angle during evaporation does not agree with the contact angle hysteresis measured using an inclined plate method due to the size effect. The average polymer concentration at which the contact line is pinned is independent of the initial solution concentration. This fact reveals that the free convection plays an impotent role before pinning. The pinning time, or the receding distance, is moreover found to be a key factor that dominates the shape and dimensions of the polymer films..
541.	Keita Kuroiwa, Tomoko Shibata, Sono Sasaki, Masaaki Ohba, Atsushi Takahara, Toyoki Kunitake, Nobuo Kimizuka, Supramolecular control of spin-crossover phenomena in lipophilic Fe(II)-1,2,4-triazole complexes, Journal of Polymer Science, Part A: Polymer Chemistry, 10.1002/pola.21601, 44, 17, 5192-5202, 2006.09, The spin-crossover properties of lipophilic, supramolecular Fe(II) complexes bridged by 4-(3-dodecyloxy)propyl-1,2,4-triazole [Fe(II)(1) ₃Cl₂] were investigated in chloroform and cast films. A purple low-spin (LS) complex in a powdery form was transformed into pale yellow high-spin (HS) polymers by dissolution in chloroform. The formation of lipophilic molecular wires in chloroform was observed with transmission electron microscopy. The casting of chloroform solutions onto solid supports produced purple, transparent films (LS state). The cast films exhibited sluggish spin-crossover (LS ⇌ HS) behavior without thermal hysteresis. On the other hand, the cocasting of equimolar dodecanol or tetradecanol with Fe(II)(1)₃Cl₂ produced composite films in which alcohol molecules were bound to the complex by ionic hydrogen bonding (ROH⋯Cl^-) and van der Waals interactions. At room temperature, the cast films exhibited regular lamellar structures before and after alcohol doping; this was confirmed by wide-angle X-ray diffraction measurements. Interestingly, the Fe(II)(1)₃Cl₂/C_nOH (n = 12 or 14) ternary films showed a reversible abrupt spin crossover accompanied by thermal hysteresis. The observed bistability was related to dynamic structural transformations between lamellar and hexagonal structures. This study provides a novel supramolecular approach to designing spin-crossover polymer films with controlled thermal bistability..
542.	Mototaka Ohnishi, Yasuharu Kozuka, Quan Lin Ye, Hirofumi Yoshikawa, Kunio Awaga, Ryosuke Matsuno, Motoyasu Kobayashi, Atsushi Takahara, Toshihiko Yokoyama, Shunji Bandow, Sumio Iijima, Phase selective preparations and surface modifications of spherical hollow nanomagnets, Journal of Materials Chemistry, 10.1039/b605472b, 16, 31, 3215-3220, 2006.08, We carried out the phase selective preparations of hollow spheres of ccp- and hcp-Co, Co₃O₄, α-Fe, Fe₃O₄ and α-Fe₂O₃ with a diameter of ca. 600 nm and a shell thickness of 40 nm, using polystyrene (PS)-bead templates. The 600 nm PS beads were uniformly coated with cobalt or iron hydroxides by means of a homogeneous precipitation method. These cobalt-salt/PS hybrid particles were calcined in air at 400 °C and were transformed into Co₃O ₄ hollow spheres. The hcp-Co hollow spheres were obtained by a reduction reaction of the Co₃O₄ particles under a stream of a 1 1 mixed gas of H₂ and N₂ at 400 °C; in contrast, the ccp-Co hollow spheres were obtained by the calcination of the parent cobalt-salt/PS particles under H₂-N₂ at 400 °C. Hollow spheres of Fe₃O₄ and α-Fe₂O ₃ were selectively prepared by calcination of iron-salt/PS particles at 400-500 °C in two different atmospheres, namely under H ₂-N₂ and in air, respectively. Furthermore, the α-Fe₂O₃ particles were reduced into α-Fe under H₂-N₂ at 350 °C without any changes in morphology. These spheres were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD) analyses. Magnetic measurements revealed a significant temperature dependence of the coercive field for the Fe₃O₄ (magnetite) particles, whereas the magnetic properties of the other particles were generally similar to those of the corresponding bulk samples. Surface chemical modifications were carried out on the Fe₃O₄ hollow spheres; the surfaces were grafted with poly(4-N-methylvinylpyridinium) brushes. This treatment was found to induce good dispersibility in water..
543.	Ryosuke Matsuno, Hideyuki Otsuka, Atsushi Takahara, Polystyrene-grafted titanium oxide nanoparticles prepared through surface-initiated nitroxide-mediated radical polymerization and their application to polymer hybrid thin films, Soft Matter, 10.1039/b601197g, 2, 5, 415-421, 2006.07, Polystyrene (PS)-grafted-titanium oxide (TiO₂) nanoparticles with a diameter of 15 nm were prepared by the 'grafting-from' method using the surface initiator for nitroxide-mediated radical polymerization (NMRP). The graft densities were estimated to be 0.04-0.28 chains nm^-2. Under this graft dense region it is assumed that surface polymer chains form a polymer brush structure in good solvents. Wide-angle X-ray diffraction suggested that the tacticity of the PS chains on the nanoparticle surface is mainly atactic. PS-grafted-TiO₂ nanoparticles were stably dispersed in good solvents for PS chains due to the steric repulsion between the grafted chains derived from the osmotic pressure effect and their affinity for the solvents. When the PS-grafted-TiO₂ particles were finely dispersed, the ultraviolet absorption due to TiO₂ was strong and the difference in absorbance between the visible and ultraviolet regions was ten or more times greater than that for non-grafted TiO₂. By adding PS-grafted-TiO₂ particles with PS matrix powder in CHCl₃, hybrid films were prepared by solvent casting. The PS-grafted-TiO₂-PS hybrid films showed high transmittance in the visible light region accompanied by ultraviolet absorption characteristic of TiO₂ due to the fine dispersion of nanoparticles in the PS matrix. Furthermore, friction tests revealed that the wear resistance of PS thin films with PS-grafted-TiO₂ was improved compared with PS film..
544.	Ryoko Iwata, Yasuhiko Iwasaki, Kazunari Akiyoshi, A. Takahara, Well-Controlled Nanobiointerface Generated from Phosphorylcholine Block Copolymers Brushes via a "Grafting From" Process, Trans. Mater. Res. Soc., Japana, Vol.30 No.3 P735-738, 2006.06.
545.	Y, Higaki, H. Otsuka, A. Takahara, A Thermodynamic Polymer Cross-Linking System Based on Radically Exchangeable Covalent Bonds, Macromolecules, Vol.39 No.6 pp.2121-2125, 2006.06.
546.	J. Fukai, Hirotaka Ishizuka, Masayuki Kaneda, M. Morita, Atsushi Tkahara, Effects of droplet size and solute concentration on drying process of polymer solution droplets deposited on homogeneous surfaces, Intern. J. . Heat and Mass Transfer, 49 pp.3561-3567, 2006.05.
547.	Y, Higaki, H. Otsuka, A. Takahara, Facile synthesis of multiblock copolymers composed of poly (tetramethylene oxide) and polystyrene using living free-radical polymerization macroinitiator, Polymer, Vol.47 No.11 pp.3784−3791, 2006.05.
548.	R. Matsuno, H. Otsuka, A. Takahara, Polystyrene-grafted titanium oxide nanoparticles prepared through surface-initiated nitroxide-mediated radical polymerization and their application to polymer hybird thin films, Soft Matter, 2 pp.415-421, 2006.05.
549.	Yuji Higaki, Hideyuki Otsuka, Atsushi Takahara, Facile synthesis of multiblock copolymers composed of poly(tetramethylene oxide) and polystyrene using living free-radical polymerization macroinitiator, polymer, 10.1016/j.polymer.2006.03.100, 47, 11, 3784-3791, 2006.05, A facile synthetic strategy for well-defined multiblock copolymers utilizing 'living' free-radical polymerization macroinitiator has been presented. Polyurethane composed of alkoxyamine initiating units and poly(tetramethylene oxide) (PTMO) segments was prepared by polyaddition of tolylene 2,4-diisocyanate terminated PTMO with an alkoxyamine-based diol. Polymerization of styrene with the polyurethane macroinitiator was carried out under nitroxide-mediated free-radical polymerization (NMRP) condition. GPC, NMR, and IR data revealed that the polymerization was accurately controlled and well-defined polystyrene chains were inserted in the main chain of macroinitiator to give the poly(tetramethylene oxide)-b-polystyrene multiblock copolymers. The synthesized multiblock copolymers were characterized by tensile test, differential scanning calorimetry, and dynamic mechanical analysis. Mechanical properties of the multiblock copolymers can be tuned by the sufficient molecular weight control of PS chains. Soft segment of PTMO and hard segment of PS were apparently compatible due to the multiblock structure of low molecular weight segments and polar urethane groups..
550.	Yuji Higaki, Hideyuki Otsuka, Atsushi Takahara, A thermodynamic polymer cross-linking system based on radically exchangeable covalent bonds, Macromolecules, 10.1021/ma052093g, 39, 6, 2121-2125, 2006.03, A thermodynamic covalent cross-linking system utilizing alkoxyamine units as thermally reversible covalent bonds was demonstrated. By heating the poly(methacrylic ester)s containing alkoxyamine units on the side chain, the cross-linking reaction was achieved as a result of a radical exchange reaction of alkoxyamine moieties. Kinetic studies have revealed that the cross-linking behavior depends remarkably on concentration and reaches equilibrium at a given reaction time, and characteristic reaction behaviors for thermodynamic reactions have been observed. The de-cross-linking reaction was carried out by heating the cross-linked polymer in the presence of an excess amount of alkoxyamine. It was found that the cross-linked points thermally dissociate and that the reaction system is reversible under stoichiometric control..
551.	N. Inoue, H. Otsuka, S.-I. Wada, A. Takahara, (Inorganic Nanofiber/Enzyme) Hybrid Hydrogel: Preparation,Characterization,and Enzymatic Activity of Imogolite/Pepsin Conjugate, Chemistry Letters, 35(2), 2006.02.
552.	Nozomi Inoue, Hideyuki Otsuka, Shin Ichiro Wada, Atsushi Takahara, (Inorganic nanofiber/enzyme) hybrid hydrogel Preparation characterization, and enzymatic activity of imogolite/pepsin conjugate, Chemistry Letters, 10.1246/cl.2006.194, 35, 2, 194-195, 2006.02, The hybrid hydrogel composed of tubular aluminosilicate nanofiber, "imogolite," and pepsin was prepared in a simple manner. We confirmed the formation of a network structure of imogolite in hydrogel by FE-SEM observations. Pepsin immobilized onto imogolite showed enzymatic activity after repeated reactions..
553.	Atsushi Takahara, Development of High-performance Experimental Systems and Fiber Science, Sen'i Gakkaishi, 10.2115/fiber.62.P_41, 62, 2, 2006.01.
554.	M. Kobayashi, A. Takahara, Synthesis and Frictional Properties of Poly(2,3-dihydroxypropyl methacrylate) Brush Prepared by Surface-initiated Atom Transfer Radical Polymerization, Chem. Lett., 10.1246/cl.2005.1582, 34, 12, 1582-1583, Vol.34 No.12 P1582-1583, 2005.12.
555.	K. Yamamoto, H. Otsuka, S.-I. Wada, D.-W. Sohn, A. Takahara, Preparation and properties of [poly(methyl methacrylate)/imogolite] hybrid via surface modification using phosphoric acid ester, Polymer, 10.1016/j.polymer.2005.10.108, 46, 26, 12386-12392, Vol.46 P12386-12392, 2005.12.
556.	A. Yanagi, H. Otsuka, A. Takahara, Adsorbent for Di-n-butyl Phthalate using Chitosan Beads with Upper- or Lower-Rim Substituted Water-soluble Calixarenes, Polymer J., 10.1295/polymj.37.939, 37, 12, 939-945, Vol.37 No.12 P939-945, 2005.12.
557.	K.-I. Akabori, K. Tanaka, T. Nagamura, A. Takahara, T. Kajiyama, Molecular Motion in Ultrathin Polystyrene Films: Dynamic Mechanical Analysis of Surface and Interfacial Effects, Macromolecules, 10.1021/ma051143e, 38, 23, 9735-9741, Vol.38 No.23 P9735-9741, 2005.11.
558.	H. Sakata, M. Kobayashi, H. Otsuka, A. Takahara, "Tribological Properties of Poly(methyl methacrylate) Brushes Prepared by Surface-Initiated Atom Transfer Radical Polymerization", Polym. J., 10.1295/polymj.37.767, 37, 10, 767-775, Vol.37 No.10 P767775, 2005.10.
559.	T. Koga, H. Otsuka, A. Takahara, Imaging of Charged Micropatterned Monolayer Surfaces by Chemical Force Microscopy, Bull. Chem. Soc., Japan, 10.1246/bcsj.78.1691, 78, 9, 1691-1698, Vol.78 No.9 P1691-1698, 2005.09.
560.	Dehui Yin, Shin Horiuchi, M. Morita, A. Takahara, Tunable Metallization by Assembly of Metal Nanoparticles in Polymer Thin Films by Photo- or Electron Beam Lithography, Langmuir, 10.1021/la0511485, 21, 20, 9352-9358, Vol.21 P9352-9358, 2005.09.
561.	Masaya Hikita, Keiji Tanaka, Tetsuya Nakamura, Tisato Kajiyama, Atsushi Takahara, Super-liquid-repellent surfaces prepared by colloidal silica nanoparticles covered with fluoroalkyl groups, Langmuir, 10.1021/la050901r, 21, 16, 7299-7302, 2005.08, A simple and easy method to prepare super-liquid-repellent surfaces is proposed. Sol-gel films were prepared by hydrolysis and condensation of alkoxysilane compounds. Both surface energy and roughness were controlled using colloidal silica particles and fluoroalkylsilane. When the fractional amounts of both colloidal silica and fluoroalkylsilane were optimized in the films, the film surface exhibited repellency to both water and oil. Finally, it was shown that the method proposed here would be applied to a simple one-pot coating for a uniform large area, and be useful for practical use..
562.	M. Morita, S. Yasutake, H. Ishizuka, Y. Sakai, J. Fukai, A. Takahara, Site-selective Coating of Polymer Thin Film Prepared by the Ink-jet Method on the Patterned Fluoroalkylsilane Monolayer Substrate, Chem. Lett., 10.1246/cl.2005.916, 34, 7, 916-917, Vol.34 No.7 P916-917, 2005.07.
563.	Koji Honda, Hirohiko Yakabe, Tomoyuki Koga, Sono Sasaki, Osami Sakata, Hideyuki Otsuka, Atsushi Takahara, Molecular aggregation structure of poly(fluoroalkyl acrylate) thin films evaluated by synchrotron-sourced grazing-incidence X-ray diffraction, Chemistry Letters, 10.1246/cl.2005.1024, 34, 7, 1024-1025, 2005.07, Molecular aggregation structure of poly(fluoroalkyl acrylate) [PFA-C _y, where y is the fluoromethylene number of the fluoroalkyl (R _f) groups] thin films was characterized by grazing-incidence X-ray diffraction (GIXD). In-plane diffractions corresponding to the hexagonal packing of the R_f groups were measured for PFA-C_y with y ≥ 8 in the surface and bulk regions. This result indicated that the R_f groups were oriented almost perpendicular to the film surface..
564.	H. Yokoyama, T. Miyamae, S. Han, T. Ishizoe, K. Tanaka, A. Takahara, N. Torikai, Spontaneously Formed Hydrophilic Surfaces by Segregation of Block Copolymers with Water-Soluble Blocks, Macromolecules, 10.1021/ma050473w, 38, 12, 5180-5189, Vol.38 No.12 P5180-5189, 2005.06.
565.	K. Yamamoto, H. Otsuka, S.-I. Wada, D.-W. Sohn, A. Takahara, Transparent polymer nanohybrid prepared by in situ synthesis of aluminosilicate nanofibers in poly(vivyl alcohol) solution, Soft Matter, 10.1039/b508669h, 1, 5, 372-377, Vol.１　P372-377, 2005.06.
566.	M. Morita, S. Yasutake, H. Ishizuka, Y. Sakai, J. Fukai, A. Takahara, Site Specific Fabrication of Polystyrene Ultrathin Films onto the Patterned Organosilane Monolayer Surfaces by the Ink-Jet Method, Trans. Mater. Res. Soc., Japana, Vol.30 No.3 P631-634, 2005.06.
567.	M. Kobayashi,A. Takahara, Synthesis and Frictional Properties of Poly(2,3-dihydroxypropyl methacrylate) Brush Prepared by Surface Initiated Polymerization on Silicon Wafer, Trans. Mater. Res. Soc., Japana, Vol.30 No.3 P647-650, 2005.06.
568.	Y. Kobashi, H. Otsuka, A. Takahara, Macromolecular Radical Crossover Reaction of Disulfide-Containing Polyester Triggered by Free-Radical Generators, Trans. Mater. Res. Soc., Japana, V0ol.30 No.3 P699-702, 2005.06.
569.	T. Muta, H. Otsuka, A. Takahara, Polymer Scrambling by Macromolecular Olefin Metathesis, Trans. Mater. Res. Soc., Japana, Vol.30 No.3 P715-718, 2005.06.
570.	Y, Higaki, H. Otsuka, A. Takahara, Dynamic Transformation of Polymer Structure by Radical Crossover Reaction, Trans. Mater. Res. Soc., Japana, Vol30 No.3 P719-722, 2005.06.
571.	R. Matsuno, H. Otsuka, A. Takahara, Preparation and Properties of Polymer Hybrids Containing Nanoparticles with Controlled Interfacial Structure, Trans. Mater. Res. Soc., Japana, Vol.30 No.3 P723-726, 2005.06.
572.	Nozomi Inoue, K. Yamamoto, H. Otsuka, S.-I. Wada, A. Takahara, Aggregation Structure and Functional Properties of (Inorganic Nanofiber/ Pepsin) Hybrid Hydrogel, Trans. Mater. Res. Soc., Japana, Vol.30 No.3 P727-730, 2005.06.
573.	Koji Honda, Masamichi Morita, Hideyuki Otsuka, Atsushi Takahara, Molecular aggregation structure and surface properties of poly(fluoroalkyl acrylate) thin films, Macromolecules, 10.1021/ma050394k, 38, 13, 5699-5705, 2005.06, The effects of side chain length on the molecular aggregation states and surface properties of poly(fluoroalkyl acrylate) [PFA-C_y, where y is the fluoromethylene number of the R_f groups] thin films were systematically investigated. Spin-coated PFA-C_y thin films were characterized by static and dynamic contact angle measurements, X-ray photoelectron spectroscopy (XPS), differential scanning calorimetry, and wide-angle X-ray diffraction. The receding contact angles showed small values for PFA-C_y with short side chain (y ≤ 6) and increased for ones with y ≥ 8. It has been revealed that PFA-C_y with y ≥ 8 was crystallized and formed ordered structures. These results suggest that the water-repellent mechanism of PFA-C_y can be attributed to the presence of highly ordered fluoroalkyl chains at the outermost surfaces. The results of XPS in the dried and hydrated states and the contact angle measurement in water indicate that the contact angle for water is lowered by exposure of the carbonyl groups to the water interface through reorientation of short fluoroalkyl chains..
574.	H. Ishida, T. Koga, M. Morita, H. Otsuka, A. Takahara, Macro- and nanotribological properties of organosilane monolayers prepared by a chemical vapor adsorption method on silicon substrates, Tribology Letters, 10.1007/s11249-004-4259-9, 19, 1, 3-8, 2005.05, Organosilane monolayers are novel ultrathin films used to control the physicochemical properties, such as friction and wear, of solid surfaces. In this study, the authors prepared alkylsilane and fluoroalkylsilane monolayers with a series of chain lengths by a chemical vapor adsorption method. The tribological properties were investigated by lateral force microscope (LFM) and friction tester. LFM nanoscale measurements of tribological properties showed that alkylsilane monolayer gave lower lateral force than the Si substrate surface. The lateral force decreased as the length of the alkyl chain increased. On the macroscale, friction test revealed that the organosilane monolayers gave lower dynamic friction coefficients than the Si substrate surface in air at room temperature. The longer the alkyl chain, the greater the wear resistance of the organosilane monolayers. Friction experiments using tetradecane as a lubricant showed better tribological properties than were obtained in air. Furthermore, microscopically linepatterned two-component organosilane monolayers were prepared and their macroscopic friction behavior was investigated. Eventhough the height difference between the two-components was less than 1 nm, friction force anisotropy between the parallel and perpendicular directions against the line pattern was observed..
575.	H. Otsuka, T. Arima, T. Koga, A. Takahara Rational Model for Chiral Recognition in a Silica-based Chiral Column: Chiral Recognition of N-(3.5-dinitrobenzoyl)phenylglycine-terminated Alkylsilane Monolayer by 2,2,2-trifluoro-1-(9-anthryl)ethanol Dertivative, Rational Model for Chiral Recognition in a Silica-based Chiral Column: Chiral Recognition of N-(3.5-dinitrobenzoyl)phenylglycine-terminated Alkylsilane Monolayer by 2,2,2-trifluoro-1-(9-anthryl)ethanol Dertivatives by Chemical Force Microscopy, J. Phys. Org. Chem.　J. Phys. Org. Chem.J. Phys. Org. Chem., 10.1002/poc.934, 18, 9, 957-961, Vol.18 P957-961, 2005.04.
576.	Atsushi Takahara, Michiko Hadano, Tomohiro Yamaguchi, Hideyuki Otsuka, Satoru Kidoaki, Takehisa Matsuda, Characterization of novel biodegradable segmented polyurethanes prepared from amino-acid based diisocyanate, Macromolecular Symposia, 10.1002/masy.200550618, 224, 207-217, 2005.04, Segmented polyurethanes (SPUs) which were expected to yield non-toxic degradation products were synthesized from lysine-based diisocyanate (LDI), 1,3-propanediol (PDO), and polycaprolactone diol (PCL). SPUs were synthesized via a standard two-step prepolymer method. The hard segment fraction was changed in order to tune the mechanical properties and the degradability. The aggregation structures of the SPUs were characterized by infrared spectroscopy and differential scanning calorimetry (DSC), temperature dependence of dynamic viscoelasticity, and small-angle X-ray scattering (SAXS). DSC and dynamic viscoelastic measurements revealed that the glass transition temperature (T _g) of the soft segment increased with an increase in the hard segment fraction. SAXS of SPUs revealed the aggregation states of hard and soft segments. Furthermore, the degradation of SPUs was investigated by exposing the polymers to a buffer solution at 310 K (pH=7.6). The degradation rate of SPUs increased with an increase in the soft segment fraction. This is because the soft segment has the hydrolyzable ester linkages and the ester linkages are susceptible to hydrolysis compared with the urethane linkages. Finally, an electrospray deposition method was used to fabricate biodegradable SPU micro-fibers. FE-SEM images showed that higher concentration of solution favored the formation of uniform biodegradable micro-fibers without beads-like structure..
577.	Go Yamaguchi, Y, Higaki, H. Otsuka, and A. Takahara, Reversible Radical Ring-Crossover Polymerization of an Alkoxyamine-Conataining Dynamic Covalent Marcocycle, Macromolecules　6316−6320, 10.1021/ma0503209, 38, 15, 6316-6320, 2005.03.
578.	Akihiro Yanagi, Hideyuki Otsuka, Atsushi Takahara, Adsorption of di-n-butyl phthalate by chitosan beads modified with water-soluble calixarenes, Chemistry Letters, 10.1246/cl.2005.218, 34, 2, 218-219, 2005.02, The binding ability of di-n-butyl phthalate (DBP) by p-sulfonatocalix[n] arenes {SCAn (n = 4, 6, 8)} and adsorption ability of DBP by chitosan beads modified with SCAn were investigated. SCA6 and SCA8 could include DBP in their hydrophobic cavities in aqueous phase. The amount of DBP adsorbed by chitosan beads modified with SCA6 was approximately 5 times as large as that for unmodified chitosan beads..
579.	Tomoyuki Koga, Masamichi Morita, Hideomi Ishida, Hirohiko Yakabe, Sono Sasaki, Osami Sakata, Hideyuki Otsuka, Atsushi Takahara, Dependence of the molecular aggregation state of octadecylsiloxane monolayers on preparation methods, Langmuir, 10.1021/la048544s, 21, 3, 905-910, 2005.02, The molecular aggregation state of octadecylsiloxane monolayers on Si-wafer substrate surfaces prepared from octadecyltrimethoxysilane (OTMS) or octadecyltrichlorosilane (OTS) was investigated on the basis of grazing incidence X-ray diffraction (GIXD), Fourier transform infrared spectroscopy (FT-IR), contact angle measurement, field emission scanning electron microscopy (FE-SEM), and scanning force microscopy (SFM). The OTMS monolayer was prepared by using the chemical vapor adsorption (CVA) method, and the OTS monolayers, which were used as reference samples, were prepared either by chemisorption (OTS-S) or by the water-cast method (OTS-W). The GIXD, FT-IR, lateral force microscopic (LFM) measurements, and FE-SEM observation revealed that the alkyl chains in the OTMS monolayers prepared using the CVA method are in an amorphous state at room temperature. According to the LFM measurement, the transition temperature from the hexagonal crystalline phase to the amorphous phase was found to be ca. 333 K for the OTS-S monolayer prepared by the chemisorption method. However, the phase transition was not observed in the OTMS monolayer prepared by the CVA method. Also, the atomic force microscopic (AFM) observation and the contact angle measurement showed that the OTMS monolayer prepared by the CVA method has a uniform surface when compared to the OTS monolayers. These results indicated that organosilane compounds in the monolayer prepared by the CVA method were immobilized on the Si-wafer substrate surface in an amorphous state, which was quite different from the hexagonal crystalline state obtained by the chemisorption and water-cast methods..
580.	Masamichi Morita, Tomoyuki Koga, Hideyuki Otsuka, Atsushi Takahara, Macroscopic-wetting anisotropy on the line-patterned surface of fluoroalkylsilane monolayers, Langmuir, 10.1021/la0485172, 21, 3, 911-918, 2005.02, Micropatterned fluoroalkylsilane monolayer surfaces with liquidphilic/liquidphobic area (line width 1-20 μm) were prepared with few defects by vacuum ultraviolet (VUV) photolithography. The anisotropic wetting of a macroscopic droplet with a 0.5-5 mm diameter on the micropatterned surfaces was investigated. The strong anisotropy of the contact angle and the sliding angle and droplet distortion for fluoroalkylsilane/silanol patterned surfaces was attributed to the difference in the energy barrier of wetting between parallel and orthogonal lines. The wetting anisotropy decreased with decreases in the liquidphilic area. Fluoroalkylsilane/alkylsilane patterned surfaces with small differences in the surface free energies of the components showed anisotropic wetting only for the low-surface-tension liquids..
581.	Hirohiko Yakabe, Keiji Tanaka, Toshihiko Nagamura, Sono Sasaki, Osami Sakata, Atsushi Takahara, Tisato Kajiyama, Grazing incidence X-ray diffraction study on surface crystal structure of polyethylene thin films, Polymer Bulletin, 10.1007/s00289-004-0329-2, 53, 3, 213-222, 2005.01, Crystal structure in thin films of melt-crystallized and annealed polyethylene (PE) was examined by grazing incidence X-ray diffraction measurements. Choosing appropriate incident angles of X-rays to the films, surface and bulk molecular aggregation states were successfully extracted. Consequently, it was found that chain packing structure in the surface region was different from that in the bulk one. Based on paracrystalline analysis for the (110) reflection and its higher-order ones of PE orthorhombic crystal, it was clarified that the ordering for the crystalline lattice was lower in the surface region. Also, apparent crystallinity in the surface was lower than the bulk one. These results indicate that disordered crystallites were preferentially formed in the surface region..
582.	Shigeki Nakahara, Masanori Motowoka, Keiji Tanaka, Atsushi Takahara, Tisato Kajiyama, Evaluation of interfacial structure in blends of polypropylene and elastomer by scanning force mircroscopy, KOBUNSHI RONBUNSHU, 10.1295/koron.62.432, 62, 9, 432-434, 2005.01, Flat cross-sections of (polypropylene/elastomer) blends were prepared by ultamicrotoming at 150 K. Then, scanning force microscopy (SFM) was applied to each cross-section to evaluate the interfacial thickness between the two phases in the blend. For this purpose, a viscoelastic mode was superior to a conventional topographic mode. The results obtained well reflected the solubility between the two components. Finally, transmission electron microscopy was applied to the sample. The TEM observations supported what was suggested on the basis of SFM results..
583.	R. Iwata, P. Suk-In, V. P. Hoven, A. Takahara, K. Akiyoshi, Y. Iwasaki, Control of Nanobiointerfaces Generated from Well-Defined Biomimetic Polymer Brushes for Protein and Cell Manipulations, Biomacromolecules, 10.1021/bm049613k, 5, 6, 2308-2314, 5(6) 2308-2314, 2004.12.
584.	T. Yamaguchi, H. Otsuka, S. Kidoaki, T. Matsuda, A. Takahara, Physicochemical Properties and Bio-degradation of Segmented Polyurethane and Poly(urethane-urea) Derived from Lysine-Based Diisocyanate, Trans. Mater. Res. Soc., Japan, 29(6) 2873-2876, 2004.12.
585.	N. Hosaka, K. Tanaka, H. Otsuka and A. Takahara, Influence of the Addition of Silsesquioxane on the Dewetting Behavior of Polystyrene Thin Film, Composite Interfaces, 10.1163/1568554041738157, 11, 4, 297-306, 11(4) 297-306, 2004.10.
586.	T. Izumi, R. Narita, K. Tanaka, A. Takahara and T. Kajiyama, Annealing effect on adhesion properties of poly(butylene terephthalate), Composite Interfaces, 10.1163/1568554041738166, 11, 4, 325-333, 11(4) 325-333, 2004.10.
587.	M. Hikita, T. Nakamura, K. Tanaka, A. Takahara, T. Kajiyama, Aggregation States and Surface Wettability in Films of Poly(styrene-block-2-perfluorooctyl ethyl acrylate) Diblock Copolymers Synthesized by Atom Transfer Radical Polymerization, Langmuir, 10.1021/la049556g, 20, 13, 5304-5310, 20 5304-5310, 2004.06.
588.	Y. Ryosho, S. Sasaki, T. Nagamura, A. Takahara, T. Kajiyama, Anisotropic-to-Isotropic Change in Lateral Force at the Surface of Single-Crystal Lamellae of High-Density Polyethylene during Low-Temperature Annealing, Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ, 10.1021/ma049969o, 37, 13, 5115-5117, 37 5115-5117, 2004.05.
589.	H. Yokoyama, K. Tanaka, A. Takahara, T. Kajiyama, K. Sugiyama, A. Hirao, Surface Segregation of Fluoroalkyl Side Group of Fluorinated Block Copolymers, Trans. Mater. Res. Soc., Japan, 29(1) 279-282, 2004.04.
590.	H. Yakabe, S. Sasaki, O. Sakata, A. Takahara, T. Kajiyama, Crystal Structure in the Near-Surface Region of Melt-Crystallized Polyethylene Films Investigated by Grazing Incidence X-ray Diffraction, Trans. Mater. Res. Soc., Japan, 29(1) 251-254, 2004.04.
591.	Takao Izumi, R. Narita, K. Tanaka, A. Takahara, T. Kajiyama, Influence of annealing treatment on the Adhesion of Poly(butylene terephthalate) and its Interfacial structure, Trans. Mater. Res. Soc., Japan, 29(1) 229-232, 2004.04.
592.	M. Hikita, N. Takizuka, K. Tanaka, A. Takahara, T. Kajiyama, Characterizations and Surface Wettability of Fluorinated Block Copolymers Synthesized by Atom Transfer Radical Polymerization, Trans. Mater. Res. Soc., Japan, 29(1) 225-228, 2004.04.
593.	K.-I. Akabori, K. Tanaka, T. Nagamura, A. Takahara, T. Kajiyama, Segmental Motion in Polystyrene Thin and Ultrathin Films Based on Dynamic Viscoelastic Measurement, Trans. Mater. Res. Soc., Japan, 29(1) 217-220, 2004.04.
594.	N. Hosaka, R. Matsunoo, K. Yamamoto, D. Kawaguchi, K. Tanaka, H. Otsuka, A. Takahara, Influence of Octacyclopentylsilsesquioxane Nanofiller on the Dewetting Behavior of Polymer Thin Film, Trans. Mater. Res. Soc., Japan, 29(1) 161-164, 2004.04.
595.	R. Matsuno, K. Yamamoto, H. Otsuka, A. Takahara, Control of Interfacial Structure and Properties of Magnetite Nanoparticle through Surface-Initiated Nitroxide-Mediated Radical Polymerization of Styrene and 3-Vinylpyridine, Trans. Mater. Res. Soc., Japan, 29(1) 157-160, 2004.04.
596.	T. Koga, M. Morita, H. Otsuka, A. Takahara, Site-Specific Arrangement of Microparticles on Organosilane Monolayer Patterned through Photolithography Process, Trans. Mater. Res. Soc., Japan, 29(1) 153-156, 2004.04.
597.	K. Yamamoto, H. Otsuka, S.-I. Wada, A. Takahara, Preparation of Polymer Nanohybrid via in situ Synthesis of Inorganic Nanofiber in Polymer Solution, Trans. Mater. Res. Soc., Japan, 29(1) 149-152, 2004.04.
598.	H. Otsuka, K. Aotani, Y, Higaki, Go Yamaguchi, A. Takahara, Synthesis Reorganization and Scrambling Behavior of Alkoxyamine-Based Dynamic Covalent Polymers by Macromolecular Radical Crossover Reaction, Trans. Mater. Res. Soc., Japan, 29(1) 145-148, 2004.04.
599.	Y, Higaki, H. Otsuka, A. Takahara, Synthesis of Block and Random Copolymers of 3-Vinylpyridine by Nitroxide-Mediated Radical Polymerization, Trans. Mater. Res. Soc., Japan, 29(1) 141-144, 2004.04.
600.	R. Matsuno, H. Otsuka and A. Takahara, Polystyrene- and Poly(3-vinylpyridine)-Grafted Magnetite Nanoparticles Prepared through Surface-Initiated Nitroxide-Mediated Radical Polymerization, Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ, 10.1021/ma035523g, 37, 6, 2203-2209, 37(5) 2203-2209, 2004.03.
601.	Y, Higaki, H. Otsuka, A. Takahara, Dynamic Formation of Graft Polymers via Radical Crossover Reaction of Alkoxyamines, Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ, 10.1021/ma035518c, 37, 5, 1696-1701, 37(5) 1696-1701, 2004.03.
602.	H. Yokoyama, K. Tanaka, A. Takahara, T. Kajiyama, Surface Structure of Asymmetric Fluorinated Block Copolymers, Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ, 10.1021/ma035191f, 37, 3, 939-945, 37(3) 939-945, 2004.02.
603.	T. Kajiyama, K. Tanaka, A. Takahara, Analysis of Surface Mobility in Polystyrene Films with Monodisperse and Bimodal Molecular Weights by Lateral Force Microscopy, J. of Polymer Science: Part A: Polymer Chemistry, 10.1002/pola.10873, 42, 3, 639-647, 42、639-647, 2004.02.
604.	Shintaro Komatsu, Atsushi Takahara, Tisato Kajiyama, Effect of cyclic fatigue conditions on nonlinear dynamic viscoelasticity and fatigue behaviors for short glass-fiber reinforced nylon6, Polymer Journal, 10.1295/polymj.35.844, 35, 11, 844-850, 2003.12, Fatigue behaviors of short glass-fiber reinforced nylon6 (GF/Ny6) under three cyclic fatigue conditions, tension-tension (T-T), tension-compression (T-C) and compression-compression (C-C), were investigated on the basis of nonlinear dynamic viscoelastic analysis. A nonlinear viscoelastic parameter (NVP) was used for quantitative evaluation of nonlinear dynamic viscoelasticity for the (GF/Ny6) during the fatigue process. The magnitude of NVP increased with a decrease in the fatigue under three cyclic fatigue conditions. Under the T-T type cyclic deformation, glass-fibers that lay parallel to the cyclic deformation direction were broken during the fatigue process. After NVP attained a constant magnitude, cracks propagated perpendicularly to the cyclic deformation direction from the glass-fiber ends and ultimately, the (GF/Ny6) was fractured. The stress distribution in the matrix nylon6 became more inhomogeneous due to both glass-fiber breakage and crack propagation, resulting in an increase in NVP. In the case of the C-C type cyclic deformation, debonding at the (glass-fiber/matrix nylon6) interface occurred during the fatigue process, and the magnitude of NVP was strongly related to the progress of interfacial debonding between glass-fibers and the matrix nylon6. Under the T-C type cyclic deformation, the magnitude of NVP increased accompanying crack growth during the tensile deformation process and also, interfacial debonding during the compressive deformation process..
605.	Yuji Higaki, Hideyuki Otsuka, Atsushi Takahara, Synthesis of well-defined poly(styrene)-b-poly(p-tert-butoxystyrene) multiblock copolymer from poly(alkoxyamine) macroinitiator, polymer, 10.1016/j.polymer.2003.09.002, 44, 23, 7095-7101, 2003.10, The stepwise insertion reaction of styrene (St) and p-tert-butoxystyrene (BOSt) into poly(alkoxyamine) macroinitiator was carried out to provide well-defined poly(St)-b-poly(BOSt) multiblock copolymers. Structural confirmation of the multiblock copolymers was accomplished by NMR and IR measurements. The model reaction also supported that the monomer insertion into the macroinitiator proceeded in accordance with a living fashion..
606.	Daisuke Kawaguchi, Keiji Tanaka, Tisato Kajiyama, Atsushi Takahara, Seiji Tasaki, Surface composition control via chain end segregation in blend films of polystyrene and poly(vinyl methyl ether), Macromolecules, 10.1021/ma034117u, 36, 18, 6824-6830, 2003.09, Surface aggregation states in miscible blends of monodisperse polystyrene (PS) and poly-(vinyl methyl ether) (PVME) were studied by X-ray photoelectron spectroscopy (XPS) in conjunction with neutron reflectivity (NR). In the case of symmetric blends in terms of degree of polymerization, N, PVME and PS were preferentially segregated at the film surface and the interface with a silicon wafer, respectively, to minimize free energy of the system. The concentration profile near the surface obtained by experiments was consistent with a mean-field prediction. Also, the surface composition in symmetric blends composed of PS terminated by fluoroalkyl groups at both ends (α,ω-PS(R_f)2) and PVME was examined. In this case, the surface enrichment of PVME was suppressed by virtue of the surface localization of fluoroalkyl end groups, and the composition was strongly dependent on N. The surface in asymmetric α,ω-PS(R_f)₂/PVME blend, in which N of α,ω-PS(R_f)₂ was much smaller than that of PVME, was mostly covered with the PS segments. The results presented imply a possibility that the surface composition in miscible polymer mixtures could be perfectly regulated combining the chain end effect with the molecular weight disparity between the components..
607.	Hirohiko Yakabe, Sono Sasaki, Osami Sakata, Atsushi Takahara, Tisato Kajiyama, Paracrystalline lattice distortion in the near-surface region of melt-crystallized polyethylene films evaluated by synchrotron-sourced grazing-incidence X-ray diffraction, Macromolecules, 10.1021/ma034526q, 36, 16, 5905-5907, 2003.08, The paracrystalline lattice distortion in the near-surface region of melt-crystallized polyethylene films was evaluated. The evaluation was done by using synchrotron-sourced grazing-incidence x-ray diffraction. The distortion of crystal lattice in the in-plane direction was estimated on the basis of the paracrystalline theory proposed by Hosemann..
608.	Keiji Tanaka, Kohsuke Hashimoto, Tisato Kajiyama, Atsushi Takahara, Visualization of active surface molecular motion in polystyrene film by scanning viscoelasticity microscopy, Langmuir, 10.1021/la034542g, 19, 17, 6573-6575, 2003.08, A monodisperse polystyrene (PS) film was spin-coated on a silicon wafer with native oxide layer and was in part scratched by a blade. Then, the surface modulus on a given area, in which PS and bared silicon were present, was two-dimensionally mapped as a function of temperature by scanning viscoelasticity microscopy. We visually present evidence that the PS surface started to soften up at a temperature much lower than the bulk glass transition temperature..
609.	Kei Ichi Akabori, Keiji Tanaka, Tisato Kajiyama, Atsushi Takahara, Anomalous surface relaxation process in polystyrene ultrathin films, Macromolecules, 10.1021/ma034001y, 36, 13, 4937-4943, 2003.07, Monodisperse polystyrene (PS) films with various thicknesses were spun-coated on silicon wafers with native oxide layer. Surface relaxation behavior in the PS films was studied as a function of thickness by lateral force microscopy (LFM). In the case of a thick PS film, a clear lateral force peak corresponding to surface α_a-relaxation process of segmental motion was observed at a temperature much lower than the bulk glass transition temperature, T_g. As the film became thinner than 3-4 times the radius of gyration of an unperturbed consistent chain, the peak on lateral force vs temperature curve started to broaden out with decreasing thickness and eventually split into two peaks. The appearance temperature of the surface α_a-relaxation peak was invariant with respect to the film thickness even in such an ultrathin state, meaning that surface T_g was insensitive to the thickness. On the other hand, the ultrathinning-induced relaxation process, called surface β-relaxation, was strongly dependent on the thickness in terms of relaxation temperature and apparent activation energy. Finally, possible origins of the surface β-relaxation process were proposed..
610.	Tisato Kajiyama, Keiji Tanaka, Atsushi Takahara, Nano-rheological properties of polymeric solid surfaces, Nihon Reoroji Gakkaishi, 10.1678/rheology.31.33, 31, 1, 33-40, 2003.06, Surface rheological analyses of polymeric solids were presented on the basis of scanning viscoelasticity microscopy (SVM) and lateral force microscopy (LFM). SVM observation for phase-separated polymer blend films revealed two-dimensional distribution of elasticity. In order to study surface thermal molecular motion of monodisperse polystyrene (PS), SVM and LFM measurements were made at various temperatures. Glass transition temperature, T_g, at the surface was discerned to be markedly lower than the corresponding bulk T_g, and the discrepancy of T_g between surface and bulk became larger with decreasing molecular weight. Such an intensive activation of thermal molecular motion at the PS surface can be explained in terms of an excess free volume induced by the segregated chain ends and a reduced cooperativity at the surface. Bulk T_g of miscible binary blends can be well expressed by the Gordon-Taylor equation. Extending this notion to surface, the surface composition in blends would be obtained by measuring surface T_g of each constituent as well as their blend. The surface composition in blend films of two PSs with different molecular weights was experimentally and systematically elucidated. The surface enrichment of a smaller molecular weight component became more remarkable with increasing molecular weight disparity between the two components due probably to an entropic effect..
611.	Keiji Tanaka, Daisuke Kawaguchi, Yasuyuki Yokoe, Tisato Kajiyama, Atsushi Takahara, Seiji Tasaki, Surface segregation of chain ends in α,ω-fluoroalkyl-terminated polystyrenes films, polymer, 10.1016/S0032-3861(03)00391-4, 44, 15, 4171-4177, 2003.06, α,ω-Fluoroalkyl-terminated polystyrenes (α,ω-PS(R_f)₂) with various molecular weights were synthesized by an anionic polymerization. Then, chain end distribution in the surface region of the α,ω-PS(R_f)₂ films was studied by angular-dependent X-ray photoelectron spectroscopy in conjunction with neutron reflectivity. The α,ω-PS(R_f)₂ films annealed under vacuum exhibited surface localization of chain ends. Since the fluoroalkyl chain ends possess a lower surface free energy compared with the main chain part, they energetically prefer to partition to the surface. The extent to which the chain ends were segregated at the surface was examined as a function of molecular weight. Also, it was presented how surface orientation of the fluoroalkyl end groups was dependent on molecular weight. On the other hand, no segregation of the chain ends was observed at the surface of the α,ω-PS(R_f)₂ film annealed in boiled water. This is because the chain ends with a lower surface free energy tend to stay away from the higher energy medium of the boiled water. This result reveals that the surface concentration of chain ends can be regulated by selecting an appropriate annealing condition based on surface thermodynamics..
612.	Hideyuki Otsuka, Koichiro Aotani, Yuji Higaki, Atsushi Takahara, Polymer scrambling Macromolecular radical crossover reaction between the main chains of alkoxyamine-based dynamic covalent polymers, Journal of the American Chemical Society, 10.1021/ja0340477, 125, 14, 4064-4065, 2003.04, A novel polymer hybridization method, "polymer scrambling", was developed on the basis of the macromolecular radical crossover reaction between the main chains of dynamic covalent polymers. The macromolecular crossover reaction was successfully monitored by GPC and NMR measurements. The present methodology is innovative for the preparation of novel polymer hybrid materials at the nanometer scale..
613.	Norifumi Fujita, Hideyuki Otsuka, Atsushi Takahara, Seiji Shinkai, Thin silica film with a network structure as prepared by surface sol-gel transcription on the poly(styrene-b-4-vinylpyridine) polymer film, Chemistry Letters, 10.1246/cl.2003.352, 32, 4, 352-353, 2003.04, Sol-gel polycondensation of tetraethyl orthosilicate (TEOS) was carried out on the cast film of poly(styrene-b-4-vinylpyridine) under basic (benzylamine), acidic (AcOH), and neutral (no catalyst) conditions. It was found that only under the acidic and neutral conditions, the phase-separated periodic structure of the copolymer is finely transcribed into the silica. This is a new, convenient method to create the thin, mosaic film from inorganic materials..
614.	Tisato Kajiyama, Keiji Tanaka, Atsushi Takahara, Surface thermal molecular motion of chain end-modified polystyrenes, Macromolecular Symposia, 10.1002/masy.200390036, 192, 265-270, 2003.03, Surface glass transition temperature, T_g^s, of three classes of monodisperse polystyrene, proton-terminated (PS-H), α,ω-diamino-terminated (α,ω-PS(NH₂)₂) and (α,ω-dicarboxy-terminated (α,ω-PS(COOH)₂), were studied by scanning force microscopy. T_g^s of all samples was discernibly lower than the corresponding bulk glass transition temperature, T_g^b. Also, T_g^s value was strongly dependent on what the chemical structure of chain end groups was. Based on the time-temperature superposition principle, apparent activation energy of the α_arelaxation process corresponding to surface segmental motion was evaluated to be approximately 230 kJ•mol^-1. This value was much smaller than the reported bulk ones, and was independent of the chemical structure of chain ends. This result implies that the cooperativity for the α_a-relaxation process at the PS surface is reduced in comparison with the bulk due probably to an existence of the free space presented to polymer segments at the surface. Hence, it was concluded that the surface α_a-relaxation process was activated by not only the chain end effect but also the reduced cooperativity at the surface..
615.	Tomoyuki Koga, Masamichi Morita, Hiroki Sakata, Hideyuki Otsuka, Atsushi Takahara, Surface Structure and Properties of Multicomponent Micropatterned Organosilane Monolayers Prepared by Stepwise Photodecomposition and Chemisorption Process, International Journal of Nanoscience, 10.1142/S0219581X02000437, 1, 5-6, 419-423, 1,5&6,419-423, 2003.01.
616.	Atsushi Takahara, Area-Selective Molecular Assembly of Organosilanes, "the Encyclopedia of Nanoscience and Nanotechnology,Dekker,New York", 2003.01.
617.	D. Kawaguchi, Keiji Tanaka,Tisato Kajiyama, Atsushi Takahara, S. Tasaki, Mobility Gradient in Surface Region of Monodisperse Polystyrene Films, Macromolecules, 10.1021/ma025667f, 36, 4, 1235-1240, 36,1235-1240, 2003.01.
618.	D. Kawaguchi, Keiji Tanaka,Tisato Kajiyama, Atsushi Takahara, S. Tasaki, Mobility Gradient in Surface Region of Monodisperse Polystyrene Films, Macromolecules, 10.1021/ma025667f, 36, 4, 1235-1240, 36,1235-1240, 2003.01.
619.	Tisato Kajiyama, Keiji Tanaka, Atsushi Takahara, Nano-rheological Properties of Polymeric Solid Surfaces, J. Soc. Rheology, Japan, 31, 1, 33-40, 31,33-40, 2003.01.
620.	Atsushi Takahara, Keiji Tanaka, M. Tozu, T. Hoshi, Tisato Kajiyama, Analysis of Surface Composition of Isotopic Polymer Blends Based on Time-of-Flight Secondary Ion Spectroscopy, Applied Surface Science, 10.1016/S0169-4332(02)00748-1, 203, 538-540, 203-204,538-540, 2003.01.
621.	Keiji Tanaka, K. Kojio, R. Kimura, Atsushi Takahara, Tisato Kajiyama, Surface Relaxation Process of Poly(methyl methacrylate) Brushes Prepared by Atom Transfer Radical Polymerization, Polym. J., 10.1295/polymj.35.44, 35, 1, 44-49, 35,44-49, 2003.01.
622.	Yuji Higaki, Hideyuki Otsuka, T. Endo, Atsushi Takahara, Polyurethane macroinitiator for controlled monomer insertion of styrene, Macromolecules, 10.1021/ma021091i, 36, 5, 1494-1499, 36,1494-1499, 2003.01.
623.	Ryousuke Matsuno, Kazuya Yamamoto, Hideyuki Otsuka, Atsushi Takahara, Polystyrene-Grafted Magnetite Nanoparticles Prepared through Surface-Initiated Nitroxyl-Mediated Radical Polymerization, Chem. Mater., 10.1021/cm020766t, 15, 1, 3-5, 15,3-5, 2003.01.
624.	Atsushi Takahara, Hiroki Sakata, Masamichi Morita, Tomo Yukikoga, Hideyuki Otsuka, Fabrication and characterization of multi-component organosilane nanofilms, Composite Interfaces, 10.1163/156855403771953713, 10, 4-5, 489-504, 2003.01, Multi-component micropatterned organosilane monolayers are fabricated on a Si-wafer substrate by stepwise site-specific vacuum ultraviolet (VUV)-ray photodecomposition and chemisorption. The introduction of different organosilane components is confirmed by X-ray photoelectron spectroscopy (XPS). Atomic force microscopic and lateral force microscopic observations reveal that the line-widths of the micropatterned surface correspond to those of the photomask. Contact angle measurement reveals that the micropatterning of the surface functional groups influences the magnitudes of surface free energy. A line pattern with high wetting contrast shows anisotropic water condensing behavior. Also, the patterned surface is used for the site-specific polymerization and site-specific adsorption of microparticles..
625.	Atsushi Takahara, Tisato Kajiyama, Surface Nano-structure and Nano-mechanical Properties of Organosilane Monolayers, Shinku/Journal of the Vacuum Society of Japan, 10.3131/jvsj.46.98, 46, 2, 98-104, 2003.01.
626.	M. Yasumoto, E. Ishiguro, K. Takemoto, T. Tomimasu, H. Kihara, N. Kamijo, T. Tsurushima, Atsushi Takahara, Kazuhiro Hara, Y. Chikaura, The X-ray microscopy project at Saga SLS, 7th International Conference on X-Ray Microscopy Journal De Physique. IV : JP, 10.1051/jp4:200300030, 104, 63-66, 2003.01, A new high resolution X-ray microscopy project has been proposed at Saga synchrotron light source, which is a third generation synchrotron light facility in Japan. Two microscopy beamlines are planned for this project. One is a scanning microscope in the water window region, and the other is a full-field imaging microscope in the multi-keV X-ray energy region. To demonstrate the feasibility of the project, the optical layout of the scanning microscope was designed. The beamline mainly consists of a 3.5 cm periodical undulator, a varied line-spacing plane grating monochorometer (600 lines/mm) and an end-station including a zone plate. Thus, the calculated X-ray properties focused on the sample position are as follows: the spot size is ∼70 nm, the monochromaticity is ∼2000, and the photon flux is 10⁹ ∼ 10¹⁰ photons/sec..
627.	Shintaro Komatsu, Atsushi Takahara, Tisato Kajiyama, Effect of interfacial interaction between glass-fiber and matrix nylon-6 on nonlinear dynamic viscoelasticity and fatigue behavior for glass-fiber reinforced nylon-6, Polymer Journal, 10.1295/polymj.34.897, 34, 12, 897-904, 2002.12, Effect of (glass-fiber/matrix nylon-6) interfacial interactions on fatigue behaviors of glass-fiber reinforced nylon-6 (GF/Ny6) under a strain controlled condition was investigated on the basis of in situ nonlinear dynamic viscoelasticity. Ny6s mixed with surface-modified and -unmodified short glass-fibers (SMSGF and SUSGF) were used as specimens. An extent of nonlinearity of dynamic viscoelasticity was expressed by nonlinear viscoelastic parameter, NVP, which was calculated from coefficients of the Fourier expanded series of the response signal during a fatigue cycle. The nonlinear dynamic viscoelasticity for both (GF/Ny6)s became remarkable with the progress of fatigue damage. The magnitude of NVP for the (SUSGF/Ny6) was always greater than that for the (SMSGF/Ny6) at a given fatigue time. Since the interface between SUSGF and Ny6 was peeled off during the fatigue test due to the weak interaction, the fatigue damage easily occurred for the (SUSGF/Ny6). Such leads to the non-uniform propagation of the imposed strain through the (SUSGF/Ny6), resulting in an increase of NVP. In the case of the (SMSGF/Ny6), the fatigue damage slowly progressed due to the strong interfacial interaction. Consequently, the nonlinearity of the dynamic viscoelasticity for the (SMSGF/Ny6) was depressed in comparison with the (SUSGF/Ny6)..
628.	Kazuya Yamamoto, Hideyuki Otsuka, Atsushi Takahara, Shin Ichiro Wada, Preparation of a novel (polymer/inorganic nanofiber) composite through surface modification of natural aluminosilicate nanofiber, Journal of Adhesion, 10.1080/00218460213740, 78, 7, 591-602, 2002.12, Imogolite is one of the aluminosilicates with a chemical formula of Al₂O₃SiO₂ (H₂O)_n, consisting of hollow nanotubes with an external diameter of about 2.5 nm and a length from several hundred nanometers to a micrometer. Atomic force microscopic (AFM) observation revealed that the imogolite molecules form a fibrous network at pH = 3.0. Since the outer surface of imogolite consists of the Al-OH group, a strong interaction can be expected between the Al-OH and the -PO(OH)₂ groups. Octadecylphosphonic acid (OPA) was chosen as a model amphiphilic molecule, and it chemisorbed onto the surface of imogolite. Surface coverage of imogolite with OPA was confirmed by infrared spectroscopy, thermogravimetric analysis, and adhesion force measurement by (AFM). The OPA-chemisorbed imogolite was dispersed in hexane whereas it forms precipitates in water. Since imogolite engages in a specific interaction with -PO(OH)₂ groups, it is expected that imogolite can be molecularly dispersed in -PO(OH)₂ group-modified poly(vinyl alcohol) (PVA). Temperature dependence of dynamic viscoelasticity exhibited a higher temperature shift of the α_a-absorption of the matrix phosphorylated PVA for the (imogolite/phosphorylated PVA) hybrid compared with that for phosphorylated PVA..
629.	D. J. Duffy, H. D. Stidham, S. L. Hsu, Sono Sasaki, Atsushi Takahara, Tisato Kajiyama, Effect of polyester structure on the interaction parameters and morphology development of ternary blends Model for high performance adhesives and coatings, Journal of Materials Science, 10.1023/A:1020826616745, 37, 22, 4801-4809, 2002.11, Studies were conducted on ternary blends consisting of poly(propylene oxide) and poly(methyl methacrylate co n-butyl methacrylate) blended with either poly(hexamethylene adipate) or poly(hexamethylene sebacate). These ternary blends form the basis for preparation of high performance polyurethane-based hot-melt adhesives and coatings. Changes in polyester structure were found to strongly alter the miscibility behavior. Binary interaction parameters for the five polymer pairs were determined experimentally, permitting calculation of the phase behavior of the ternary polymer blends. Results predicted by the model are in excellent agreement with experimental observations. The influence of miscibility in the melt on the morphology development is also discussed..
630.	Naoya Torikai, Michihiro Furusaka, Hideki Matsuoka, Yuki Matsushita, Mitsuhiro Shibayama, Atsushi Takahara, M. Takeda, Seiji Tasaki, Hitoshi Yamaoka, Instrumental Design and Performance of a New Pulsed Neutron Reflectometer (ARISA) for Free Surface at KENS, Appl. Phys. A, 10.1007/s003390101095, 74, S264-S266, 74,S264-S266, 2002.01.
631.	A. Sakai, Keiji Tanaka, Tisato Kajiyama, Atsushi Takahara, Thermal Molecular Motion at Surface of Atactic Polypropylene Films, Polymer, 10.1016/S0032-3861(02)00340-3, 43, 19, 5109-5115, 43,5109-5115, 2002.01.
632.	Atsushi Takahara, K. Kojio, Tisato Kajiyama, Effect of Aggregation State on Nanotribological Behaviors of Organosilane Monolayers, Ultramicroscopy, 10.1016/S0304-3991(02)00100-6, 91, 1-4, 203-213, 91,203-113, 2002.01.
633.	A. M. Heintz, R. L. McKiernan, S. P. Gido,J. Penelle, S. L. Hsu, Sono Sasaki, Atsushi Takahara, Tisato Kajiyama, Crystallization Behavior of Strongly Interacting Chains, Macromolecules, 10.1021/ma011794k, 35, 8, 3117-3125, 35, 8,3117-3125, 2002.01.
634.	Yuji Higaski, Atsushi Takahara, Tisato Kajiyama, Deformation Conditions-Nonlinear Viscoelasticity Relationships for HDPE Solid-State Extrudate under Cyclic Fatigue, J. Soc. Rheolgy, 30, 3, 147-153, 30,147-153, 2002.01.
635.	Keiji Tanaka, Tisato Kajiyama, Atsushi Takahara, S. Tasaki, A Novel Method to Examine Surface Composition in Mixtures of Chemically Identical Two Polymers with Different Molecular Weights, Macromolecules, 10.1021/ma011960o, 35, 12, 4702-4706, 35,4702-4706, 2002.01.
636.	Kazuya Yamamoto, Hideyuki Otsuka, Shin-Ichiro Wada, Atsushi Takahara, Preparation of Novel (Polymer/Inorganic Nanofiber) Composite through Surface Modification of Natural Aluminosilicate Nanofiber, J. Adhesion, 78,591-602, 2002.01.
637.	K. Noda, M. Tsuji, Atsushi Takahara, Tisato Kajiyama, Aggregation Structure and Molecular Motion of (Glass-Fiber/Matrix Nylon 66) Interface in Short Glass-FIiber Reinforced Nylon 66 Composites, Polymer, 10.1016/S0032-3861(02)00200-8, 43, 14, 4055-4062, 43,4055-4062, 2002.01.
638.	Sono Sasaki, Y. Sakaki, Atsushi Takahara, Tisato Kajiyama, Microscopic Lamelaar Orientation in High-Density Polyethylene Band Spherulites Studied by Scanning Probe Microscopy, Polymer, 10.1016/S0032-3861(02)00158-1, 43, 12, 3441-3446, 43,3441-3446, 2002.01.
639.	H.-Q. Xiang, Keiji Tanaka, Atsushi Takahara, Tisato Kajiyama, Spectroscopic and Electrochemical Characterizations of Dilithium Octacyanophthalocyanine Langmuir-Blodgett Films, Langmuir, 10.1021/la011401a, 18, 6, 2223-2228, 18,2223-28, 2002.01.
640.	Fengchao Xie, H. F. Zhang, Fuk Kay Lee, Binyang Du, Ophelia K. C. Tsui, Y. Yokoe, Keiji Tanaka, Atsushi Takahara, Tisato Kajiyama,Tianbai He, Effect of Low Surface Energy Chain Ends on the Glass Transition Temperature of Polymer Thin Films, Macromolecules, 10.1021/ma011689a, 35, 5, 1491-1492, 35,1491-1492, 2002.01.
641.	Atsushi Takahara, Y. Hara, K. Kojio, Tisato Kajiyama, Plasma Protein Adsorption Behavior onto the Surface of Phase-separated Organosilane Monolayers on the basis of Scanning Force Microscopy, Coll. Surf. B., 10.1016/S0927-7765(01)00231-4, 23, 2-3, 141-152, 23,141-152, 2002.01.
642.	Tomoyuki Koga, Hideyuki Otsuka, Atsushi Takahara, Area-Selective Fabrication of Polyaniline/Poly(styrenesulfonic acid) Composite Ultrathin Films on Micropatterned Aminosilane Grafted Surfaces, Trans. Materials Research Society, 27,497-500, 2002.01.
643.	Tomoyuki Koga, Hideyuki Otsuka, Atsushi Takahara, Fabriaction of Three-Component Micropatterned Organosilane Monolayer by a Stepwise Photolithography Process, Chem. Lett., 10.1246/cl.2002.1196, 12, 1196-1197, 1196-1197, 2002.01.
644.	Hideyuki Otsuka, Koichiro Aotani, Yuji Higaki, Atsushi Takahara, A Dynamic (Reversible) Covalent Polymer: Radical Crossover Behaviour of TEMPO-containing Poly(alkoxyamine ester)s, Chem. Commun., 10.1039/b209193c, 23, 2838-2839, 2838-2839, 2002.01.
645.	Seiji Higashi, Atsushi Takahara, Tisato Kajiyama, Deformation conditions - Nonlinear viscoelasticity relationship for HDPE solid-state extrudate under cyclic fatigue, Nihon Reoroji Gakkaishi, 10.1678/rheology.30.147, 30, 3, 147-153, 2002.01, Fatigue behavior of HDPE extrudates was investigated on the basis of nonlinear dynamic viscoelastic analyses. The HDPE extrudate was prepared by a solid-state extrusion at an extrusion temperature of 353 K with an extrusion ratio of 11.1. Fatigue tests were carried out under the conditions of strain-controlled frequency of 11 Hz and environmental temperature of 303 K. Three deformation conditions were applied to fatigue tests: tension-tension, tension-compression and compression-compression deformation. Relationship between stress and strain amplitudes during fatigue process indicated that in the cases of tension-compression and compression-compression deformations, fatigue lifetime remarkably decreased with increasing dynamic strain amplitude. Nonlinear viscoelasticity during fatigue process was evaluated quantitatively by nonlinear viscoelastic parameter NVP. With increasing imposed strain amplitude, nonlinear viscoelasticity under compression-compression deformation became more remarkable because kink-bands were formed and stress distribution became inhomogeneous. Analyses of hysteresis loss during fatigue process indicated that nonlinear viscoelasticity was closely related to hysteresis loss consumed for irreversible structural change. In particular, in the case of compression-compression deformation, nonlinearity of viscoelasticity increased remarkably with hysteresis loss consumed for structural change due to kink-band formation..
646.	N. Satomi, Keiji Tanaka, Atsushi Takahara, T. Kajiyama, T. Ishizone, S. Nakahama, Surface molecular motion of monodisperse α,ω-diamino-terminated and α,ω-dicarboxy-terminated polystyrenes, Macromolecules, 10.1021/ma010126w, 34, 25, 8761-8767, 2001.12, Surface glass transition behaviors of monodisperse α,ω-diamino-terminated and α,ω-dicarboxy-terminated polystyrenes (α,ω-PS(NH₂)₂ and α,ω-PS(COOH)₂) were studied by scanning force microscopy and were compared with the results of proton-terminated polystyrene (PS-H). All surface glass transition temperatures, T_g^s, of PS-H, α,ω-PS(NH₂)₂, and α,ω-PS(COOH)₂ were discernibly lower than each corresponding bulk glass transition temperature, T_g^b. However, the magnitude of T_g^s was strongly dependent on the chemical structure of chain end groups, because the surface concentration of chain ends varied with the surface free energy difference between the main chain part and the chain end portion, via the surface segregation or surface depletion of chain ends. This result makes it clear that chain end chemistry is one of determining factors on the magnitude of T_g^s. On the basis of the time-temperature superposition principle applied to the scanning rate dependence of lateral force as a function of temperature, the apparent activation energy, ΔH^‡, of the α_a-relaxation process corresponding to micro-Brownian motion at the surface was evaluated to be approximately 230 kJ mol^-1. This value is much smaller than the reported bulk ones and is independent of the chemical structure of chain ends. This result implies that the cooperativity for the α_a-relaxation process at the PS surface is reduced in comparison with the bulk, probably due to the existence of the free space presented to polymer segments at the surface. Hence, it was concluded that the surface α_a-relaxation process was activated by not only the chain end effect but also the reduced cooperativity at the surface. Finally, possible other factors determining on the magnitude of T_g^s were discussed..
647.	Ken Kojio, Keiji Tanaka, Atsushi Takahara, Tisato Kajiyama, Novel method to prepare organosilane monolayers on solid substrate, Bulletin of the Chemical Society of Japan, 10.1246/bcsj.74.1397, 74, 8, 1397-1401, 2001.08, A novel and convenient method to prepare organosilane monolayers was proposed. Pure water was put onto a cleaned silicon wafer and then a toluene solution of n-trichloro(octadecyl)silane (OTS) was spread on it. X-ray photo-electron spectroscopy and atomic force microscopic observation revealed that an OTS monolayer was successfully formed on the solid substrate after the water was evaporated. The static water contact angle of the silicon wafer covered with the OTS monolayer was 105°. Molecular aggregation states of the OTS monolayer were examined by electron diffraction, Fourier transform infrared spectroscopic, X-ray reflectivity, and grazing incidence X-ray diffraction measurements. The prepared OTS monolayer was in a two-dimensional hexagonal crystalline state at 293 K and alkyl chains of the OTS molecules were oriented normal to the surface. Also, the alkyl chains in the monolayer were highly ordered, although the experimental procedure for the monolayer preparation was quite simple. The development of this novel method to prepare a low energy surface will contribute to the material science as well as having industrial applications..
648.	Atsushi Takahara, Yukiko Hara, Ken Kojio, Tisato Kajiyama, Characterization of the surface structural, mechanical, and thermal properties of benzocyclobutene dielectric polymers using scanned probe microscopy, Macromolecular Symposia, 10.1002/1521-3900(200103)167:13.0.CO;2-D, 167, 213-226, 2001.06, Scanning probe microscopy (SPM) techniques are used to characterize surfaces related to the processing of benzocyclobutene (BCB) dielectric thin films. Thermally cured resins and photodefineable resins are sold under the trade name CYLCOTENE™ ¹⁾ for electronic applications. TappingMode AFM (TMAFM) imaging is used to follow changes in adhesion promoter morphology upon baking to help explain adhesion performance. Power spectral density (PSD) analysis of TMAFM images of plasma treated BCB surfaces are unique and can be used to 'fingerprint' processes. Selective oxidation of the BCB surface can be used to fabricate a phase imaging standard for TMAFM. Near surface modulus of the BCB materials is 3.6 ± 0.2 GPa and the hardness is 0.38 ± 0.2 GPa measured by depth-sensing nanoindentation. Creep recovery of indents can be used to qualitatively distinguish between thermal and photocureable materials. A heated tip in a scanning thermal microscope can induce the thermal curing of BCB over micron sized areas. Local thermal analysis with the same probe allows the measurement of the changes in the glass transition, T _g, at the surface with cure temperature..
649.	Kazuya Yamamoto, Hideyuki Otsuka, Shin-Ichiro Wada, Atsushi Takahara, Preparation of Novel Green-Hybrid from "Imogolite" Nanofiber and Poly(vinyl alcohol), Polymeric Materials: Science Enginerring, 84,593-594, 2001.01.
650.	Tomoyuki Koga, Hideyuki Otsuka, Atsushi Takahara, In situ Preparation of Self-assembled Polyaniline/Poly(styrene sulfonic acid) Composite Ultra Thin Films on Aminosilane Grafted Surfaces, Trans Mater. Res. Soc. Jpn., 26,889-892, 2001.01.
651.	Kazuya Yamamoto, Hideyuki Otsuka, Shin-Ichiro Wada, Atsushi Takahara, Surface Modification of "Imogolite" Nanofiber for Nanocomposite Applications, Trans Mater. Res. Soc. Jpn., 26,893-896, 2001.01.
652.	Kazuya Yamamoto, Hideyuki Otsuka, Shin-Ichiro Wada, Atsushi Takahara, Surface Modification of Aluminosilicate Nanofiber "Imogolite", Chem. Lett., 11, 1162-1163, 1162-1163, 2001.01.
653.	X. Jiang, C.-Z. Yang, Keiji Tanaka, Atsushi Takahara, Tisato Kajiyama, Effect of Chain End Group on Surface Glass Transition Temperature of Thin Polymer Film, Phys. Lett., 10.1016/S0375-9601(01)00150-5, 281, 5-6, 363-367, A281,363-367, 2001.01.
654.	K. Noda, Atsushi Takahara, Tisato Kajiyama, Fatigue Failire Mechanisms of Short Glass-Fiber Reinforced Nylon 66 Based on Nonlinear Dynamic Viscoelastic Measurement, Polymer, 10.1016/S0032-3861(00)00897-1, 42, 13, 5803-5811, 42,5803-5811, 2001.01.
655.	K. Kojio, Atsushi Takahara, Tisato Kajiyama, Aggregation Structure and Surface Properties of Immobilized Fluoroalkylsilane and Their Mixed Monolayers, "ACS Symp. Ser. 787, Fluorinated Surfaces, Coatings, and Films", 31-47, 2001.01.
656.	H. Sugihara, Atsushi Takahara, Tisato Kajiyama, Mechanical Nanofabrication of Lignoceric Acid Monolayer with Atomic Force Microscopy, J. Vac.Sci. Tech.B, 10.1116/1.1347042, 19, 2, 593-595, 19,593-595, 2001.01.
657.	Atsushi Takahara, Y. Hara, K. Kojio, Tisato Kajiyama, Scanning Force Microscopic Study of Protein Adsorption on the Surface of Organosilane Monolayers Prepared by the Langmuir-Blodgett Method, Macromol. Symp., 10.1002/1521-3900(200103)167:13.0.CO;2-Y, 167, 271-284, 167,273-286, 2001.01.
658.	H.-Q. Xiang, Keizi Tanaka, Atsushi Takahara, Tisato Kajiyama, Reversible Reduction and Reoxidation of Langmuir-Blodgett Films of Octacyanophthalocyanine Dilithium Complex, Chem. Lett., 10.1246/cl.2001.536, 6, 536-537, 536-537, 2001.01.
659.	D. Kawaguchi, Keiji Tanaka, Atsushi Takahara, Tisato Kajiyama, SurfaceMobile Layer of Polystyrene Film Below Bulk Glass Transition Temperature, Macromolecules, 10.1021/ma010012k, 34, 18, 6164-6166, 18,6164-6166, 2001.01.
660.	N. Satomi, Keiji Tanaka, Atsushi Takahara, Tisato Kajiyama, Effect of Internal Bulk Phase on Surface Voscoelastic Properties by Scanning Probe Microscopy, Macromolecules, 10.1021/ma001831s, 34, 18, 6420-6423, 18,6420-6423, 2001.01.
661.	Ken Kojio, Keiji Tanaka, Atsushi Takahata, Tisato Kajiyama, New Method to Prepare Organosilane Monolayers on Solid Substrate, Bull. Chem. Soc., Japan, 74,1397-1401, 2001.01.
662.	X. Jiang, C.-Z. Yang, Keiji Tanaka, Atsushi Takahara, Tisato Kajiyama, Surface Realaxation Behavior of Proton- and Perfluoroalkyl-terminated Poly(2-vinylpyridine) Films, Polymer, 10.1016/S0032-3861(01)00384-6, 42, 21, 8959-8964, 42,8959-8964, 2001.01.
663.	Kazuya Yamamoto, S.-I. Wada, Hideyuki Otsuka, Atsushi Takahara, Surface Modification of Imogolite for Nanocomposite Application, Trans. Materials Research Society, Japan, 26,893-896, 2001.01.
664.	Tomoyuki Koga, Hideyuki Otsuka, Atsushi Takahara, In situ Formation of Polyaniline/Polystyrene Sulfonic Acid Thin Film on Aminosilane Grafted Surfaces, Trans. Materials Research Society, Japan, 26,889-892, 2001.01.
665.	Naoya Torikai, M. Furusaka, Hideki Matsuoka, Y. Matsushita, Mitsuhiro Shibayama, Atsushi Takahara, M. Takeda, Seiji Tasaki, Hitoshi Yamaoka, A New Thermal Neutron Reflectometer for Free Surface at KENS? ARISA, Proceeding of 15th Meeting of the International Collaboration on Advanced Neutron Sources, 443-449, 2001.01.
666.	Kazuya Yamamoto, Hideyuki Otsuka, S.-I. Wada, Atsushi Takahara, Surface Modification of Aliminosilicate Nanofiber “Imogolite”, Chem. Lett., 11, 1162-1163, 11, 2001.01.
667.	Kazuya Yamamoto, Hideyuki Otsuka, Shin Ichiro Wada, Atsushi Takahara, Surface modification of aluminosilicate nanofiber "Imogolite", Chemistry Letters, 10.1246/cl.2001.1162, 11, 1162-1163, 2001.01, The nanostructure of natural aluminosilicate nanofiber "imogolite" under acidic conditions was directly confirmed by observation with atomic force microscope (AFM) for the first time. The outer surface of imogolite was successfully hydrophobidized by chemisorption of a phosphonic acid derivative with an alkyl chain..
668.	Ken Kojio, Atsushi Takahara, Tisato Kajiyama, Aggregation Structure and Surface Properties of Immobilized Fluoroalkylsilanes and Their Mixed Monolayers, ACS Symposium Series, 787, 31-47, 2001, Stable fluoroalkyl, alkyl and mixed fluoroalkyl/alkyl monolayers were prepared on solid substrates by the Langmuir method. The n-octadecyltrichlorosilane (OTS), 18-nonadecenylrichlorosilane (NTS) and [3-(perfluorododecyl)propyloxy]triethoxysilane (FDOPTES) in monolayers were in a crystalline state at 293 K, as by electron diffraction (ED) studies. In contrast, the n-dodecyltrichlorosilane (DDTS) and [2-(perfluorooctyl)ethyl] -trichlorosilane (FOETS) monolayers with shorter hydrophobic chains were in an amorphous state at 293 K. Molecular images of the crystalline OTS and FDOPTES monolayers were acquired with high-resolution atomic force microscopy (AFM). The direct observation of the molecular arrangement of the crystalline OTS and FDOPTES was successfully achieved The (10) spacings for these monolayers corresponded well to the cross section area of the alkyl and fluoroalkyl chains. It was revealed from the contact angle measurements that the magnitudes of surface free energies of the fluoroalkylsilane monolayers were higher than of the alkylsilane monolayers. The surface free energy of the crystalline fluoroalkylsilane monolayer (FDOPTES monolayer) was higher than that of the amorphous monolayers due to high orientation of the fluoromethyl end groups at the monolayer surface. AFM observation revealed that the (crystalline OTS/amorphous FOETS) mixed monolayer was in a phase-separated state due to the crystallization of the OTS molecules. The (crystalline NTS/amorphous FOETS) mixed monolayer also showed a phase separation. By oxidation of the NTS phase in the (NTS/FOETS) mixed monolayer, a phase-separated structure with large suface energy gap can be constructed. The surface properties of the mixed monolayer was evaluated based on lateral force microscopy (LFM) and adhesion force measurement. Literatures cited..
669.	Atsushi Takahara, Kensuke Nakamura, Keiji Tanaka, Tisato Kajiyama, Polymer battery R&D in the U.S., Macromolecular Symposia, 10.1002/1521-3900(200010)159:13.0.CO;2-O, 159, 229-245, 2000.12, Polymer electrolytes that have been developed for battery applications fall into two general classes, neat or "pure" polymer and plasticized or gel in which the polymer is combined with a conducting organic electrolyte. The polyethylene oxide (PEO) and its modifications are typical of the "pure" polymer electrolytes. They have poor conductivity at room temperatures, but at elevated temperatures, their conductivity is of the order of 10 ^-3 to 10 ^-4 S/cm. The PEO electrolytes have found application in the high temperature (>60°C) lithium metal anode battery systems. The high temperature necessary for good operation makes them unsuitable for use in small consumer appliances. The polymer electrolyte battery development activities have resulted in several high performance battery systems now just entering the market. Not all of the developments have resulted in commercial cell production. The commercialization activities of high performance lithium-ion (Li-Ion) batteries have been based on two general plastic polymer systems: poly-vinylidene difluoride-hexafluoropropylene copolymer (PVdF-HFP) and polyacrylates. The polymer cells are expected to have advantages in manufacturing, flexibility, thin cell formats and lightweight packaging. Important parameters in PVdF gel electrolyte performance include the electrolyte type (combination of organic carbonates), temperature, and HFP copolymer content. Li-Ion coin cells fabricated with a polyolefin separator with either liquid electrolyte or with the PVdF gel polymer electrolyte have equivalent performance..
670.	Ken Kojio, Atsushi Takahara, Tisato Kajiyama, Molecular aggregation state and molecular motion of organosilane monolayers prepared at the air/water interface, Langmuir, 10.1021/la0004303, 16, 24, 9314-9320, 2000.11, Relationships between the molecular aggregation state and the molecular motion of organosilane monolayers with various chain lengths prepared by the Langmuir-Blodgett (LB) method were investigated by lateral force microscopic, Fourier transform-infrared (FT-IR) spectroscopic, and electron diffraction (ED) measurements. The lateral force of the organosilane monolayers increased with increasing their chain length. This is mainly because the intermolecular cohesive energy is proportional to the number of carbons in a chain. The lateral force of the alkylsilane monolayer was compared with that of the fluoroalkylsilane monolayer for the corresponding alkyl chain length. Consequently, the fluoroalkylsilane monolayer showed higher lateral force than the alkylsilane one. Temperature-dependent ED and FT-IR measurements revealed that the molecular aggregation state of the n-octadecyltrichlorosilane (OTS) monolayer changed from the rectangular lattice to the amorphous state via the hexagonal lattice with increasing temperature. The transition temperatures, rectangular to hexagonal and hexagonal to amorphous, were found to be 240 and 333 K, respectively. The distinct lateral force decrease was concurrently observed for the OTS monolayer at 240 and 333 K. The remarkable decrement of the lateral force at 240 K might be attributed to the decreasing molecular density and the activation of molecular motion (rotational motion along the molecular axis) owing to the rectangular-hexagonal crystal transition. And, the second remarkable depression of the lateral force observed at 333 K might come from the activation of thermal molecular motion due to the melting of alkyl chains..
671.	Atsushi Takahara, Yukiko Hara, Ken Kojio, Tisato Kajiyama, Scanning force microscopic observation of protein adsorption on the surface of organosilane monolayers prepared by Langmuir-Blodgett method, Washington,DC. Meeting American Chemical Society, Polymer Preprints, Division of Polymer Chemistry, 41, 2, 1442-1443, 2000.08, The (alkyltrichlorosilane/fluoroalkyltrichlorosilane) mixed monolayer with various surface chemistry was prepared as a model surface for protein-surface interaction studies. The interaction of protein at the solid-liquid interface was examined using bovine serum albumin (BSA). The protein-monolayer surface interaction was determined based on atomic force microscopy (AFM)..
672.	Masami Yanagida, Atsushi Takahara, Tisato Kajiyama, Construction of C₆₀ monolayer based on structural relaxation on the water surface, Bulletin of the Chemical Society of Japan, 10.1246/bcsj.73.1429, 73, 6, 1429-1435, 2000.06, A C₆₀ monolayer was constructed by a multi-step creep method for the first time. In the case that a dilute C₆₀ benzene solution of 1 x 10^-5 M (1 M = 1 mol dm^-3) was spread on the water surface, C₆₀ molecules formed into highly organized 2-dimensional crystalline domains. On the other hand, in the case of the conventional continuous compression method up to a low surface pressure below 15 mN m^-1, the C₆₀ monolayer-like aggregates were formed with a lot of vacancies. Each monolayer-like C₆₀ aggregate was easily collapsed into small fragments and changed into 3-dimensional aggregates at a high surface pressure above 20 mN m^-1. The C₆₀ film could not full up the vacancies during continuous compression, since the C₆₀ molecules formed rigid aggregates. These results clearly indicate that structural relaxation at a low surface pressure was required to construct the defect-diminished C₆₀ monolayer. The occupied area of a C₆₀ molecule in the monolayer prepared by the multi-step creep method was in good agreement with that of a 2-dimensional C₆₀ crystal calculated from lattice constants of a 3-dimensional C₆₀ crystal. The surface morphology of the C₆₀ monolayer prepared by the multi-step creep method was homogeneous, and C₆₀ molecules in the monolayer were closely and regularly packed in a hexagonal array. The hexagonal packing of the C₆₀ molecules was confirmed on the basis of atomic force microscopic and electron diffraction observations..
673.	Tisato Kajiyama, Keiji Tanaka, Noriaki Satomi, Atsushi Takahara, Surface rheology of polymeric solids, Chinese Journal of Polymer Science (English Edition), 18, 3, 239-248, 2000.05, Surface molecular motions of amorphous polymeric solids have been directly measured on the basis of scanning viscoelasticity microscopic (SVM) and lateral force microscopic (LFM) measurements. SVM and LFM measurements were carried out for films of conventional monodisperse polystyrene (PS) with sec-butyl and proton-terminated end groups at room temperature. In the case of the number-average molecular weight, M_n, less than ca. 4.0 × 10⁴, the surface was in a glass-rubber transition state even though the bulk glass transition temperature, T_g was far above room temperature, meaning that the surface molecular motion was fairly active compared with that in the bulk. LFM measurements of the monodisperse PS films at various scanning rates and temperatures revealed that the time-temperature superposition was applicable to the surface mechanical relaxation behavior and also that the surface glass transition temperature, T_g^σ, was depressed in comparison with the bulk one even though the magnitude of M_n was fairly high at 1.40 × 10⁵. The surface molecular motion of monodisperse PS with various chain end groups was investigated on the basis of temperature-dependent scanning viscoelasticity microscopy (TDSVM). The T_g^σs for the PS films with M_n of 4.9 × 10³ to 1.45 × 10⁶ measured by TDSVM were smaller than those for the bulk one, with corresponding M_ns, and the T_g^σs for M_ns smaller than ca. 4.0 × 10⁴ were lower than room temperature (293 K). The active thermal molecular motion at the polymeric solid surface can be interpreted in terms of an excess free volume near the surface region induced by the surface localization of chain end groups. In the case of M_n = ca. 5.0 × 10⁴, the T_g^σs for the α,ω-diamino-terminated PS (α,ω-PS(NH₂)₂) and α,ω-dicarboxy-terminated PS (α,ω-PS(COOH)₂) films were higher than that of the PS film. The change of T_g^σ for the PS film with various chain end groups can be explained in terms of the depth distribution of chain end groups at the surface region depending on the relative hydrophobicity..
674.	T. Kajiyama, K. Tanaka, N. Satomi, A. Takahara, Surface glass transition temperatures of monodisperse polystyrene films by scanning force microscopy, Science and Technology of Advanced Materials, 10.1016/S1468-6996(99)00005-4, 1, 1, 31-35, 2000.03, Surface molecular motion of monodisperse polystyrene (PS) films was examined by scanning viscoelasticity microscopy (SVM) in conjunction with lateral force microscopy (LFM). The dynamic storage modulus, E¹, and loss tangent, tan δ, at a PS film surface with a smaller number-average molecular weight, M_n, than 40k were found to be smaller and larger than those for the bulk sample even at room temperature, meaning that the PS surface is in a glass-rubber transition state or a fully rubbery one at this temperature if the M_n, is small. In order to elucidate quantitatively how vigorous the molecular motion at the PS surface is, SVM and LFM measurements were made at various temperatures. The glass transition temperature, T_g, at the surface was discerned to be markedly lower than its bulk T_g, and the discrepancy of T_g between surface and bulk becomes larger with the decreasing M_n. Such an intensive activation of thermal molecular motion at the PS surfaces can be explained in terms of an excess free volume in the vicinity of the film surface induced by the preferential segregation of chain end groups..
675.	T. Fujii, Atsushi Takahara, Tisato Kajiyama, Scanning Force Microscopic Study of Polyethylene Single Crystals Prepared by a Self-Seeding MethodACS Symp. Ser., Microstructure and Microtribology of Polymer Surfaces, 741,336-345, 2000.01.
676.	Atsushi Takahara, S.-R. Ge, Ken Kojio, Tisato Kajiyama, In situ Atomic Force Microscopic Observation of Albumin Adsorption onto Phase-separated Organosilane Monolayer Surfaces, J. Biomater. Sci., Polym. Ed, 10.1163/156856200743535, 11, 1, 111-120, 11,111-120, 2000.01.
677.	N. Miki, Keiji Tanaka, Atsushi Takahara, Tisato Kajiyamam, Secondary Ion Mass Spectroscopic Analysis of Copper Migration at the Copper/Polyimide Interface, J. Vac. Sci. Tech. B, 10.1116/1.591191, 18, 1, 313-316, 18,313-316, 2000.01.
678.	Ken Kojio, Atsushi Takahara, Tisato Kajiyama, Molecuilar Aggregation State of n-Octadecyltrichlorosilane Monolayers Prepared by the Langmuir andChemisorption Methods, Langmuir, 10.1021/la9909042, 16, 8, 3932-3936, 16,3932-3936, 2000.01.
679.	Tiaro Kajiyama, Keiji Tanaka, N. Satomi, Atsushi Takahara, Surface Rheology of Polymeric Solids, Chinese J. Polym. Sci., 18, 3, 239-248, 18,239-248, 2000.01.
680.	Tisato Kajiyama, Keiji Tanaka, N. Satomi, Atushi Takahara, Surface Glass Transition Behaviors of Monodisperse Polystyrene Films by Scanning Force Microscopy, Sci. Tech. Adv. Mater., 1,31-35, 2000.01.
681.	Keiji Tanaka, Atushi Takahara, Tisato Kajiyama, Rheological Analysis of Surface Relaxation Process of Monodisperse Polystyrene Films, Macromolecules, 10.1021/ma000406w, 33, 20, 7588-7593, 33,7588-7593, 2000.01.
682.	Ken Kojio, Atsushi Takahara, Tisato Kajiyama, Formation Mechanism of n-Octadecyltrichlorosilane Monolayer Prepared at Air/Water Interface, Coll & Surf. A, 10.1016/S0927-7757(00)00444-1, 169, 1-3, 295-306, 169,295-306, 2000.01.
683.	Tisato Kajiyama, N. Satomi, Y. Yokoe, D. Kawaguchi, Keiji Tanaka, Atshushi Takahara, Effect of End Group Chemistry on Surface Molecular Motion of Monodisperse Polystyrene Films, Macromol. Symp., 159,35, 2000.01.
684.	Atushi Takahara, K. Nakamura, Keiji Tanaka, Tisato Kajiyama, Surface Aggregation Structure and Surface Mechanical Properties of Binary Polymer Blend Thin Films, Macromol. Symp., 10.1002/1521-3900(200010)159:13.0.CO;2-U, 159, 89-96, 159,89-96, 2000.01.
685.	Tisato Kajiyama, D. Kawaguchi, A. Sakai, N. Satomi, Keiji Tanaka, Atushi Takahara, Determination Factors on Surface Glass Transition Temperatures of Polymeric Solids, High Performance Polymers, 10.1088/0954-0083/12/4/314, 12, 4, 587-597, 12,587-597, 2000.01.
686.	Norihiko Miki, Atsushi Takahara, Tisato Kajiyama, Effect of precursor solvent on the copper migration behavior at the (polyimide/copper) interface, KOBUNSHI RONBUNSHU, 10.1295/koron.57.233, 57, 4, 233-243, 2000.01, Copper (Cu) migration at the interface of (polyimide(PI)/Cu) bilayers prepared from various precursors was investigated on the basis of dynamic secondary ion mass spectroscopic (D-SIMS) analysis. The Cu migration into the PI phase at the (PI/Cu) interface was clearly detected from the D-SIMS profiles. The Cu migration state depended on the presence of carboxyl groups of PI precursor during the interface formation and on the properties of solvents. On the basis of the D-SIMS profiles, a model of the Cu migration state at the (PI/Cu) interface was proposed. The model consisted of an interfacial region formed by the interpercolation of each component and a diffusional region formed by the diffusion of precursor molecules complexed with Cu. The degree of gradual decrease of Cu secondary-ion intensity from the (PI/Cu) interface to the PI surface ((PI/air)interface) depended on the polarity of solvents. The interfacial region as well as the diffusional one was formed for the specimen prepared from the precursor solutions of aprotic polar solvent. On the other hand, only the interfacial region was formed for the specimen prepared from the precursor solutions of protic solvent. Therefore, it was concluded that the Cu migration state mainly depends on the complex formation with Cu and the diffusion capability of the PI precursor, while the contribution of the solvent was very small..
687.	Ken Kojio, Atsushi Takahara, Tisato Kajiyama, Aggregation structure and surface properties of 18-nonadecenyltrichlorosilane monolayer and multilayer films prepared by the Langmuir method, ACS Symposium Series, 729, 332-352, 1999.12, The 18-nonadecyltrichlorosilane (NTS) monolayer with a vinyl end group was prepared by the Langmuir method. The monolayer with a hydrophilic carboxylated surface was subsequently obtained by oxidation of the vinyl end group. For the multilayer preparation, the NTS monolayer was immobilized onto the hydrophilic carboxylated NTS (NTS_COOH) monolayer. The NTS multilayer film was obtained by repetitions of depositions and oxidations. Aggregation structure of the NTS multilayer film was evaluated on the basis of X-ray reflectivity (XR), Brewster angle infrared (IR) spectroscopic measurements, electron diffraction (ED) and atomic force microscopic (AFM) observations. It was revealed that the NTS multilayer film with a well-ordered structure could be prepared by the Langmuir method. The local height control was performed by utilizing the phase-separated mixed monolayer being composed of the NTS and [2-(perfluorooctyl)ethyl]trichlorosilane (FOETS) molecule. The (NTS/FOETS) mixed monolayer showed phase-separated structure like sea-island, whose domain and matrix phases were composed of crystalline NTS and amorphous FOETS molecules, respectively. The (NTSCooH/FOETS) mixed monolayer with the hydrophilic domain and the hydrophobic matrix was obtained by selective oxidization of the NTS phase in the (NTS/FOETS) mixed monolayer. Furthermore, the local height control on the NTS_COOH phase of the (NTS_COOH/_FOETS) mixed monolayer was performed by chemisorption of NTS from the solution. The height increase in the NTS_COOH phase was confirmed by AFM and lateral force microscopy (LFM)..
688.	Xiqun Jiang, Keiji Tanaka, Atsushi Takahara, Seiichi Nakahama, Tisato Kajiyama, Chain end group-induced surface ordering in poly(styrene-b-4-vinylpyridine) symmetric diblock copolymer films, Polymer Journal, 31, 11 pt 2, 1015-1020, 1999.12, The proton-terminated and fluoroalkyl-terminated poly(styrene-b-4-vinylpyridine) [P(St-b-4VP)] symmetric diblock copolymers were synthesized by a sequential anionic polymerization. The surface chemical composition, surface morphology and surface mechanical properties of the diblock copolymer thin films were investigated on the basis of the angular-dependent X-ray photoelectron spectroscopic (ADXPS) measurement and transmission electron microscopic (TEM) observations. The XPS results revealed that in the case of the proton-terminated P(St-b-4VP) film, the surface weight fraction of poly(4-vinyl pyridine)(P4VP) decreased dramatically after annealing above the glass transition temperature, Tg of P(St-b-4VP), resulting in the formation of polystyrene (PS) surface layer in order to minimize the interfacial free energy at air-polymer interface. Whereas, in the cases of the fluoroalkyl-terminated P(St-b-4VP) films [P(St-b-4VP)-C₂C^F_X where -C₂C^F_X shows fluoroalkyl end group], the surface weight fraction of P4VP decreased slightly and still was more than 30% even after the annealing treatment. TEM observation revealed that the lamellar structure was formed in all P(St-b-4VP). The surface order and orientation of lamellar structure were strongly influenced by the chain end group species. That is, in the case of the proton-terminated P(St-b-4VP) film, the lamellar structure was oriented parallel to the film surface and the outermost layer was composed of PS. On the other hand, in the case of P(St-b-4VP)-C₂C^F_X, the well-developed lamellae was tilted ca. 45 deg to the film surface and the alternating PS and P4VP layers were exposed to the air interface. These results indicate that the surface order and orientation of microphase-separated lamellar structure strongly depend on the chemical structure of the chain end group..
689.	Masami Yanagida, Atsushi Takahara, Tisato Kajiyama, Construction of defect-diminished fatty acid Langmuir-Blodgett film and its optical waveguide properties, Bulletin of the Chemical Society of Japan, 10.1246/bcsj.72.2795, 72, 12, 2795-2802, 1999.12, A Langmuir-Blodgett (LB) film for a optical planar waveguide with a low optical propagation loss could be constructed from highly organized fatty acid monolayers prepared by a cooling multi-step creep method. The cooling multi-step creep method is the novel preparation technique to form a defect- diminished monolayer on the water surfaces on the basis of both the structural relaxation induced by area-creep and the control of thermal molecular motions in the monolayer. The fatty acid monolayer prepared by the cooling multi-step creep method was morphologically homogeneous and mechanically stable, even at a high surface pressure where the monolayer prepared by a conventional continuous compression method easily collapsed. The crystallographical and structural regularities of the monolayer and the LB film prepared by the cooling multi-step creep method were remarkably improved, compared with those of the monolayer and the LB film prepared by the conventional continuous compression method. The LB film waveguides prepared by the cooling multi-step creep method were morphologically homogeneous and structurally regular and could propagate incident light with a low optical propagation loss..
690.	Atsushi Takahara, Tisato Kajiyama, Effect of end group-substrate interaction on aggregation structure of polystyrene ultrathin films, Polymer Journal, 31, 1, 89-95, 1999.12, The aggregation structure of proton-, monocarboxyl-, and dicarboxyl terminated polystyrene (PS) ultrathin films spin-coated onto different substrate surfaces was investigated on the basis of atomic force microscopy (AFM). In the case of the monocarboxyl- and dicarboxyl-terminated PS ultrathin films spin-coated onto Si-wafer, the dewetting occurred after annealing above their bulk glass transition temperatures. In contrast, those (monocarboxyl and dicarboxyl-terminated PS ultrathin films spin-coated) onto aminosilane-treated Si-wafer did not dewet even after annealing above the bulk T_g, owing to the specific interaction between -COOH and -NH₂ groups of aminosilane onto the Si-wafer..
691.	Tomokazu Fujii, Atsushi Takahara, Tisato Kajiyama, Scanning force microscopic study of polyethylene single crystals prepared by a self-seeding method, ACS Symposium Series, 741, 336-345, 1999.12, The surface structures of high-density polyethylene (HDPE) single crystals with weight average molecular weight, Mw=32k, 120k and 520k prepared by a self-seeding method were investigated by atomic force microscopy (AFM) and lateral force microscopy (LFM). A characteristic lozenge shape lamellar crystal of ca. 12 nm thick was observed with AFM. The contrast of lateral force of the HDPE single crystal in LFM images was observed between adjacent sectors, which means that the chain folding directions were different. The magnitude of lateral force in LFM measurement increased with scanning angle, θ, which was defined as the angle between scanning direction of the cantilever and {110}, that is the growth face of the HDPE single crystal. These results indicate that the surfaces of the HDPE single crystals prepared by a self-seeding method exhibit regular sharp chain folding along {110} at the surface. Furthermore, it was suggested that the folding structure of the HDPE single crystal surface might depend on the crystallization methods, such as isothermal crystallization or self-seeding one..
692.	Tomokazu Fujii, Atsushi Takahara, Tisato Kajiyama, Scanning force microscopic study of surface structure of polyethylene single crystals, KOBUNSHI RONBUNSHU, 56, 12, 845-849, 1999.12, The surface structure of high-density polyethylene (HDPE) single crystals prepared by the self-seeding method was investigated by atomic force microscopy (AFM) and lateral force microscopy (LFM). Characteristic lozenge-shaped lamellar crystals of ca. 5 μm long and ca. 12 nm thick were observed with AFM. The contrast of the lateral force between neighboring sectors of the HDPE single crystal surface could be detected when the scanning direction was different between neighboring sectors. The magnitude of the lateral force increased with an increase of the scanning angle, θ, with respect to the (110) plane. These results indicate that the surfaces of the HDPE single crystals with M_w=23k, 32k, 93k, 120k, and 520k prepared by the self-seeding method was composed of regular sharp chain-folds. It has been reported that the folding structure of the HDPE single crystal surface with M_w=520k prepared sporadically by a conventional isothermal crystallization method was switchboard-like structure. These results apparently indicate that the folding structure of the HDPE single crystal surface depends on the crystallization process or method..
693.	Noriaki Satomi, Atsushi Takahara, Tisato Kajiyama, Determination of surface glass transition temperature of monodisperse polystyrene based on temperature-dependent scanning viscoelasticity microscopy, Macromolecules, 10.1021/ma981850q, 32, 13, 4474-4476, 1999.06, The thermal molecular motion at the outermost surface of the polystyrene (PS) film was measured directly on the basis of temperature-dependent scanning viscoelasticity microscopy (SVM). It was possible to compare directly the surface and bulk thermal molecular motions of the polymeric solid film. The comparison lead to the conclusion that the surface is in a glass-rubber transition state or a rubbery state even at room temperature..
694.	Atsushi Yamashita, Atsushi Takahara, Tisato Kajiyama, Aggregation structure and fatigue characteristics of (nylon 6/clay) hybrid, Composite Interfaces, 10.1163/156855499X00071, 6, 3, 247-258, 1999.01, A nylon 6/montmorillonite clay hybrid (NCH) with montmorillonite of 2 wt% was prepared. Transmission electron microscopy (TEM) of NCH revealed that the silicate layers of montmorillonite were molecularly dispersed in nylon 6 matrix. Wide angle X-ray diffraction (WAXD) study revealed that crystallites formed in both NCH and nylon 6 were the y-form, and the crystallite size in NCH was larger than that in nylon 6. The temperature dependence of dynamic viscoelasticity of NCH revealed that the magnitude of αa-absorption of amorphous phase of nylon 6 in NCH was smaller than nylon 6, suggesting the restriction of thermal molecular motion in NCH due to the strong ionic interaction between nylon 6 and silicate layers. The fatigue lifetime for NCH was longer than that for nylon 6 and nylon 6 reinforced with surface-modified short glass-fiber(SMSGF/N6) under the identical fatigue conditions, even though they showed almost the same moduli. Fatigue fracture criterion based on energy loss dissipated for irreversible structural change was investigated for NCH, and it was revealed that the total viscoelastic energy loss dissipated for irreversible structural change up to fatigue failure of NCH was larger than that for nylon 6 and (SMSGF/N6). This indicates that the fatigue strength of NCH is superior to that of nylon 6 and (SMSGF/N6)..
695.	Atsushi Takahara, Analysis of Fatigue Lifetime of Polymeric Fibers and Polymeric Solids in Terms of Nonlinear Dynamic Viscoelastic Measurements, sen'i gakkaishi, 10.2115/fiber.55.10_P343, 55, 10, 1999.01.
696.	El Sayed Ahmed Mounir, Atsushi Takahara, Tisato Kajiyama, Effect of chain end group-substrate interaction on surface molecular motion of polystyrene ultrathin films, Polymer Journal, 10.1295/polymj.31.550, 31, 6, 550-556, 1999.01, Surface molecular motions of monodisperse proton-terminated polystyrene (PS-H), monocarboxyl-terminated PS (PSCOOH) and dicarboxyl-terminated PS (α,ω-PS(COOH)₂) ultrathin films were investigated on the basis of lateral force microscopic (LFM) measurement at 293 K, as a function of number-average molecular weight, M_n, and chain end functionality. In the case of the PS-H thin films with M_n = 19.7 k and 40.4 k spin-coated onto Si-wafer, the surface molecular motion was activated in a glass-rubber transition state at 293 K due to the excess free volume induced by a surface localization of chain end groups. Also, in the cases of the PSCOOH (M_n = 9.7 k, 45.9 k) and the α,ω-PS(COOH)₂ (M_n = 12.0 k, 51.7 k) ultrathin films spin-coated onto Si-wafer and their annealed ones at 393 K for 8 h, the surface molecular motion was also enhanced even at room temperature due to a weak ionic interaction between Si-OH of substrate and -COOH end group. On the other hand, the PSCOOH (M_n = 9.7 k, 45.9 k), and the α,ω-PS(COOH)₂ (M_n = 12.0 k, 51.7 k) spin-coated ultrathin films onto aminosilane-treated Si-wafer did not show any distinct activation of surface mobility owing to a specific interaction between NH₂-group of aminosilane-treated Si-wafer and -COOH end group of PS, being independent of annealing temperature, M_n and functionality..
697.	Tisato Kajiyama, Atsushi Takahara, Surface Phase-separated Structures of Multiphase Polymer Thin Films, Sen'i Gakkaishi, 10.2115/fiber.55.P57, 55, 2, 1999.01.
698.	Tisato Kajiyama, Noriaki Satomi, Keiji Tanaka, Atsushi Takahara, Surface, thermal and mechanical characteristics of polymeric solids, Macromolecular Symposia, 10.1002/masy.19991430114, 143, 171-183, 1999.01, Surface molecular motions of amorphous polymeric solids have been directly measured on the basis of lateral force microscopic (LFM) and scanning viscoelasticity microscopic (SVM) measurements. SVM measurement revealed that the molecular motion at the surface of the monodisperse polystyrene (PS) film with Mn less than ca.30k was fairly activated compared with that in a bulk region, mainly due to the surface segregation of chain end groups. Tempereature dependent LFM and SVM measurement revealed that the surface glass transition temperature, Tg of the monodisperse PS film was lower than the bulk one, even though Mn was fairly large as 140k and also, that the time-temperature superposition was applicable to the surface relaxation process. The chain end group segregation at the air/PS interface was verified from the dynamic secondary ion mass spectroscopic (DSIM S) depth profiling of the proton and deuterium ion for the end-labeled deutrated-PS (dPS) film. These results suggest that the surface Tg is depressed due to an increase in free volume near surface region, being induced by the preferential surface localization of chain end groups..
699.	A. Takahara, X. Jiang, N. Satomi, K. Tanaka, T. Kajiyama, Analysis of surface mechanical properties of polymer blend ultrathin films by scanning force microscopy, Key Engineering Materials, 137, 79-86, 1998.12, Scanning viscoelasticity microscopy (SVM) is used in studies of the surface mechanical properties of polymeric solids. It was revealed that the surface molecular motion is fairly different from bulk one due to the surface segregation of chain end groups. The two-dimensional mapping of the surface mechanical properties for the polymer blend ultrathin films was carried out on nanometer scale..
700.	A. Yamashita, S. Higashi, S. T. Komatsu, A. Takahara, T. Kajiyama, Fatigue analyses of short glass fibre-reinforced nylon 6 on the basis of dynamic viscoelastic measurements under cyclic fatigue, Key Engineering Materials, 137, 147-154, 1998.12, Fatigue behaviors of glass fiber-reinforced Nylon 6 were studied based on dynamic viscoelastic measurements during the fatigue process. The fatigue strength of glass fiber reinforced Nylon 6 was greatly improved by strengthening the interfacial adhesion between glass fiber and matrix polymers. The heat generation rate under cyclic fatigue for Nylon 6 reinforced with surface-unmodified short glass fiber was always larger than that reinforced with surface-modified short glass fiber because of the large net imposed strain amplitude to the matrix polymers. This might be attributed to the interfacial debonding under cyclic fatigue. A fatigue fracture criterion based on the magnitude of hysteresis energy loss being consumed for a structural change was established for the (Nylon 6/short glass fiber) composites in consideration of glass fiber-matrix polymer interfacial interaction..
701.	Atsushi Takahara, Shouren Ge, Ken Kojio, Tisato Kajiyama, Scanning Force Microscopy of Surface Structure and Surface Mechanical Properties of Organotrichlorosilane Monolayers Prepared by Langmuir Method, ACS Symposium Series, 694, 204-222, 1998.12, Organochlorosilane monolayers were polymerized on the water surface and immobilized onto the silicon wafer surface by Langmuir method. The electron diffraction (ED) pattern of the n-octadecyltrichlorosilane(OTS) monolayer revealed that OTS molecules were regularly arranged in a hexagonal array with the (10) spacing of ca. 0.42 nm. On the other hand, ED study revealed that the [2-(perfluorooctyl)ethyl]trichlorosilane (FOETS) monolayer was amorphous state at room temperature. The high-resolution atomic force microscopic (AFM) image of the OTS monolayer in a scan area of 10×10 nm² exhibited the individual methyl groups of which packing was a hexagonal array in a similar molecular arrangement concluded by the ED study. AFM observation of the (OTS/FOETS) mixed monolayer revealed that the crystalline OTS circular domains of ca. 1-2 μm in diameter were surrounded by a sea-like amorphous FOETS matrix, even though the molar fraction of OTS was above 75%. Phase separation was observed for monolayer prepared from FOETS and non-polymerizable and crystallizable amphiphile such as lignoceric acid (LA). The phase separation of the (alkylsilane/fluoroalkylsilane) mixed monolayer might be attributed to both the crystallizable characteristics of alkylsilane molecules and faster spreading of FOETS molecules on the water surface. The mixed monolayer of crystalline alkylsilane (OTS) and amorphous alkylsilane (n-dodecyltrichlorosilane, DDTS) formed phase-separated structure on the water surface because of the crystallizable characteristics of OTS. Lateral force microscopic (LFM) observation revealed that the order of the magnitude of lateral force generated against the silicon nitride tip was crystalline Si substrate >crystalline n-triacontyltrichlorosilane (TATS) domain> crystalline n-dococyltrichlorosilane (DOTS) domain> amorphous FOETS matrix > crystalline OTS domain>amorphous DDTS matrix. On the other hand, scanning viscoelasticity microscopic observation revealed that the order of the magnitude of modulus was Si substrate > crystalline OTS domain > amorphous FOETS matrix..
702.	Tao Liang, Atsushi Takahara, Koichi Saito, Tisato Kajiyama, Effects of main chain rigidity on nonlinear dynamic viscoelasticity and fatigue performance for polymeric fibres, polymer, 10.1016/S0032-3861(97)10219-1, 39, 22, 5387-5392, 1998.10, Fatigue performance of polymeric fibres with different molecular chain rigidity was investigated based on zone nonlinear dynamic viscoelastic analyses under tension-type cyclic straining. Poly(vinyl alcohol), Nylon 6(poly(ε-caprolactam)), poly(ethylene terephthalate), poly(p-phenylene terephtalamide) and Vectran (a copolyester of p-hydroxy benzoate (HBA) and 2-hydroxy-t-naphthoic acid (HNA)) fibres were used as specimens. Nonlinear dynamic viscoelasticity and fatigue performance of polymeric fibres strongly depend on the chain rigidity. The polymeric fibres with rigid molecular chains showed pronounced nonlinear viscoelastic characteristics compared with those with flexible ones. Also, based on the zone nonlinear dynamic viscoelastic analyses, it was found that the nonlinear viscoelastic behaviours of polymeric fibres was predominantly induced in the recovery process rather than in the tensile process during a single period of cyclic deformation, and the more remakable nonlinear viscoelastic behaviour was exhibited in the zone with higher strain rate. The polymeric fibre which exhibited remarkable nonlinear dynamic viscoelasticity showed extremely poor fatigue performance..
703.	Keiji Tanaka, Xiqun Jiang, Kensuke Nakamura, Atsushi Takahara, Tisato Kajiyama, Takashi Ishizone, Akira Hirao, Sei Ichi Nakahama, Effect of chain end chemistry on surface molecular motion of polystyrene films, Macromolecules, 10.1021/ma9712561, 31, 15, 5148-5149, 1998.07.
704.	Tisato Kajiyama, Keiji Tanaka, Noriaki Satomi, Atsushi Takahara, Surface relaxation process of monodisperse polystyrene film based on lateral force microscopic measurements, Macromolecules, 10.1021/ma971274i, 31, 15, 5150-5151, 1998.07.
705.	Xiqun Jiang, Keiji Tanaka, Atsushi Takahara, Tisato Kajiyama, Effect of chain end group hydrophobicity on surface aggregation structure of poly(styrene-block-4-vinylpyridine) symmetric diblock copolymer films, polymer, 10.1016/S0032-3861(97)00567-3, 39, 12, 2615-2620, 1998.06, Proton-terminated polystyrene-block-poly(4-vinylpyridine) (P(St-b-4VP)-H) and 3,3,3-trifluoropropyldimethylsilane-terminated polystyrene-block-poly(4-vinylpyridine) (P(St-b-4VP)-C₂C^F) symmetric diblock copolymers were synthesized by a living anionic polymerization. Differential scanning calorimetry (DSC) measurements revealed that both diblock copolymers were in a microphase-separated state in the bulk. The results of X-ray photoelectron spectroscopy (XPS) measurements revealed that in the case of the P(St-b-4VP)-H film, the surface weight fraction of poly(4-vinylpyridine) (P4VP) decreased drastically on annealing at 432 K for 90 h in order to minimize the magnitude of the free energy at the air-polymer interface, whereas in the case of the P(St-b-4VP)-C₂C^F film, the surface P4VP weight fraction was almost the same as the bulk value even after annealing at 423 K for 90 h. Also, scanning force microscopy observations (SFM) were in good agreement with the XPS results. These results clearly indicate that the surface molecular aggregation state of the hydrophobic-hydrophilic diblock copolymer film can be controlled by the hydrophobicity of the chain end groups..
706.	Tisato Kajiyama, Keiji Tanaka, Atsushi Takahara, Surface segregation of the higher surface free energy component in symmetric polymer blend films, Macromolecules, 10.1021/ma971247s, 31, 11, 3746-3749, 1998.06.
707.	Atsushi Takahara, Ken Kojio, Tisato Kajiyama, Aggregation structure and surface properties of immobilized polyalkylsiloxane ultrathin films prepared at the air/water interface, American Chemical Society, Polymer Preprints, Division of Polymer Chemistry, 39, 1, 501-502, 1998.03.
708.	Ken Kojio, Shouren Ge, Atsushi Takahara, Tisato Kajiyama, Molecular aggregation state of n-octadecyltrichlorosilane monolayer prepared at an air/water interface, Langmuir, 14, 5, 1998.03, Molecular arrangement of polymerized n-octadecyltrichlorosilane (OTS, CH₃(CH₂)₁₇SiCl₃) monolayer transferred onto hydrophilic substrate by an upward drawing method was investigated with a transmission electron microscope (TEM) and an atomic force microscope (AFM). The electron diffraction (ED) pattern of the OTS monolayer revealed that the OTS molecules were regularly arranged in a hexagonal array with a (10) spacing of ca. 0.42 nm. The high-resolution AFM image of the OTS monolayer in a scan area of 10 × 10 nm² exhibited the individual methyl group of which packing was a hexagonal array in a similar molecular arrangement concluded on the basis of the ED study. Also, the point defect in the crystalline OTS monolayer was successfully observed for the first time..
709.	Ken Kojio, Shouren Ge, Atsushi Takahara, Tisato Kajiyama, Molecular aggregation state of n-octadecyltrichlorosilane monolayer prepared at an air/water interface, Langmuir, 10.1021/la970040p, 14, 5, 971-974, 1998.03, Molecular arrangement of polymerized n-octadecyltrichlorosilane (OTS, CH₃(CH₂)₁₇SiCl₃) monolayer transferred onto hydrophilic substrate by an upward drawing method was investigated with a transmission electron microscope (TEM) and an atomic force microscope (AFM). The electron diffraction (ED) pattern of the OTS monolayer revealed that the OTS molecules were regularly arranged in a hexagonal array with a (10) spacing of ca. 0.42 nm. The high-resolution AFM image of the OTS monolayer in a scan area of 10 × 10 nm² exhibited the individual methyl group of which packing was a hexagonal array in a similar molecular arrangement concluded on the basis of the ED study. Also, the point defect in the crystalline OTS monolayer was successfully observed for the first time..
710.	Keiji Tanaka, Atsushi Takahara, Tisato Kajiyama, Surface molecular aggregation structure and surface molecular motions of high-molecular-weight polystyrene/low-molecular-weight poly(methyl methacrylate) blend films, Macromolecules, 10.1021/ma9709866, 31, 3, 863-869, 1998.02, Surface molecular aggregation structure and surface molecular motions of high-molecular-weight polystyrene/low-molecular-weight poly(methyl methacrylate) (HMW-PS/LMW-PMMA) blend films were investigated on the basis of X-ray photoelectron spectroscopic measurements and scanning force microscopic observations. Monodisperse PS with M_n = 1450k, where M_n denotes the number-average molecular-weight, and monodisperse PMMAs with M_n 1.2k, 4.2k, 40.5k, 144k, and 387k were used as HMW-PS and LMW-PMMAs, respectively. Static contact angle measurements revealed that the magnitudes of surface free energy, γ, of PMMAs for all M_ns studied here were higher than that of PS with M_n = 1450K. In the case of the (HMW-PS/LMW-PMMA) blend films, in which the M_n for each PMMA was less than 144K, PMMA was preferentially segregated at the air-polymer interface, even though PMMA had a main chain with a higher γ compared with that of PS. It was found from scanning viscoelasticity microscopic measurements that the surface molecular motion of the (PS with M_n = 1450k/ PMMA with M_n = 4.2k) blend film was fairly activated in comparison with that of the bulk one due to the surface segregation of LMW-PMMA. The surface enrichment of LMW-PMMA can be explained by enthalpic and entropie terms as follows. (1) Since the magnitudes of γ of both chain end groups of a polymer chain synthesized by an ordinary living anionic polymerization are smaller than that of the main chain part, the chain end groups are preferentially segregated at the surface. Therefore, the chain end effect at the air-polymer interface becomes more remarkable with a decrease of M_n, due to an increases in the number density of chain end groups. (2) Since polymeric chains existing in a surface region are compressed along the direction perpendicular to the film surface, the surface chains take smaller conformational entropy in a confined state compared with that of bulk chains. The difference in conformational entropy between the surface chain and the bulk one, that is, the conformational entropic penalty of the polymeric chain at the surface, decreases with a decrease in M_n. Then, when the enthalpic and entropic effects mentioned above overcome the γ difference of main chain parts between PS and PMMA, PMMA with higher γ is stably enriched at the blend film surface..
711.	Liusheng Chen, Ming Ni, Shijun Jia, Xigao Jin, Shouren Ge, Atsushi Takahara, Tisato Kajiyama, AFM Observation of Single-Chain PMMA Particles, Journal of Macromolecular Science - Physics, 10.1080/00222349808220476, 37, 3, 339-348, 1998.01, Atomic force microscopy (AFM) has been applied to observe single-chain polymethylmethacrylate (PMMA) particles that were stored for six months at room temperature after being sprayed from very dilute solutions in good solvents, good/poor mixed solvents, and a theta solvent. Nearly monodisperse PMMA standards of molecular weights ranging from 7.90 × 10⁴ to 1.3 × 10⁶ were used to investigate the effect of molecular weight (MW) on the size of the single-chain PMMA particles. These single-chain particles showed close to spherical shapes. The morphology of single-chain PMMA particles of a given molecular weight has found to be identical in spite of different solvents used for solution spraying. Molecular weight dependence of the particle dimension was also found. The diameters of single-chain PMMA particles after correction of tip-geometry effect were compared with the values estimated from molecular weight and density..
712.	Shouren Ge, Ken Kojio, Atsushi Takahara, Tisato Kajiyama, Bovine serum albumin adsorption onto immobilized organotrichlorosilane surface Influence of the phase separation on protein adsorption patterns, Journal of Biomaterials Science, Polymer Edition, 10.1163/156856298X00479, 9, 2, 131-150, 1998.01, Octadecyltrichlorosilane (OTS) and [2-(perfluorooctyl)ethyl]trichlorosilane (FOETS) monolayers and their mixed monolayer were polymerized on a water subphase and subsequently immobilized onto a silicon wafer surface by covalent bonding. Atomic force microscopic (AFM) observation of the mixed (OTS/FOETS) monolayer revealed the formation of a phase-separated structure. Protein-adsorption behavior onto the monolayers was investigated in situ on the basis of an attenuated total reflection Fourier transform infrared (ATR-FT-IR) spectroscopic flow cell method and the morphology of the monolayer surface-adsorbed bovine serum albumin (BSA) was observed by AFM. Protein adsorption behavior observed by ATR-FT-IR flow cell method revealed that the amount of BSA adsorption onto the OTS and FOETS monolayers increased remarkably at an initial experimental stage and attained a steady state within a few minutes at pH 7.5. The amount of steady state adsorption was c. 0.18-0.2 μgcm^-2. AFM observation of the monolayer after exposure to BSA solution suggested that BSA adsorbed in the end-on adsorption state on OTS monolayer and side-on one in the FOETS monolayer, respectively. However, in the case of the mixed (OTS/FOETS) monolayer, ATR-FT-IR flow cell experiment revealed that the amount of steady state adsorption of BSA was suppressed. Also, AFM observation revealed that at pH 7.5, BSA preferentially adsorbed onto the FOETS phase of the mixed (OTS/FOETS) monolayer, which had a higher interfacial free energy against water. On the other hand, BSA adsorbed homogeneously onto the OTS and FOETS phases at the isoelectric point of BSA (pH 4.7). These results indicate that the preferential adsorption of BSA onto the FOETS phase in the mixed (OTS/FOETS) monolayer system is due to: (1) the minimization of the interfacial free energy between a monolayer surface and an aqueous solution; and (2) the electrostatic repulsion between BSA molecules bearing negative charges..
713.	Tisato Kajiyama, Noppadol Khuwattanasil, Atsushi Takahara, Electric field induced structural change for poly(vinylidene fluoride-co-trifluoroethylene) ultrathin films studied by scanning Maxwell stress microscope, Journal of Vacuum Science and Technology B: Microelectronics and Nanometer Structures, 16, 1, 121-124, 1998.01, Poly(vinylidene fluoride-co-trifluoroethylene) [P(VDF/TrFE), VDF 75 mol %] ultrathin films of 10 nm thickness were prepared on gold coated silicon wafer substrates by a spin-coating method and their aggregation states were investigated by Fourier transform infrared reflection absorption spectroscopic measurement. It was found that P(VDF/TrFE) formed a ferroelectric phase even in a confined state such as an ultrathin film. The electric field was locally imposed on the ultrathin film through a gold coated cantilever tip. The change of dipole moment orientation of P(VDF/TrFE) was evaluated by measuring surface potential change, performed by scanning Maxwell stress microscopy (SMM). The SMM images revealed that the local dipole moment orientation of P(VDF/ TrFE) in ultrathin films could be changed by an application of electric field through an atomic force microscope tip..
714.	Ken Kojio, Shouren Ge, Atsushi Takahara, Tisato Kajiyama, Interaction between Polymeric Organosilane Monolayer and Plasma Protein, KOBUNSHI RONBUNSHU, 10.1295/koron.55.344, 55, 6, 344-352, 1998.01, The n-octadecyltrichlorosilane (OTS) and the [2-(perfluorooctyl)ethyl]trichlorosilane (FOETS) monolayers, and their mixed monolayer were used as the model systems for the study of protein adsorption behavior because of their remarkable surface stability. The attenuated total reflection infrared (ATR-FT-IR) flow cell studies revealed that the adsorption amount of bovine serum albumin (BSA) onto each OTS and FOETS monolayer steeply increased in an initial stage of adsorption experiment and attained an equilibrium within a few minutes at pH 7.5. In the case of the (OTS/ FOETS) (50/50 mol/mol) mixed monolayer, the amount of protein adsorption was suppressed. AFM observation in a BSA solution at pH 7.5 revealed that BSA was preferentially adsorbed onto the FOETS phase of the (OTS/FOETS) mixed monolayer, while selective adsorption of BSA onto the FOETS phase was not observed at the isoelectric point of BSA (pH 4.7). Furthermore, [(3-mercaptopropyl)trimethoxysilane (MTS)/FOETS] mixed monolayer with reactive -SH group in domain was prepared. Then, the BSA was selectively immobilized onto the MTS phase..
715.	Atsushi Takahara, Kenji Yamada, Tisato Kajiyama, Motowo Takayanagi, Evaluation of fatigue lifetime and elucidation of fatigue mechanism in plasticized poly(vinyl chloride) in terms of dynamic viscoelasticity, Journal of Applied Polymer Science, 10.1002/app.1980.070250407, 25, 4, 597-614, 1980.01, The fatigue behavior of plasticized poly(vinyl chloride) was investigated by means of a tension–compression‐type fatigue apparatus. Complex elastic modulus and mechanical loss tangent were obtained continuously with time under the conditions of constant ambient temperature as a function of imposed strain amplitude. Brittle failure was observed under the conditions of low ambient temperatures and small strain amplitudes, or forced convection of air, whereas thermal failure was observed under the conditions of high ambient temperatures, or large strain amplitudes and natural convection of air. In the case of brittle failure, the dynamic storage modulus E′ exhibited a maximum and the loss tangent tanδ exhibited a minimum on approaching the point of failure. In the case of thermal failure, E′ decreased and tanδ increased monotonously until the onset of thermal failure. It was found that failure occurs when the effective energy loss reaches a certain magnitude depending on an ambient temperature. The fatigue criterion was represented schematically from a standpoint of self‐heating. When the heat generation rate of the specimen under cyclic staining is larger than that of the heat transfer to the surroundings, thermal failure takes place. In this case, the specimen temperature increases up to a limiting constant temperature corresponding to the α‐absorption temperature. When the heat generation rate is nearly equal to that of the heat transfer to the surroundings, the specimen temperature does not change appreciably and brittle failure takes place..
716.	M. Takayanagi, Atsushi Takahara, K. Yamada, T. Kajiyama, FATIGUE PHENOMENA OF SOLID POLYMERS IN TERMS OF VISCOELASTICITY., Pap presented at Jt ACS/JCS (Am Chem Soc/Jpn Chem Soc) Meet Am Chem Soc Div Polym Chem Prepr, 20, 1, 263-266, 1979.01, Studies on fatigue of solid polymers have been approached along two distinct paths; one is phenomenological studies such as the detailed examinations of crack nucleation and crack propagation, and the other approach involves molecular considerations, being associated with bond breakage, chain orientation and so on. In clarifying the fatigue characteristics of polymeric materials, it is also important to investigate the variation of viscoelasticity during the fatigue process. In this paper, the variation of dynamic viscoelastic properties during fatigue process are measured at various ambient temperatures and imposed strain amplitudes. The data are effective in clarifying the fatigue mechanisms and proposing the fat criteria for solid polymers. Detailed description is made on plasticized poly(vinyl chloride) as a typical case..
717.	Yoshifumi Amamoto, Hideyuki Otsuka, Atsushi Takahara, Synthesis and Characterization of Polymeric Nanogels, Nanomaterals for the Life Science, 10, 10, 27-57.
718.	Gerard Calleja, Axel Houdayer, Sylvie Etienne-Calas, David Bourgogne, Valerie Flaud, Gilles Silly, Sota Shibahara, Atsushi Takahara, Alex Jourdan, Andre Hamwi, Bruno Ameduri, Conversion of Poly(ethylene-alt-tetrafluoroethylene) Copolymers into Polytetrafluoroethylene by Direct Fluorination: A Convenient Approach to Access New Properties at the ETFE Surface, Journal of Polymer Science part A: Polymer Chemistry, 10.1002/POLA, 49, 7, 1517-1527.
719.	Naoyuki Morishige, Yuki Takagi, Tai-ichiro Chikama, Atsishi Takahara, Teruo Nishida, Three-Dimensional Analysis of Collagen Lamellae in the Anterior Stroma of the Human Cornea Visualized by Second Harmonic Generation Imaging Microscopy, Investigative Ophthalmology & Visual Science, 52, 2, 911-915.
720.	Wei Ma, Hideyuki Otsuka, Atsushi Takahara, Poly(methyl methacrylate) grafted imogolite nanotubes prepared through sulface-initiated ARGET ATRP, Chem. Commun., 10.1039/c1cc10661a, 47, 5813-5815.
721.	Wei Ma,Jungeun Kim,Hideyuki Otsuka, Atsushi Takahara, Surface Modification of Individual Imogolite Nanotubes with Alkyl Phosphate from an Aqueous Solution, Chemistry Letters, 10.1246/cl.2011.159, 40, 2, 159-161.
722.	Rui Xue Li, Shu Mei Liu, Jian Qing Zhao, Hideyuki Otsuka, Atsushi Takahara, Preparation and characterization of cross-linked β-cyclodextrin polymer/Fe3O4 composite nanoparticles with core-shell structures, Chinese Chemical Letters, 10.1016/j.cclet.2010.09.014, 22, 217-220.

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