Authorship：Last author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：Polymer Journal  

In this study, a Pd-polymeric porous immobilized catalyst is prepared for the Suzuki–Miyaura coupling reactions by employing a Bayesian optimization method to optimize the catalyst. This research represents the first endeavor to utilize machine learning for the optimization of polymer-immobilized catalysts and provides a novel perspective on utilizing machine learning for the optimization of complex materials.

DOI： 10.1038/s41428-024-00923-8

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Repository Public URL： https://hdl.handle.net/2324/7337522

Language：English   Publishing type：Research paper (scientific journal)   Publisher：ACS Applied Materials and Interfaces  

Although thin-film composite membranes have achieved great success in CO2 separation, further improvements in the CO2 permeance are required to reduce the size and cost of the CO2 separation process. Herein, we report the fabrication of composite membranes with high CO2 permeability using a laser-patterned porous membrane as the support membrane. High-aspect-ratio micropatterns with well-defined micropores on their surface were carved on microporous polymer supports by a direct laser writing process using a short-pulsed laser. By using a Galvano scanner and optimizing the laser conditions and target materials, in-plane micropatterns, such as microhole arrays, microline grating, microlattices, and out-of-plane hierarchical micropatterns, were created on porous membranes. An aqueous suspension of hydrogel microparticles doped with an amine-based mobile carrier was sprayed onto the patterned surface to form a defect-free thin separation layer. The surface area of the separation layer on the patterned support is up to 80% larger than that of flat pristine membranes, resulting in a 52% higher CO2 permeance (1106 GPU) with a CO2/N2 selectivity of 172. The laser-patterned porous membranes allow the development of inexpensive and high-performance functional membranes not only for CO2 separation but also for other applications, such as water treatment, cell culture, micro-TAS, and membrane reactors.

DOI： 10.1021/acsami.4c01260

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Authorship：Last author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：ChemPlusChem  

Continuous-flow syntheses using immobilized catalysts can offer efficient chemical processes with easy separation and purification. Porous polymers have gained significant interests for their applications to catalytic systems in the field of organic chemistry. The porous polymers are recognized for their large surface area, high chemical stability, facile modulation of surface chemistry, and cost-effectiveness. It is crucial to immobilize transition-metal catalysts due to their difficult separation and high toxicity. Supported phosphine ligands represent a noteworthy system for the effective immobilization of metal catalysts and modulation of catalytic properties. Researchers have been actively pursuing strategies involving phosphine-metal complexes supported on porous polymers, aiming for high activities, durabilities, selectivities, and applicability to continuous-flow systems. This review provides a concise overview of phosphine-metal complexes supported on porous polymers for continuous-flow catalytic reactions. Polymer catalysts are categorized based on pore sizes, including micro-, meso-, and macroporous polymers. The characteristics of these porous polymers are explored concerning their efficiency in immobilized catalysis and continuous-flow systems.

DOI： 10.1002/cplu.202400039

DOI： 10.1002/cplu.202400039

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Other Link： https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/cplu.202400039

Open data URL： https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/cplu.202400039

Authorship：Lead author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：Chemistry Letters  

Synthetic polymers with molecular recognition ability were investigated. Well-defined chemical structures of biopolymers were mimicked by controlled polymerization. In particular, the preparation and molecular recognition of de novo designed glycopolymers were studied. Glycopolymers such as block polymers, star polymers, and microgels were prepared. The designed glycopolymers showed strong molecular recognition against target proteins and viruses.

DOI： 10.1021/acsami.3c15966

Authorship：Lead author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：Chemistry Letters  

Synthetic polymers with molecular recognition ability were investigated. Well-defined chemical structures of biopolymers were mimicked by controlled polymerization. In particular, the preparation and molecular recognition of de novo designed glycopolymers were studied. Glycopolymers such as block polymers, star polymers, and microgels were prepared. The designed glycopolymers showed strong molecular recognition against target proteins and viruses.

DOI： 10.1093/chemle/upad012

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Other Link： https://academic.oup.com/chemlett/article/53/2/upad012/7457604?login=true#google_vignette

Language：English   Publishing type：Research paper (scientific journal)  

Photoinduced electron/energy transfer-reversible addition–fragmentation chain transfer (PET-RAFT) polymerization enables the production of well-controlled synthetic polymers under mild conditions by using visible-light energy. Although flow reactors are suitable for photoreactions in terms of light penetration, contamination of photocatalysts occurs in a homogeneous system and necessitates product purification. Immobilizing the photocatalysts onto supports can eliminate the need for this purification step and enhance the potential for industrial applications of PET-RAFT polymerization. Herein, we report the development of a packed-bed flow photoreactor wherein a photocatalyst for PET-RAFT polymerization, zinc tetraphenylporphyrin, was immobilized onto packed silica particles. Continuous PET-RAFT polymerization of a model monomer (N,N-dimethylacrylamide) was achieved without leakage of the porphyrin molecules. The effects of various reaction conditions, such as the residence time, catalyst density, and target molecular weight, on the polymerization reaction were evaluated. This work contributes to the realization of a facile and practical manufacturing process for highly valuable synthetic polymers.

DOI： doi.org/10.1021/acs.iecr.3c03496

Language：English   Publishing type：Research paper (scientific journal)  

High-mobility group box 1 (HMGB1) is a multifunctional protein. Upon injury or infection, HMGB1 is passively released from necrotic and activated dendritic cells and macrophages, where it functions as a cytokine, acting as a ligand for RAGE, a major receptor of innate immunity stimulating inflammation responses including the pathogenesis of cerebral ischemia/reperfusion (I/R) injury. Blocking the HMGB1/RAGE axis offers a therapeutic approach to treating these inflammatory conditions. Here, we describe a synthetic antibody (SA), a copolymer nanoparticle (NP) that binds HMGB1. A lightly cross-linked N-isopropylacrylamide (NIPAm) hydrogel copolymer with nanomolar affinity for HMGB1 was selected from a small library containing trisulfated 3,4,6S-GlcNAc and hydrophobic N-tert-butylacrylamide (TBAm) monomers. Competition binding experiments with heparin established that the dominant interaction between SA and HMGB1 occurs at the heparin-binding domain. In vitro studies established that anti-HMGB1-SA inhibits HMGB1-dependent ICAM-1 expression and ERK phosphorylation of HUVECs, confirming that SA binding to HMGB1 inhibits the proteins’ interaction with the RAGE receptor. Using temporary middle cerebral artery occlusion (t-MCAO) model rats, anti-HMGB1-SA was found to accumulate in the ischemic brain by crossing the blood–brain barrier. Significantly, administration of anti-HMGB1-SA to t-MCAO rats dramatically reduced brain damage caused by cerebral ischemia/reperfusion. These results establish that a statistical copolymer, selected from a small library of candidates synthesized using an “informed” selection of functional monomers, can yield a functional synthetic antibody. The knowledge gained from these experiments can facilitate the discovery, design, and development of a new category of drug.

DOI： https://doi.org/10.1021/jacs.3c06799

Language：English   Publishing type：Research paper (scientific journal)   Publisher：Chemistry - An Asian Journal  

Carbohydrates are involved in life activities through the interactions with their corresponding proteins (lectins). Pathogen infection and the regulation of cell activity are controlled by the binding between lectins and glycoconjugates on cell surfaces. A deeper understanding of the interactions of glycoconjugates has led to the development of therapeutic and preventive methods for infectious diseases. Glycopolymer is one of the classes of the materials present multiple carbohydrates. The properties of glycopolymers can be tuned through the molecular design of the polymer structures. This review focuses on research over the past decade on the design of glycopolymers with the aim of developing inhibitors against pathogens and manipulator of cellular functions.

DOI： 10.1002/asia.202300643

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Royal Society of Chemistry  

Synthetic cryoprotectants with macromolecular structures are desirable as alternatives to commonly used ones. Herein, we prepared an amphipathic polymer library and evaluated the cryoprotective ability of the polymers by facile screening using red blood cells. The cryoprotective properties of the amphipathic polymers was independent of both the log P values of the hydrophobic groups and the ice recrystallization inhibition activity.

DOI： 10.1039/d3ma00251a

DOI： 10.1039/D3MA00251A

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Open data URL： https://pubs.rsc.org/en/content/articlehtml/2023/ma/d3ma00251a

Language：English   Publishing type：Research paper (scientific journal)   Publisher：Chemistry - A European Journal  

Metal centers that can generate coordinatively unsaturated metals in accessible and stable states have been developed using synthetic polymers with sophisticated ligand and scaffold designs, which required synthetic efforts. Herein, we report a simple and direct strategy for producing polymer-supported phosphine-metal complexes, which stabilizes mono-P-ligated metals by modulating the electronic properties of the aryl pendant groups in the polymer platform. A three-fold vinylated PPh_3 was copolymerized with a styrene derivative and a cross-linker to produce a porous polystyrene-phosphine hybrid monolith. Based on the Hammett substituent constants, the electronic properties of styrene derivatives were modulated and incorporated into the polystyrene backbone to stabilize the mono-P-ligated Pd complex via Pd-arene interactions. Through NMR, TEM, and comparative catalytic studies, the polystyrene-phosphine hybrid, which induces selective mono-P-ligation and moderate Pd-arene interactions, demonstrated high catalytic durability for the cross-coupling of chloroarenes under continuous-flow conditions.

DOI： 10.1002/chem.202301847

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Repository Public URL： https://hdl.handle.net/2324/7148419

Authorship：Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：American Chemical Society  

Self-folding behavior of amphiphilic polymers in aqueous environments mimics the structures of biomacromolecules (e.g., proteins). Since both the three-dimensional structure (static) and the molecular flexibility (dynamic) of a protein are essential for its biological functions, the latter should be considered when designing synthetic polymers that are intended to mimic proteins. Herein, we investigated the correlation between the self-folding behavior of amphiphilic polymers and their molecular flexibility. We synthesized amphiphilic polymers by subjecting N,N-dimethylacrylamide (hydrophilic) and N-benzylacrylamide (hydrophobic) to living radical polymerization. Polymers containing 10, 15, and 20 mol % of N-benzylacrylamide demonstrated self-folding behavior in an aqueous phase. The spin–spin relaxation time (T_2) of the hydrophobic segments decreased with the percent collapse of the polymer molecules, indicating that mobility was restricted by the self-folding behavior. Furthermore, comparison of the polymers with random and block sequences revealed that the mobility of hydrophobic segments was not affected by the component of the local segments.

DOI： 10.1021/acsmacrolett.3c00182

DOI： 10.1021/acsmacrolett.3c00182

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：MDPI  

Continuous flow reactors with immobilized catalysts are in great demand in various industries, to achieve easy separation, regeneration, and recycling of catalysts from products. Oxidation of alcohols with 4-amino-TEMPO-immobilized monolith catalyst was investigated in batch and continuous flow systems. The polymer monoliths were prepared by polymerization-induced phase separation using styrene derivatives, and 4-amino-TEMPO was immobilized on the polymer monolith with a flow reaction. The prepared 4-amino-TEMPO-immobilized monoliths showed high permeability, due to their high porosity. In batch oxidation, the reaction rate of 4-amino-TEMPO-immobilized monolith varied with stirring. In flow oxidation, the eluent permeated without clogging, and efficient flow oxidation was possible with residence times of 2–8 min. In the recycling test of the flow oxidation reaction, the catalyst could be used at least six times without catalyst deactivation.

DOI： 10.3390/polym14235123

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Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：Royal Society of Chemistry  

Cyclic polymers, which have a different topology from that of linear polymers, show potential as novel nanomaterials. In this communication, we report the synthesis of well-defined cyclic glycopolymers that have functional units for biomolecular recognition and evaluated their physical properties including molecular mobility. The suppressed molecular mobility of the cyclic glycopolymers was found to weaken their interactions with target proteins, demonstrating the influence of polymer topology on molecular recognition.

DOI： 10.1039/d2py00941b

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Angewandte Chemie - International Edition  

Synthetic polymer nanoparticles (NPs) that recognize and neutralize target biomacromolecules are of considerable interest as “plastic antibodies”, synthetic mimics of antibodies. However, monomer sequences in the synthetic NPs are heterogeneous. The heterogeneity limits the target specificity and safety of the NPs. Herein, we report the synthesis of NPs with uniform monomer sequences for recognition and neutralization of target peptides. A multifunctional oligomer with a precise monomer sequence that recognizes the target peptide was prepared via cycles of reversible addition–fragmentation chain transfer (RAFT) polymerization and flash chromatography. The oligomer or blend of oligomers was used as a chain transfer agent and introduced into poly(N-isopropyl acrylamide) hydrogel NPs by radical polymerization. Evaluation of the interaction with the peptides revealed that multiple oligomers in NPs cooperatively recognized the sequence of the target peptide and neutralized its toxicity. Effect of sequence, combination, density and molecular weight distribution of precision oligomers on the affinity to the peptides was also investigated.

DOI： 10.1002/anie.202206456

DOI： 10.1002/anie.202206456

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Language：English   Publishing type：Research paper (scientific journal)  

Synthetic polymer nanoparticles (NPs) that recognize and neutralize target biomacromolecules are of considerable interest as “plastic antibodies”, synthetic mimics of antibodies. However, monomer sequences in the synthetic NPs are heterogeneous. The heterogeneity limits the target specificity and safety of the NPs. Herein, we report the synthesis of NPs with uniform monomer sequences for recognition and neutralization of target peptides. A multifunctional oligomer with a precise monomer sequence that recognizes the target peptide was prepared via cycles of reversible addition–fragmentation chain transfer (RAFT) polymerization and flash chromatography. The oligomer or blend of oligomers was used as a chain transfer agent and introduced into poly(N-isopropyl acrylamide) hydrogel NPs by radical polymerization. Evaluation of the interaction with the peptides revealed that multiple oligomers in NPs cooperatively recognized the sequence of the target peptide and neutralized its toxicity. Effect of sequence, combination, density and molecular weight distribution of precision oligomers on the affinity to the peptides was also investigated.

DOI： 10.1002/ange.202206456

Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：American Chemical Society  

Commercialized oligosaccharides such as GM1 are useful for biological applications but generally expensive. Thus, facile access to an effective alternative is desired. Glycopolymers displaying both carbohydrate and hydrophobic units are promising materials as alternatives to oligosaccharides. Prediction of the appropriate polymer structure as an oligosaccharide mimic is difficult, and screening of the many candidates (glycopolymer library) is required. However, repeating polymerization manipulation for each polymer sample to prepare the glycopolymer library is time-consuming. Herein, we report a facile preparation of the glycopolymer library of GM1 mimics by photoinduced electron/energy transfer-reversible addition–fragmentation chain-transfer (PET-RAFT) polymerization. Glycopolymers displaying galactose units were synthesized in various ratios of hydrophobic acrylamide derivatives. The synthesized glycopolymers were immobilized on a gold surface, and the interactions with cholera toxin B subunits (CTB) were analyzed using surface plasmon resonance imaging (SPRI). The screening by SPRI revealed the correlation between the log P values of the hydrophobic monomers and the interactions of the glycopolymers with CTB, and the appropriate polymer structure as a GM1 mimic was determined. The combination of the one-time preparation and the fast screening of the glycopolymer library provides a new strategy to access the synthetic materials for critical biomolecular recognition.

DOI： 10.1021/acsomega.2c00719

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Authorship：Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：American Chemical Society  

Synthetic polymers with well-defined structures allow the development of nanomaterials with additional functions beyond biopolymers. Herein, we demonstrate de novo design of star-shaped glycoligands to interact with hemagglutinin (HA) using well-defined synthetic polymers, with the aim of developing an effective inhibitor for the influenza virus. Prior to the synthesis, the length of the star polymer chains was predicted using the Gaussian model of synthetic polymers, and the degree of polymerization required to achieve multivalent binding to three carbohydrate recognition domains (CRDs) of HA was estimated. The star polymer with the predicted degree of polymerization was synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization, and 6’-sialyllactose was conjugated as the glycoepitope for HA. The designed glycoligand exhibited the strongest interaction with HA as a result of the multivalent binding. This finding demonstrated that the biological function of the synthetic polymer could be controlled by precisely defining the polymer structures.

DOI： /10.1021/acs.biomac.1c01483

DOI： /10.1021/acs.biomac.1c01483

CiNii Research

Language：English   Publisher：The Chemistry Society of Japan  

One of the new strategies to treat autoimmune diseases is to target Siglec, a membrane protein receptor with the ability to suppress immune responses. Herein, we synthesized glycopolymers carrying 3'-sialyllactose in various glycounit densities. RAW 264.7 macrophages transfected to express secreted alkaline phosphatase (SEAP) were used to evaluate the immunosuppression ability of the glycopolymers. The inhibition of the signal transmission was dependent on the glycounit densities of the glycopolymers, and was maximized at the moderate density (70%).

DOI： 10.1246/cl.210740

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Open data URL： https://academic.oup.com/chemlett/article/51/3/308/7395176?login=true

Language：English   Publishing type：Research paper (scientific journal)   Publisher：Biomacromolecules  

Synthetic polymers with well-defined structures allow the development of nanomaterials with additional functions beyond biopolymers. Herein, we demonstrate de novo design of star-shaped glycoligands to interact with hemagglutinin (HA) using well-defined synthetic polymers with the aim of developing an effective inhibitor for the influenza virus. Prior to the synthesis, the length of the star polymer chains was predicted using the Gaussian model of synthetic polymers, and the degree of polymerization required to achieve multivalent binding to three carbohydrate recognition domains (CRDs) of HA was estimated. The star polymer with the predicted degree of polymerization was synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization, and 6′-sialyllactose was conjugated as the glycoepitope for HA. The designed glycoligand exhibited the strongest interaction with HA as a result of multivalent binding. This finding demonstrated that the biological function of the synthetic polymer could be controlled by precisely defining the polymer structures.

DOI： 10.1021/acs.biomac.1c01483

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PubMed

Repository Public URL： http://hdl.handle.net/2324/4793641

Language：English   Publishing type：Research paper (scientific journal)  

One of the new strategies to treat autoimmune diseases is to target Siglec, a membrane protein receptor with the ability to suppress immune responses. Herein, we synthesized glycopolymers carrying 3′-sialyllactose in various glycounit densities. RAW 264.7 macrophages transfected to express secreted alkaline phosphatase (SEAP) were used to evaluate the immunosuppression ability of the glycopolymers. The inhibition of the signal transmission was dependent on the glycounit densities of the glycopolymers, and was maximized at the moderate density (70%).

Other Link： https://www.journal.csj.jp/doi/full/10.1246/cl.210740

Repository Public URL： http://hdl.handle.net/2324/4793646

Language：English   Publishing type：Research paper (scientific journal)  

Carbohydrates on cell surfaces are known to interact not only with lectins but also with other carbohydrates; the latter process is known as a carbohydrate–carbohydrate interaction. Such interactions are observed in complex oligosaccharides. It would be surprising if these interactions were observed in simple monosaccharides of mannose. In this study, the interaction between glycopolymers carrying monosaccharides of mannose was quantitatively investigated by quartz crystal microbalance measurements. We measured the interactions with glycopolymers carrying mannose, galactose and glucose. Surprisingly, the interaction between the glycopolymers and mannose was much stronger than that between other saccharides.

DOI： 10.1039/D1TB02344F

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Repository Public URL： http://hdl.handle.net/2324/4793644

Language：English   Publishing type：Research paper (scientific journal)   Publisher：Reaction Chemistry and Engineering  

The effect of monolith structure and monolith reactor inner diameter on the residence time distribution (RTD), and the relationship between RTD and the catalytic efficiency of the asymmetric aldol addition reaction between p-nitrobenzaldehyde and cyclohexanone were examined. A monolith column containing L-proline as a catalyst was prepared using poly(ethylene glycol) (PEG) as the porogen. The monolith column prepared with PEG with a molecular weight of 6000 Da displayed a narrow pore size distribution and showed a controlled RTD. The performance of monolith reactors with different inner diameters (micro- and millireactors, 0.53 and 4.00 mm) was compared: the microreactor displayed a narrower RTD and a higher turnover number for the asymmetric aldol addition reaction than the millireactor. The different linear flow velocities in the microreactor did not affect the catalytic reaction efficiency and enantioselectivity, demonstrating that the RTDs can be controlled regardless of the flow velocity.

DOI： 10.1039/D1RE00386K

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Repository Public URL： http://hdl.handle.net/2324/4793643

Language：English   Publishing type：Research paper (scientific journal)  

Thermocells are thermoelectrochemical conversion systems for harvesting low-temperature thermal energy. Liquid-state thermocells are particularly desirable because of low cost and their high conversion efficiency at temperatures around physiological temperature, and they have, thus, been extensively studied. However, the performance of the thermocells has to be improved to utilize them as energy chargers and/or batteries. Recently, we reported that a liquid-state thermocell driven by the volume phase transition of hydrogel nanoparticles showed highly efficient thermoelectric conversion with Seebeck coefficient (Se) of −6.7 mV K–1. Here, we report the design rationale of the thermocells driven by the phase transition. A high Se of −9.5 mV K–1 was achieved at temperature between 36 and 40 °C by optimizing choice and amount of redox chemical species. The figure of merit (ZT) of the thermocell was improved by selecting appropriate electrolyte salt to increase the ionic conductivity and prevent the precipitation of nanoparticles. Furthermore, screening of nanoparticles revealed the high correlation between Se and the pH shift generated as a result of phase transition of the nanoparticles. After optimization, the maximum ZT of 8.0 × 10–2 was achieved at a temperature between 20 and 70 °C.

DOI： 10.1021/acsami.1c07266

Language：English   Publishing type：Research paper (scientific journal)  

The “carbohydrate module method” is a promising approach for oligosaccharide mimetics using polymeric materials. However, it is difficult to predict the optimal structure for a particular oligosaccharide mimetic, and an efficient strategy for the synthesis and evaluation of glycopolymers is desirable. In this study, a screening of glycopolymers for the “carbohydrate module method” by a combination of photoinduced electron/energy transfer-reversible addition–fragmentation chain-transfer (PET-RAFT) polymerization and surface plasmon resonance imaging (SPRI) is demonstrated. The facile and fast screening of synthetic glycomimetics was achieved, and the glycopolymer with the optimal structure as a GM1 mimetic strongly interacted with the cholera toxin B subunit.

DOI： 10.1039/D1CC04394C

Repository Public URL： http://hdl.handle.net/2324/4706206

Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.2116/analsci.21P042

Language：English   Publishing type：Research paper (scientific journal)  

Molecular mobility is important for interactions of biofunctional polymers with target molecules. Monomer structures for synthetic biofunctional polymers are usually selected based on their compatibility with polymerization systems, whereas the influence of monomer structures on the interaction with target molecules is hardly considered. In this report, we evaluate the correlation between the monomer structures of glycopolymers and their interactions with concanavalin A (ConA) with respect to the molecular mobility. Two types of glycopolymers bearing mannose are synthesized with acrylamide or acrylate monomers. Despite the similar structures, except for amide or ester bonds in the side chains, the acrylate-type glycopolymers exhibit stronger interaction with ConA both in the isothermal titration calorimetry measurement and in a hemagglutination inhibition assay. Characterization of the acrylate-type glycopolymers suggests that the higher binding constant arises from the higher molecular mobility of mannose units, which results from the rotational freedom of ester bonds in their side chains.

DOI： 10.1021/acs.biomac.1c00553

Repository Public URL： http://hdl.handle.net/2324/4706207

Language：English   Publishing type：Research paper (scientific journal)  

The development of robust and thin CO2 separation membranes that allow fast and selective permeation of CO2 will be crucial for rebalancing the global carbon cycle. Hydrogels are attractive membrane materials because of their tunable chemical properties and exceptionally high diffusion coefficients for solutes. However, their fragility prevents the fabrication of thin defect-free membranes suitable for gas separation. Here, we report the assembly of defect-free hydrogel nanomembranes for CO2 separation. Such membranes can be prepared by coating an aqueous suspension of colloidal hydrogel microparticles (microgels) onto a flat, rough, or micropatterned porous support as long as the pores are hydrophilic and the pore size is smaller than the diameter of the microgels. The deformability of the microgel particles enables the autonomous assembly of defect-free 30–50 nm-thick membrane layers from deformed ∼15 nm-thick discoidal particles. Microscopic analysis established that the penetration of water into the pores driven by capillary force assists the assembly of a defect-free dense hydrogel layer on the pores. Although the dried films did not show significant CO2 permeance even in the presence of amine groups, the permeance dramatically increased when the membranes are adequately hydrated to form a hydrogel. This result indicated the importance of free water in the membranes to achieve fast diffusion of bicarbonate ions. The hydrogel nanomembranes consisting of amine-containing microgel particles show selective CO2 permeation (850 GPU, αCO2/N2 = 25) against post-combustion gases. Acid-containing microgel membranes doped with amines show highly selective CO2 permeation against post-combustion gases (1010 GPU, αCO2/N2 = 216) and direct air capture (1270 GPU, αCO2/N2 = 2380). The membrane formation mechanism reported in this paper will provide insights into the self-assembly of soft matters. Furthermore, the versatile strategy of fabricating hydrogel nanomembranes by the autonomous assembly of deformable microgels will enable the large-scale manufacturing of high-performance separation membranes, allowing low-cost carbon capture from post-combustion gases and atmospheric air.

DOI： 10.1021/acsami.1c06447

Language：Japanese   Publishing type：Research paper (scientific journal)  

The bioinert interfaces that prevent adhesion of proteins and cells are important for biomaterial applications. In order to design a bioinert interface, the immobilization of an appropriate functional group and the control of molecular density is required. Dendrimer was modified with triethylene glycol (TEG) to display a dense brush structure. TEG with different density and terminal groups were immobilized with a dendrimer template and thiol terminated molecules. The inhibitory effect on protein and bacteria binding was investigated. The physical property of the interface was measured by QCM-admittance to clarify the factor of the bioinert property.

DOI： 10.2116/analsci.20P388

Repository Public URL： http://hdl.handle.net/2324/4479684

Language：Japanese   Publishing type：Research paper (scientific journal)  

DOI： doi.org/10.1016/j.eurpolymj.2020.110044

Repository Public URL： http://hdl.handle.net/2324/4479609

Language：Japanese   Publishing type：Research paper (scientific journal)  

2020,8, 10101-10107

DOI： doi.org/10.1039/DoTB02093A

Repository Public URL： http://hdl.handle.net/2324/4479697

Language：Japanese   Publishing type：Research paper (scientific journal)  

DOI： doi.org/10.1021/jacs.0c08600

Language：Japanese   Publishing type：Research paper (scientific journal)  

Hybridization of porous synthetic polymer and sophisticated ligands play an important role in transition‐metal catalysis for chemical transformations at laboratory and industrial levels. A monolithic porous polymer, which is a single piece with continuous macropores, is desired for high permeability, fast mass transfer properties, high stability, and easy modification. Herein, we first develop a monolithic porous polystyrene containing three‐fold cross‐linked PPh3 (M‐PS‐TPP ) for transition‐metal catalysis. The monolithic and macroporous structure of M‐PS‐TPP was fabricated via polymerization‐induced phase separation using porogenic solvent. Moreover, the M‐PS‐TPP was synthesized using different feed ratios of divinylbenzene (DVB) for site‐isolation and mono‐P‐ligating behavior of PPh3. 31P CP/MAS NMR analysis revealed that the different selectivity of M‐PS‐TPP s was obtained in formation of mono‐P‐ligation toward PdII. The macroporous properties and controlled mono‐P‐ligating behavior of M‐PS‐TPP facilitated the challenging Pd‐catalyzed Suzuki‐Miyaura cross‐coupling reaction of chloroarenes.

DOI： doi.org/10.1002/cctc.202000651

Repository Public URL： http://hdl.handle.net/2324/4706208

Language：Japanese   Publishing type：Research paper (scientific journal)  

DOI： doi.org/10.1021/acs.iecr.0c02404

Repository Public URL： http://hdl.handle.net/2324/4479611

Language：Japanese   Publishing type：Research paper (scientific journal)  

DOI： doi.org/10.1039/DoMA00149J

Language：English   Publishing type：Research paper (scientific journal)  

Controlled polymerization through living radical polymerization is widely studied. Controlled polymerization enables synthetic polymers with precise structures, which have the potential for excellent bio-functional materials. This review summarizes the applications of controlled polymers, especially those via living radical polymerization, to biofunctional materials and conjugation with biomolecules. In the case of polymer ligands like glycopolymers, the polymers control the interactions with proteins and cells based on the precise polymer structures. Living radical polymerization enables the conjugation of polymers to proteins, antibodies, nucleic acids and cells. Those polymer conjugations are a sophisticated method to modify bio-organisms. The polymer conjugations expand the potential of biofunctional materials and are useful for understanding biology.

DOI： 10.1039/c9tb02418b

Language：English   Publishing type：Research paper (scientific journal)  

Abiotic ligands that bind to specific biomolecules have attracted attention as substitutes for biomolecular ligands, such as antibodies and aptamers. Radical polymerization enables the production of robust polymeric ligands from inexpensive functional monomers. However, little has been reported about the production of monodispersed polymeric ligands. Herein, we present homogeneous ligands prepared via radical polymerization that recognize epitope sequences on a target peptide and neutralize the toxicity of the peptide. Taking advantage of controlled radical polymerization and separation, a library of multifunctional oligomers with discrete numbers of functional groups was prepared. Affinity screening revealed that the sequence specificity of the oligomer ligands strongly depended on the number of functional groups. The process reported here will become a general step for the development of abiotic ligands that recognize specific peptide sequences.

DOI： 10.1002/anie.201910558

Language：English   Publishing type：Research paper (scientific journal)  

Effective screening methods for the development of glycopolymers as molecular recognition materials are desirable for the discovery of novel biofunctional materials. A glycopolymer library was prepared to obtain guidelines for the design of glycopolymers for the recognition of cholera toxin B subunits (CTB). Glycopolymers with varying ratios of hydrophobic and sugar units were synthesized by reversible addition fragmentation chain transfer polymerization. N-tert-Butylacrylamide, N-phenylacrylamide, and N-cyclohexylacrylamide as hydrophobic units were copolymerized in the polymer backbone, and galactose, which contributes to CTB recognition, was introduced into the side chains by "post-click" chemistry. The thiol-terminated glycopolymers were immobilized on a gold surface. The polymer immobilization substrate was analyzed in terms of interaction with galactose recognition proteins (CTB, peanut agglutinin, and Ricinus communis agglutinin I) using surface plasmon resonance imaging. The polymers with high ratios of sugar and hydrophobic units had the strongest interactions with the CTB, which was different from the trend with peanut agglutinin and Ricinus communis agglutinin I. The binding constant of the CTB with the glycopolymer with hydrophobic units was 4.1 × 10⁶ M^-1, which was approximately eight times larger than that of the polymer without hydrophobic units. A correlation was observed between the log P value and the binding constant, indicating that the hydrophobic interaction played an important role in binding. New guidelines for the design of recognition materials were obtained by our screening method.

DOI： 10.1021/acsomega.9b02877

Language：English   Publishing type：Research paper (scientific journal)  

We investigated synthetic biomacromolecules to control molecular interactions. Multifunctional glycopolymers for molecular recognition were prepared via living radical polymerization and post-click chemistry with orthogonal Huisgen and thiol-epoxy reactions. The synthesis of the polymer backbone and the subsequent side-chain introduction successfully proceeded in high yield. The multifunctional glycopolymers had a tri-block structure: the first and third blocks contained mannose, and the second block contained either a positively or negatively charged group or a neutral hydrophilic group. The molecular recognition of the glycopolymers toward lectin was evaluated via fluorescence quenching measurements. Because of the electrostatic interaction, the binding constant varied in the following order: positively charged glycopolymer (PT110) > negatively charged glycopolymer (NT110). The effect of the electrostatic interactions was modest compared with the effect of the carbohydrate–lectin binding. These results suggested that the carbohydrate–lectin interaction was an important factor in the molecular recognition of glycopolymers. This study provides guidelines for the preparation of multifunctional polymers, such as biomaterials.

DOI： 10.1038/s41428-019-0244-x

Language：English   Publishing type：Research paper (scientific journal)  

The present invention relates generally to compositions and methods comprising abiotic, synthetic polymers with affinity and specificity to proteins. The synthetic polymers are an improvement over biological agents by providing a simpler, less expensive, and customizable platform for binding to proteins. In one embodiment, the compositions and methods relate to synthetic polymers with affinity and specificity to vascular endothelial growth factor (VEGF). In one embodiment, the compositions are useful for treating diseases and disorders related to the overexpression of VEGF. In one embodiment, the compositions are useful for treating cancer. In one embodiment, the compositions are useful for detecting VEGF levels from biological samples. In one embodiment, the compositions are useful for detecting overexpression of VEGF from biological samples. In one embodiment, the compositions are used to diagnose cancer.

Language：English   Publishing type：Research paper (scientific journal)  

DOI： doi/10.1021/acs.biomac.9b00515

Language：English   Publishing type：Research paper (scientific journal)  

The precise design of synthetic polymer ligands using controlled polymerization techniques provides an advantage for the field of nanoscience. We report the topological design of glyco-ligands based on synthetic polymers for targeting hemagglutinin (HA, lectin on the influenza virus). To achieve precise arrangement of the glycounits toward the sugar-binding pockets of HA, triarm star glycopolymers were synthesized. The interaction of the star glycopolymers with HA was found to depend on the length of the polymer arms and was maximized when the hydrodynamic diameter of the star glycopolymer was comparable to the distance between the sugar-binding pockets of HA. Following the formula of multivalent interaction, the number of binding sites in the interaction of the glycopolymers with HA was estimated as 1.8–2.7. Considering one HA molecule has three sugar-binding pockets, these values were reasonable. The binding mode of synthetic glycopolymer–ligands toward lectins could be tuned using controlled radical polymerization techniques.

DOI： 10.1021/acs.bioconjchem.9b00134

Repository Public URL： http://hdl.handle.net/2324/2320611

Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1002/pola.29344

Repository Public URL： http://hdl.handle.net/2324/2320610

Language：English   Publishing type：Research paper (scientific journal)  

A monolayer membrane containing gelling polymer particles having at least one of a basic functional group and an acidic functional group, and having a thickness of less than 5 μm. A composite having a porous carrier and gelling polymer particles having at least any one of a basic functional group and an acidic functional group and filling up the surface pores of the porous carrier. The invention can provide a novel material capable of efficiently separating an acid gas from a mixed gas.

Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1002/asia.201900053

Repository Public URL： http://hdl.handle.net/2324/2320131

Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1021/acs.langmuir.8b01527

Other Link： https://pubs.acs.org/doi/abs/10.1021/acs.langmuir.8b01527

Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1038/ s41428-018-0102-2

Language：English   Publishing type：Research paper (scientific journal)  

We have synthesized and immobilized PEGMA500-Phosmer to Ti6Al4V surfaces by a simple procedure to reduce bacteria-associated infection without degrading the cell response. Adhered bacteria coverage was lessened to 1% on polymer-coated surfaces when exposed to Escherichia coli, Staphylococcus epidermidis, and Streptococcus mutans. Moreover, PEGMA500-Phosmer and homoPhosmer coatings presented better responses to MC3T3-E1 preosteoblast cells when compared with the results for PEGMA2000-Phosmer-coated and raw Ti alloy surfaces. The behavior of balancing bacterial inhibition and cell attraction of the PEGMA500-Phosmer coating was explained by the grafted phosphate groups, with an appropriate PEG brush length facilitating greater levels of calcium deposition and further fibronectin adsorption when compared with that of the raw Ti alloy surface.

DOI： 10.1021/acsami.8b07757

Other Link： https://pubs.acs.org/doi/abs/10.1021/acsami.8b07757

Language：English   Publishing type：Research paper (scientific journal)  

Protein affinity reagents are widely used in basic research, diagnostics and separations and for clinical applications, the most common of which are antibodies. However, they often suffer from high cost, and difficulties in their development, production and storage. Here we show that a synthetic polymer nanoparticle (NP) can be engineered to have many of the functions of a protein affinity reagent. Polymer NPs with nM affinity to a key vascular endothelial growth factor (VEGF165) inhibit binding of the signalling protein to its receptor VEGFR-2, preventing receptor phosphorylation and downstream VEGF165-dependent endothelial cell migration and invasion into the extracellular matrix. In addition, the NPs inhibit VEGF-mediated new blood vessel formation in Matrigel plugs in vivo. Importantly, the non-toxic NPs were not found to exhibit off-target activity. These results support the assertion that synthetic polymers offer a new paradigm in the search for abiotic protein affinity reagents by providing many of the functions of their protein counterparts.

DOI： 10.1038/nchem.2749

Other Link： https://www.nature.com/articles/nchem.2749

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

Previous studies have clearly shown the importance of the multivalent effect in saccharide–protein interactions. To investigate the multivalent effect, the use of multivalent compounds or “glycoclusters” is indispensable, and many groups have reported syntheses of glycocluster compounds. Examples of glycoclusters include liposomes with glycolipids, glycocalixarenes, glycocyclodextrins, glycopeptides, and glycopolymers. Among the various synthetic glycoclusters, glycopolymers have been the subject of much attention . In this review, we define glycopolymers as polymers carrying pendant saccharides. Since glycopolymers have larger valencies than other multivalent compounds, they show the largest amplification effects in molecular recognition. Glycopolymers are able to be prepared as nanomaterials by controlled polymerization. In this section of the review, we discuss glycopolymers and their application for biotechnology.

DOI： 10.1021/acs.chemrev.5b00247

Language：English   Publishing type：Research paper (scientific journal)  

Modification of the interface properties on hydroxyapatite and tooth enamel surfaces was investigated to fabricate bacterial resistance in situ. A series of copolymers containing pendants of poly(ethylene glycol) methyl ether methacrylate (PEGMA) and ethylene glycol methacrylate phosphate (Phosmer) were polymerized by conventional free radical polymerization and changing the feed ratio of monomers. The copolymers were immobilized on hydroxyapatite and tooth enamel via the affinity of phosphate groups to hydroxyapatite to form the stable and durable polymer brushes on the surfaces. The amounts of polymer immobilized depended on the phosphate group ratio in the copolymers. Surface modification altered the interfacial properties of hydroxyapatite and inhibited bacterial adhesion. Copolymers containing 40–60% PEGMA segments showed a significant inhibitory effect on bacterial adhesion of S. epidermidis both in the presence and absence of plaque model biomacromolecules.

DOI： 10.1021/acsbiomaterials.5b00349

Language：Japanese  

Language：Japanese   Publishing type：Research paper (scientific journal)  

Herein we revealed the design rationale of thermally responsive gel particle (GP) films that reversibly capture and release large amounts of CO2 over a narrow temperature range (30–75 °C). The pKa value of ammonium ions in the GPs at both the CO2 capture temperature (30 °C) and release temperature (75 °C) is found to be the primary factor responsible for the stoichiometry of reversible CO2 capture by the amines in the GP films. The pKa values can be tuned by the properties of GPs such as volume phase transition temperature (VPTT), size, swelling ratio, and the imprinted microenvironment surrounding the amines. The optimal GP obtained according to the design rationale showed high capture capacity (68 mL CO2 per g dry GPs, 3.0 mmol CO2 per g dry GPs), although the regeneration temperature was as low as 75 °C. We anticipate that GP films that reversibly capture other acidic and basic gases in large amounts can also be achieved by the pKa tuning procedures.

DOI： 10.1039/C5SC01978H

Language：English   Publishing type：Research paper (scientific journal)  

A copolymer with α-d-mannose (Man) and trimethoxysilane (TMS) units was synthesized for immobilization on siliceous matrices such as a sensor cell and membrane. Immobilization of the trimethoxysilane-containing copolymer on the matrices was readily performed by incubation at high heat. The recognition of lectin by poly(Man-r-TMS) was evaluated by measurement with a quartz crystal microbalance (QCM) and adsorption on an affinity membrane, QCM results showed that the mannose-binding protein, concanavalin A, was specifically bound on a poly(Man-r-TMS)-immobilized cell with a higher binding constant than bovine serum albumin. The amount of concanavalin A adsorbed during permeation through a poly(Man-r-TMS)-immobilized membrane was higher than that through an unmodified membrane. Moreover, the concanavalin A adsorbed onto the poly(Man-r-TMS)-immobilized membrane was recoverable by permeation of a mannose derivative at high concentration.

DOI： 10.1021/am2014713

Language：English   Publishing type：Research paper (international conference proceedings)  

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

DOI： doi:10.1016/j.colsurfb.2011.01.003

Language：English   Publishing type：Research paper (scientific journal)  

DOI： doi:10.1246/bcsj.2010030

Language：Japanese   Publishing type：Research paper (scientific journal)  

DOI： doi:10.1295/koron.67.584

Publishing type：Research paper (scientific journal)  

DOI： 10.1246/bcsj.20100094

Language：English   Publishing type：Research paper (scientific journal)  

DOI： doi:10.1246/cl.2010.923

Other Link： http://www.jstage.jst.go.jp/article/cl/39/9/923/_pdf

Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1021/bc100053x

Other Link： http://pubs.acs.org/doi/abs/10.1021/bc100053x?prevSearch=tomohiro%2Bfukuda&searchHistoryKey=

Language：English   Publishing type：Research paper (scientific journal)  

DOI： doi:10.1038/pj.2009.321

Other Link： http://www.nature.com/pj/journal/v42/n2/full/pj2009321a.html

Language：English   Publishing type：Research paper (scientific journal)  

DOI： doi:10.4052/tigg.21.324

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (international conference proceedings)  

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

Language：Japanese  

Language：Japanese   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1021/bm025714b

Language：English   Publishing type：Research paper (scientific journal)  

DOI： doi:10.1016/S0003-2697(02)00318-4

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

Language：Japanese   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

Publisher：European Journal of Organic Chemistry  

Continuous-flow organic transformations using immobilized catalysts are crucial for green and sustainable chemistry. Cross-linked polymer ligands offer high stability, ease of recovery through filtration, and thus enhance performance in continuous-flow reactions via transition-metal catalysis. Additionally, the cross-linking structure of the polymer support creates a unique reaction platform that controls the coordination behavior of the supported ligands and stabilizes the metal catalysts. However, insights into the material-based design for preparing highly active and durable immobilized metal catalysts are still limited. In this report, we propose a straightforward approach to boost both selective mono-coordination and effective stabilization of metal complexes. We developed threefold cross-linked polystyrene-triphenylphosphine hybrid monoliths with cross-linking structures adjusted by varying the content of divinylbenzene as co-cross-linker. The coordination behaviors and metal-support interactions of these monoliths were evaluated, highlighting the importance of co-cross-linker content in site-isolating phosphine units and stabilizing metal centers via arene-metal interactions on the polystyrene network. By optimizing the cross-linking structure, the monolith catalysts demonstrated exceptionally high catalytic activity and durability in Pd-catalyzed C−Cl transformations, such as Suzuki–Miyaura cross-couplings and Buchwald-Hartwig aminations in continuous flow. This underscores the utility of our monolith system in challenging transition-metal catalysis.

DOI： 10.1039/D5SC00612K

Publisher：European Journal of Organic Chemistry  

Continuous-flow organic transformations using immobilized catalysts are crucial for green and sustainable chemistry. Cross-linked polymer ligands offer high stability, ease of recovery through filtration, and thus enhance performance in continuous-flow reactions via transition-metal catalysis. Additionally, the cross-linking structure of the polymer support creates a unique reaction platform that controls the coordination behavior of the supported ligands and stabilizes the metal catalysts. However, insights into the material-based design for preparing highly active and durable immobilized metal catalysts are still limited. In this report, we propose a straightforward approach to boost both selective mono-coordination and effective stabilization of metal complexes. We developed threefold cross-linked polystyrene-triphenylphosphine hybrid monoliths with cross-linking structures adjusted by varying the content of divinylbenzene as co-cross-linker. The coordination behaviors and metal-support interactions of these monoliths were evaluated, highlighting the importance of co-cross-linker content in site-isolating phosphine units and stabilizing metal centers via arene-metal interactions on the polystyrene network. By optimizing the cross-linking structure, the monolith catalysts demonstrated exceptionally high catalytic activity and durability in Pd-catalyzed C−Cl transformations, such as Suzuki–Miyaura cross-couplings and Buchwald-Hartwig aminations in continuous flow. This underscores the utility of our monolith system in challenging transition-metal catalysis.

DOI： 10.1039/D4RE00597J

Publisher：European Journal of Organic Chemistry  

Continuous-flow organic transformations using immobilized catalysts are crucial for green and sustainable chemistry. Cross-linked polymer ligands offer high stability, ease of recovery through filtration, and thus enhance performance in continuous-flow reactions via transition-metal catalysis. Additionally, the cross-linking structure of the polymer support creates a unique reaction platform that controls the coordination behavior of the supported ligands and stabilizes the metal catalysts. However, insights into the material-based design for preparing highly active and durable immobilized metal catalysts are still limited. In this report, we propose a straightforward approach to boost both selective mono-coordination and effective stabilization of metal complexes. We developed threefold cross-linked polystyrene-triphenylphosphine hybrid monoliths with cross-linking structures adjusted by varying the content of divinylbenzene as co-cross-linker. The coordination behaviors and metal-support interactions of these monoliths were evaluated, highlighting the importance of co-cross-linker content in site-isolating phosphine units and stabilizing metal centers via arene-metal interactions on the polystyrene network. By optimizing the cross-linking structure, the monolith catalysts demonstrated exceptionally high catalytic activity and durability in Pd-catalyzed C−Cl transformations, such as Suzuki–Miyaura cross-couplings and Buchwald-Hartwig aminations in continuous flow. This underscores the utility of our monolith system in challenging transition-metal catalysis.

DOI： 10.1002/ejoc.202400974

Web of Science

Scopus

Publisher：RSC Applied Polymers  

We conducted an experiment to compare the predicted outcomes with the practical results of synthesizing four-dimensional (4D) hydrogels and observing their 4D motion. We employed a computer simulator and utilized PET-RAFT and orthogonal chemistry methods. To initiate the study on 4D materials, we employed the swelling method and controlled it by utilizing visible light synthesis. To regulate the irradiation time of blue light, we employed cinnamoyl ethyl acrylate as an orthogonal system to control crosslinking density. Various physical properties were assessed using a rheometer. Our findings confirmed that the movement could be controlled by adjusting the swelling ratio of the upper and lower parts, thereby implementing a bi-layer design based on differences in crosslinking density. This study highlights the successful synthesis of hydrogels with diverse physical properties and demonstrates the potential of 4D materials through the orthogonal synthesis technique.

DOI： 10.1039/d4lp00232f

Scopus

Language：English   Publishing type：Research paper (scientific journal)   Publisher：RSC Applied Polymers  

We prepared polystyrene-based polymer gels containing iron porphyrin and evaluated the effects of the cross-linked structures on the photoreduction of carbon dioxide to carbon monoxide. The amount of generated carbon monoxide was influenced by the diffusion of the substrates into the gel structures.

DOI： 10.1039/D4LP00135D

DOI： 10.1039/D4LP00135D

Scopus

Other Link： https://doi.org/10.1039/D4LP00135D

Language：English   Publishing type：Research paper (scientific journal)   Publisher：Langmuir  

Molecular assemblies that transform in response to pH and saccharide concentration are promising nanomaterials in the field of biomedicine, and polymeric micelles of amphiphilic polymers with phenylboronic acids (PBAs) have been studied. Herein, we report the impact of zwitterions on the acidity constant for the collapse and the glucose sensitivity of a polymeric micelle produced from a diblock copolymer comprising polyacrylamides with PBA and zwitterionic carboxybetaine (PAEBB-b-PCBAAm). The diblock copolymer was synthesized through reversible addition-fragmentation chain-transfer polymerization followed by deprotection. PAEBB-b-PCBAAm produced micellar aggregates in aqueous solutions at a neutral pH, and the polymeric micelles collapsed at a pH of 11.0 because the PBA transformed into a hydroxyboronate anion. The pKa decreased in the presence of glucose owing to boronate ester formation. The PCBAAm chain significantly increased the pH at which the molecular assemblies dissociated. This is probably because the pKa of boronic acid increased through the dipolar interaction of zwitterions, and/or the zwitterionic polymer corona is valid for screening of PBA ionization and electrostatic repulsion of boronate anions. This study on the modulation of pKa through the zwitterionic interaction can facilitate the molecular design of pH- and saccharide-responsive biomaterials.

DOI： 10.1021/acs.langmuir.4c01075

Web of Science

Scopus

PubMed

Language：English   Publishing type：Research paper (scientific journal)   Publisher：Journal of Materials Chemistry B  

Carbohydrate-based membranes that show molecular recognition ability are interesting mimics of biointerfaces. Herein, we prepared glycopolymer membranes on QCM-D sensor chips using a solvent-assisted method and investigated their interactions with a target lectin. The membrane containing the glycopolymer with a random arrangement of the carbohydrate units adsorbed more lectin than that containing the glycopolymer with an organized block of carbohydrate units.

DOI： 10.1039/d3tb02663a

DOI： 10.1039/d3tb02663a

Web of Science

Scopus

PubMed

CiNii Research

Language：English   Publishing type：Research paper (scientific journal)   Publisher：ACS Applied Materials and Interfaces  

Here, we report the design rationale of CO2 separation membranes with micropatterned surface structures. Thin film composite (TFC) membranes with micropatterned surface structures were fabricated by spray coating amine-containing hydrogel particles on the top of micropatterned porous support membranes, which were synthesized by a polymerization-induced phase separation process in a micromold (PIPsμM). The pore size of the support membranes was optimized by tuning the proportion of good and poor solvents for the polymerization process so that the microgels would be assembled as a defect-free separation layer. The relationship between the size of the micropatterned structures on the surface of the support membrane and the thickness of the separation layer was optimized to maximize the surface area of the separation layer. The rationally designed micropatterned TFC membrane showed a CO2 permeability (835.8 GPU) proportional to the increase in surface area relative to the flat membrane with a high CO2/N2 selectivity of 58.7. The rational design for micropatterned TFC membranes will enable the development of inexpensive and high-performance functional membranes not only for CO2 separation but also for other applications such as water treatment and membrane reactors.

DOI： 10.1021/acsami.3c15966

Web of Science

Scopus

PubMed

Language：English   Publisher：American Chemical Society (ACS)  

Photoinduced electron/energy transfer-reversible addition–fragmentation chain transfer (PET-RAFT) polymerization enables the production of well-controlled synthetic polymers under mild conditions by using visible-light energy. Although flow reactors are suitable for photoreactions in terms of light penetration, contamination of photocatalysts occurs in a homogeneous system and necessitates product purification. Immobilizing the photocatalysts onto supports can eliminate the need for this purification step and enhance the potential for industrial applications of PET-RAFT polymerization. Herein, we report the development of a packed-bed flow photoreactor wherein a photocatalyst for PET-RAFT polymerization, zinc tetraphenylporphyrin, was immobilized onto packed silica particles. Continuous PET-RAFT polymerization of a model monomer (N,N-dimethylacrylamide) was achieved without leakage of the porphyrin molecules. The effects of various reaction conditions, such as the residence time, catalyst density, and target molecular weight, on the polymerization reaction were evaluated. This work contributes to the realization of a facile and practical manufacturing process for highly valuable synthetic polymers.

DOI： 10.1021/acs.iecr.3c03496

Web of Science

Scopus

CiNii Research

Language：Japanese   Publishing type：Research paper (other academic)   Publisher：The Society of Polymer Science, Japan  

<p>Glycopolymers, polymers with sugars in the side chains of polymers, are biobased polymers. Glycopolymers can be synthesized mainly by addition polymerization with the vinyl sugar derivatives, and are unique materials that allow the use of synthetic polymer technology for sugars, which is otherwise difficult to handle. Glycopolymers are useful for the development of water-soluble polymers, amphiphilic polymers, and biofunctional materials. As physical properties, glycopolymers possess physicochemical properties such as water-solubility and amphiphilicity, as well as self-assembling properties. In addition, because of their saccharide-accumulated structure, glycopolymers have strong molecular recognition properties based on the multivalent effect and interact strongly with proteins, cells, pathogens, and other substances. The molecular recognizability can be controlled by precision polymerization and fused with other materials to create bio-devices.</p>

DOI： 10.1295/kobunshi.73.4_147

CiNii Research

Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：Bulletin of the Chemical Society of Japan  

Heterogeneous catalysts composed of a vitamin B12 derivative with a polymer or mesoporous silica were synthesized and characterized. These two types of catalysts were used in alkane oxidation reactions with mCPBA oxidant, and improved catalytic efficiency was obtained using the polymer supported B12 catalyst with a monolith structure compared to that of the monomeric B12 catalyst. The catalytic effects were also evaluated in several alkane substrates and the polymer supported B12 catalyst showed a better performance in all reactions compared to the silica-supported B12 catalyst.

DOI： 10.1246/bcsj.20220161

Web of Science

Scopus

Language：Japanese   Publishing type：Research paper (scientific journal)  

A microparticle counter based on a metal mesh device was developed. The metal mesh device had a lattice-shaped structure with well-regulated holes of 1.8 μm. The collection percentages of differently sized microparticles using the metal mesh device were determined by flow cytometry. The cut-off point and hole size of the metal mesh device were identical. Polystyrene microparticles were detected from changes in the spectroscopic properties of the metal mesh device. When microparticles were trapped on the holes of the metal mesh device, the transmittance in the infrared spectra decreased. Microparticles smaller than the holes were not detected by the metal mesh device, whereas 2 and 3 μm microparticles were detected. Polystyrene and silica microparticles could be counted using the metal mesh device via calibration curves between the concentration of microparticles and the change level in the transmittance of the metal mesh device. The separation of microparticles from a mixture suspension using the metal mesh device was evaluated. Unlike a microfiber filter, only 2 μm microparticles were collected from coexisting 1 μm microparticles by the metal mesh device. Owing to its high separation ability, the metal mesh device selectively detected 2 μm microparticles in coexisting 10-equivalence 1 μm microparticles.

DOI： 10.1016/j.apt.2021.04.002

Language：English   Publishing type：Research paper (scientific journal)  

A microparticle counter based on a metal mesh device was developed. The metal mesh device had a lattice-shaped structure with well-regulated holes of 1.8 μm. The collection percentages of differently sized microparticles using the metal mesh device were determined by flow cytometry. The cut-off point and hole size of the metal mesh device were identical. Polystyrene microparticles were detected from changes in the spectroscopic properties of the metal mesh device. When microparticles were trapped on the holes of the metal mesh device, the transmittance in the infrared spectra decreased. Microparticles smaller than the holes were not detected by the metal mesh device, whereas 2 and 3 μm microparticles were detected. Polystyrene and silica microparticles could be counted using the metal mesh device via calibration curves between the concentration of microparticles and the change level in the transmittance of the metal mesh device. The separation of microparticles from a mixture suspension using the metal mesh device was evaluated. Unlike a microfiber filter, only 2 μm microparticles were collected from coexisting 1 μm microparticles by the metal mesh device. Owing to its high separation ability, the metal mesh device selectively detected 2 μm microparticles in coexisting 10-equivalence 1 μm microparticles.

DOI： doi.org/10.1016/j.apt.2021.04.002

Language：Japanese   Publishing type：Research paper (scientific journal)  

DOI： 10.1038/s41428-020-00407-5

Language：Japanese   Publishing type：Research paper (scientific journal)  

DOI： doi.org/10.1039/d0tb00849d

Language：English   Publishing type：Research paper (scientific journal)  

Electrostatic interaction between synthetic polymer nanoparticles (NPs) and proteins is of considerable importance in the design of NPs that capture, neutralize, and deliver target molecules in a biological milieu. Ionizable functional groups, such as carboxylic acids and amines, are often introduced to NPs to tune the affinity with target bio-macromolecules through electrostatic attraction and repulsion. However, acids/bases are not always ionized at a physiological pH because acidities of the functional groups depend on the microenvironment around the acids/bases that are imprinted during the polymerization process. Here, we show that electrostatic interaction between acid-/base-containing NPs and target proteins strongly depends on the pH of the solution during the NP polymerization process. To prepare NPs that capture target proteins by electrostatic interactions at physiological pH, NPs must be polymerized within a pH range where the acid/base monomer is ionized. Acid-/base-containing NPs that exhibit completely different interactions with the proteins can be prepared by changing the polymerization pH without changing monomer compositions. Our results indicate that polymerization pH should be carefully tuned to design acid-/base-containing NPs that show desired affinity to all proteins in a biological milieu and to proteins of interest.

DOI： 10.1021/acsabm.0c00390

Language：English   Publishing type：Research paper (scientific journal)  

DOI： doi/10.1038/s41428-019-0298-9

Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1039/D0RA02803G

Language：Japanese   Publishing type：Research paper (scientific journal)  

DOI： 10.2116/analsci.21P042

Language：Japanese   Publishing type：Research paper (scientific journal)  

フロー合成による化学合成プロセスが精密有機合成の分野で注目されている．実用的かつ高効率なフロー合成を実現するため，洗練されたフローシステムおよびよく設計された固定化触媒は強力な手段である．多孔質モノリスは，三次元的な貫通孔をもち大きな比表面積および高い透過性能を有する一塊の多孔質体である．本研究では，O-Acryloyl-trans-4-hydroxy-L-proline hydrochlorideを共重合したAcrylamide骨格の多孔質モノリスを作製し，その多孔性を評価した．また，作製したモノリスを不斉アルドール付加反応に応用し，その触媒活性について評価した．モノリスは，ポロゲンとして用いるアルコール（Ethanol, 1-Butanol, 1-Octanol, あるいは1-Dodecanol）により多孔質モノリスの細孔直径および比表面積を制御することができた．また，そのモノリスを用いてフローシステムを構築し，12 hの滞留時間においてフロー条件下で不斉アルドール付加反応を行った．すべてのモノリスは61–74%のeeでフロー不斉アルドール付加反応を達成した．これは，有機分子触媒L-Prolineを導入した多孔質高分子モノリスを用いて，フロー不斉合成を達成した初めての例である

DOI： doi.org/10.1252/kakoronbunshu.46.77

Repository Public URL： http://hdl.handle.net/2324/4479695

Language：English   Publishing type：Research paper (scientific journal)  

The mixed-ligand system consisting of tris(2-aminoethyl)amine (TREN) and tris(2-dimethylaminoethyl)amine (Me₆-TREN) during the Cu(0) wire-catalyzed single electron transfer-living radical polymerization (SET-LRP) of methyl acrylate (MA) in "programmed" biphasic mixtures of the dipolar aprotic solvents NMP, DMF, and DMAc with H₂O is reported. Kinetic and chain end analysis studies by NMR and MALDI-TOF before and after thio-bromo "click" reaction demonstrated that Me₆-TREN complements and makes the less expensive TREN a very efficient ligand in the absence of externally added Cu(II)Br₂. Statistical analysis of the kinetic data together with control experiments demonstrated that this mixed-ligand effect enhanced the apparent rate constant of propagation, monomer conversion, and molecular weight control. The most efficient effect was observed at a 1/1 molar ratio between these two ligands, suggesting that in addition to a fast exchange between the two ligands, a new single dynamic ligand generated by hydrogen bonding may be responsible for the mixed ligand observed.

DOI： 10.1021/acs.biomac.9b01282

Language：English   Publishing type：Research paper (scientific journal)  

To establish effective chemical transformations, catalytic systems with advantages such as high activity, recyclability, durability, and operability have attracted considerable attention. One of the strategies for the development of high-performance catalytic systems is the use of polymer hydrogels. In this focus review, an overview of our research using poly(N-isopropyl acrylamide)-based hydrogel particles and macroporous monoliths as molecular catalysts and loading matrices for palladium catalysts is summarized.

DOI： 10.1038/s41428-020-0323-z

Language：Japanese   Publishing type：Research paper (scientific journal)  

Phase separation micromolding (PSμM) is an effective technique for fabricating porous membranes with micropatterned structures. However, reports on procedures to control the size and number of open pores on the patterned surface are scarce, which often limits the use of the surface-patterned membranes. This work presents a systematic study on tailoring open pores on the patterned surface of polyethersulfone (PES) membranes prepared by the PSμM procedure. The composition of the solvent and the concentration of PES in the casting solution were optimized to tune the size and number of pores on the membrane surfaces formed on a flat substrate during the nonsolvent-induced phase separation (NIPS) process. The surface porosity changed significantly and macrovoids appeared when the flat substrate was replaced by a micropatterned substrate. The vapor-induced phase separation process was applied prior to the NIPS process to prevent the formation of macrovoids. The composition of the casting solution was tuned again to prepare micropatterned porous PES membranes with open pores on the patterned surface. We observed that the size and number of pores were different depending on the pore locations on the patterned surface, which was caused by different solvent/nonsolvent demixing dynamics resulting from the physical discontinuity of micro-patterned membranes.

DOI： doi.org/10.1038/s41428-019-0298-9

Language：English   Publishing type：Research paper (scientific journal)  

DOI： doi/10.1021/acsapm.9b00940

Language：English   Publishing type：Research paper (scientific journal)  

DOI： doi.org/10.1039/C9FD00018F

Language：English   Publishing type：Research paper (scientific journal)  

DOI： doi.org/10.1246/cl.190293

Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.2116/analsci.18P498

Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1038/s41428-019-0170-y

Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1038/s41428-019-0170-y

Language：Japanese   Publishing type：Research paper (scientific journal)  

DOI： https://doi.org/10.1016/j.jconrel.2018.12.033

Language：Japanese   Publishing type：Research paper (scientific journal)  

DOI： DOI: 10.1021/acsami.8b11397

Language：Others   Publishing type：Research paper (scientific journal)  

When proteins are attached to microstructures such as a metal mesh device, changes in their optical properties occur. These changes have been characterized based on actual measurements in the infrared region of the spectrum. We have previously theoretically and experimentally demonstrated the optical changes associated with streptavidin. Here, we investigate three types of proteins: avidin, BSA, and lysozyme. The three proteins were adsorbed onto three types of metal mesh devices having different resonant frequencies, and the corresponding spectra were measured in the infrared region. The change in the frequency of the dip point in the spectrum was extracted to quantitatively determine the quantity of protein; these results were correlated with the quantitative measurements obtained by electrophoresis. By examining three types of different proteins, it was verified that a variety of proteins can be measured based on the optical characteristics of metal mesh devices.

DOI： 10.2116/analsci.17P523

Other Link： https://www.jstage.jst.go.jp/article/analsci/34/7/34_17P523/_article/-char/ja/

Language：Japanese   Publishing type：Research paper (scientific journal)  

DOI： DOI: 10.1021/acsabm.8b00096

Language：Japanese   Publishing type：Research paper (scientific journal)  

A metal mesh device has a structure in which through-holes of the same shape are periodically placed on a thin metal film, and the selection of such a structure makes it possible to sense objects of various sizes. In this study, we showed the structure of the metal mesh device and the relationship between the detectable optical domain and the size of the objects to be measured. In addition, from measurement of changes in electromagnetic wave transmission characteristics of the metal mesh device due to specific adsorption of particles with a mean diameter of 100 nm with surface modification with Streptavidin to a metal mesh device fixed with biotin, we showed that even large particles can be sensed. Based on these examinations, we showed that, by using a metal mesh device with detectable optical domain corresponding to the size of objects, even objects that are larger than protein can be sensed.

DOI： doi.org/10.2116/analsci.17P506

Language：English   Publishing type：Research paper (scientific journal)  

DOI： DOI: 10.1021/acsomega.7b00909

Language：English   Publishing type：Research paper (scientific journal)  

Four types of phosphorylated 2-hydroxyethyl methacrylate and poly(ethylene glycol) methyl ether methacrylate (PEGMA) block copolymers were synthesized by reversible addition fragmentation chain transfer (RAFT) polymerization and post-phosphorylation. These polymers were composed of different phosphate segments and similar PEG brushes. Polymers with defined phosphate segments were investigated to determine the optimal bonding affinity to hydroxyapatite (HAp). Polymers containing short phosphate segments (as low as 23 mer) were capable of immobilizing on HAp surfaces in situ in a short coating time with considerable durability. After surface modification, the dense PEG brushes altered the interfacial properties of HAp. The protein adsorption on the polymer-grafted HAp was drastically reduced compared with the bare HAp. Furthermore, the presence of the PEG brushes on the HAp surface resulted in bacterial inhibition. The polymer with the shortest phosphate segment (23 mer) showed superior inhibition ability.

DOI： 10.1016/j.colsurfb.2017.09.038

Language：Japanese   Publishing type：Research paper (scientific journal)  

The arrangement of sugars in glycopolymers contributes to their recognition. The molecular recognition of proteins was controlled by the living radical polymerization of glycopolymers. The glycopolymers were prepared by the copolymerization of propargyl methacrylate (Pr-MA) and triethyleneglycol methacrylate (TEG-MA) via living radical polymerization with a reversible addition–fragmentation glycopolymer chain transfer (RAFT) reagent and by subsequent sugar conjugation by click chemistry. The block copolymers were prepared by the polymerization of Pr-MA and TEG-MA. The molecular recognition of glycopolymers was analyzed using the fluorescence quenching of lectin and found to be dependent on the glycopolymer structures. Two-site binding of glycopolymers to concanavalin A (ConA) was attained by both the glycopolymer with a 105-mer and the tri-block glycopolymer with a 103-mer. Glycopolymers with either a 27- or 54-mer showed much weaker interaction because of one-site binding. The molecular recognition of the glycopolymer was controlled by the arrangement and size of the sugar cluster and not by the sugar density.

DOI： DOI: 10.1039/C7CC07107H (Communication)

Language：English   Publishing type：Research paper (scientific journal)  

pKa tuning of Brønsted acids in synthetic nano-materials is of great importance for the design of ion exchange and bio-/molecular-separation media and polymer catalysis. It has been reported that hydrogel nanoparticles with carboxylic acids that show large and reversible pKa shifts in response to thermal stimuli can be prepared by copolymerization of N-isopropylacrylamide (NIPAm), acrylic acids (AAc) and N,N′-methylene bisacrylamide (BIS) via the proton imprinting polymerization process. However, the reported range of pKa shifts is limited to the range of 5.3 to 7.5. In this study, we report a procedure to prepare proton imprinted NPs that show pKa shifts in the tuned pKa range and demonstrate applications of the NPs. pKa values ranging from 4.3 to 8.7 were achieved by designing the structure of monomers containing carboxylic acids and applying the proton imprinting procedure. It was demonstrated that proton-imprinted NPs with different pKa values could be used for the reversible and selective protonation of target molecules which have specific pKa values. Our results establish the generality of the proton imprinting procedure and provide a guide for designing stable and inexpensive materials for sophisticated purification processes.

DOI： 10.1039/C7TB02107K

Other Link： http://pubs.rsc.org/-/content/articlehtml/2017/tb/c7tb02107k

Language：Japanese   Publishing type：Research paper (scientific journal)  

We designed glycopolymers carrying sialyl oligosaccharides by “post-click” chemistry and evaluated the interaction with the influenza virus. The glycopolymer structures were synthesized in a well-controlled manner by reversible addition–fragmentation chain transfer polymerization and the Huisgen reaction. Acrylamide-type monomers were copolymerized to give hydrophilicity to the polymer backbones, and the hydrophilicity enabled the successful introduction of the oligosaccharides into the polymer backbones. The glycopolymers with different sugar densities and polymer lengths were designed for the interaction with hemagglutinin on the virus surface. The synthesized glycopolymers showed the specific molecular recognition against different types of influenza viruses depending on the sugar units (6′- or 3′-sialyllactose). The sugar density and the polymer length of the glycopolymers affected the interaction with the influenza virus. Inhibitory activity of the glycopolymer against virus infection was demonstrated.

DOI： DOI: 10.1021/acs.biomac.7b01426

Language：English   Publishing type：Research paper (scientific journal)  

Vimentin, desmin, glial fibrillary acidic protein (GFAP) and peripherin belong to type III intermediate filament family and are expressed in mesenchymal cells, skeletal muscle cells, astrocytes and peripheral neurons, respectively. Vimentin and desmin possess N‐acetyl‐d‐glucosamine (GlcNAc)‐binding properties on cell surfaces. The rod II domain of these proteins is a GlcNAc‐binding site, which also exists in GFAP and peripherin. However, the GlcNAc‐binding activities and behaviors of these proteins remain unclear. Here, we characterized the interaction and binding behaviors of these proteins, using various well‐defined GlcNAc‐bearing polymers synthesized by radical polymerization with a reversible addition‐fragmentation chain transfer reagent. The small GlcNAc‐bearing polymers strongly interacted with HeLa cells through vimentin expressed on the cell surface and interacted with vimentin‐, desmin‐, GFAP‐ and peripherin‐transfected vimentin‐deficient HeLa cells. These proteins present high affinity to GlcNAc‐bearing polymers, as shown by surface plasmon resonance. These results show that type III intermediate filament proteins possess GlcNAc‐binding activities on cell surfaces. These findings provide important insights into novel cellular functions and physiological significance of type III intermediate filaments.

DOI： DOI: 10.1111/gtc.12535

Language：English   Publishing type：Research paper (scientific journal)  

抄録
Biosensing of protein adsorption with metal mesh device (MMD) was investigated by computational calculations and experiments. Electromagnetic field computation was carried out with a single unit cell of MMD. Equivalent circuit model of MMD on the single unit cell was assumed, and the biosensing with MMD was analyzed in detail by computational calculation and experimental measurements. The dip frequency of MMD was shifted by adsorption of protein on MMD. The shift of dip frequency of MMD was proportional to the amount of protein adsorption. The sensitivity of MMD biosensing was dependent on the microstructure of MMD, and proportional to the square of the dip frequency. The refinement of MMD structure can improve the sensitivity of protein detection

DOI： 10.2116/analsci.33.1033

Other Link： https://www.jstage.jst.go.jp/article/analsci/33/9/33_1033/_article/-char/ja/

Language：English   Publishing type：Research paper (scientific journal)  

Microalgae offer great potential for the production of biofuel, but high photosynthetic activity is demanded for the practical realisation of microalgal biofuels. To this end, it is essential to evaluate the photosynthetic activity of single microalgal cells in a heterogeneous population. In this study, we present a method to monitor the photosynthetic activity of microalgae (in particular Euglena gracilis, a microalgal species of unicellular, photosynthetic, flagellate protists as our model organism) at single‐cell resolution by Raman spectroscopy with deuterium from deuterium oxide (D2O) as a tracking probe. Specifically, we replaced H2O in culture media with D2O up to a concentration of 20 % without disturbing the growth rate of E. gracilis cells and evaluated C−D bond formation as a consequence of photosynthetic reactions by Raman spectroscopy. We used the probe to monitor the kinetics of the C−D bond formation in E. gracilis cells by incubating them in D2O media under light irradiation. Furthermore, we demonstrated Raman microscopy imaging of each single E. gracilis cell to discriminate deuterated cells from normal cells. Our results hold great promise for Raman‐based screening of E. gracilis and potentially other microalgae with high photosynthetic activity by using D2O as a tracking probe.

DOI： 10.1002/cbic.201700314

Language：English   Publishing type：Research paper (scientific journal)  

In this study, macroporous materials, called glycomonoliths, were produced from saccharide-containing monomers, and used for affinity bioseparation of proteins in a continuous-flow system. The porous structure formation of the glycomonoliths involved polymerization-induced phase separation of the polyacrylamide unit. The pore size could be controlled between several hundred nanometers and several micrometers by changing the alcohol used as the porogenic solvent during the preparation of the monolith. The glycomonolith pores allowed for the permeation of solutions through the monoliths, which meant that they could be used in a continuous-flow system. The adsorption capacities of the glycomonoliths for the saccharide-binding protein (concanavalin A) were larger than that of a glycopolymer-grafted material because of the higher saccharide densities in the monoliths than the grafted material. When concanavalin A was eluted from the glycomonolith, the concentration of concanavalin A in the effluent was up to 11 times higher than that in the feed solution. The adsorption of concanavalin A to the glycomonolith was specific, even in the presence of other proteins.

DOI： 10.1039/C6TB02930B

Language：English   Publishing type：Research paper (scientific journal)  

To obtain a temperature-responsive CO2 absorbent with a high amine content, temperature-responsive gel particles (GPs) consisting of poly(N-isopropylacrylamide-co-polyvinylamine) (poly(NIPAm-co-VAm)) were designed and prepared. Stable poly(N-isopropylacrylamide) GPs with a high N-vinylformamide (NVF) content were prepared in aqueous media by optimization of the concentrations of the surfactant and monomers used in the polymerization step. GPs with a high polyvinylamine (pVAm) content up to 3.2 mmol amine per g GPs (~30 mol%) were prepared as a stable aqueous solution via the complete and selective hydrolysis of pNVF in the poly(NIPAm-co-NVF) GPs in a methanol solution, then dialyzed against water. The GPs with 3.2 mmol amine per g GPs pVAm showed a volume phase transition at a temperature of ~65 °C. Conductivity experiments established that the aqueous solution of the poly(NIPAm-co-VAm) GPs reversibly absorbed CO2 in response to a small thermal stimulus (30–75 °C). In addition, the foaming of amine-functionalized GP solutions during CO2 bubbling was prevented by increasing the amount of crosslinking in the GPs.

DOI： doi:10.1038/pj.2017.28

Language：Japanese   Publishing type：Research paper (scientific journal)  

A macroporous monolith comprising a polymer gel matrix was developed for application in continuous-flow catalytic reactions. Nanosized Pd(0) particles were loaded in a poly(N-isopropylacrylamide)-gel-based monolith by Pd(II) adsorption and subsequent reduction. The permeability of the Pd(0)-loaded monolith was compared with a commercial membrane filter with a pore size of several micrometers. The Pd(0)-loaded monolith exhibited excellent productivity in a continuous-flow Suzuki coupling reaction. Moreover, the Pd(0)-loaded monolith showed sustained performance over a 7-day period without Pd leaching.

DOI： 10.1246/cl.170360

Language：Japanese   Publishing type：Research paper (scientific journal)  

DOI： doi.org/10.1295/koron.2016-0046

Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1002/macp.201600570

Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1002/app.44385

Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1038/pj.2016.99

Language：Japanese   Publishing type：Research paper (scientific journal)  

The specific binding and uptake of protein molecules to individual hydrogel nanoparticles is measured with real-time single nanoparticle surface plasmon resonance imaging (SPRI) microscopy. Nanoparticles that adsorb onto chemically modified gold thin films interact with traveling surface plasmon polaritons and create individual point diffraction patterns in the SPRI microscopy differential reflectivity images. The intensity of each point diffraction pattern depends on the integrated refractive index of the nanoparticle; an increase in this single nanoparticle point diffraction intensity (∆%RNP) is observed for nanoparticles that bind proteins. SPRI adsorption measurements can be used to measure an average increase in ∆%RNP that can be correlated with bulk dynamic light scattering measurements. Moreover, the distribution of ∆%RNP values observed for individual nanoparticles can be used to learn more about the nature of the protein-nanoparticle interaction. As a first example, the binding of the lectin Concanavalin A to 180 nm N-isopropylacrylamide hydrogel nanoparticles that incorporate a small percentage of mannose sugar monomer units is characterized.

DOI： 10.1021/acs.jpcc.6b05700

Language：Japanese   Publishing type：Research paper (scientific journal)  

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DOI： 10.1038/pj.2016.44

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DOI： 10.1021/jacs.5b12600

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DOI： 10.1021/jacs.5b12600

Language：Japanese   Publishing type：Research paper (scientific journal)  

Glycosaminoglycans (GAGs) are polysaccharides found in living systems that have key biological roles and function as polyelectrolytes owing to their large number of sulfate groups. There have been many reports describing the syntheses of GAGs and the development of GAG mimetics and analogs. The preparation of such GAG mimics has utilized versatile methods ranging from total syntheses to synthetic polymer chemistry approaches. The core of GAG mimetic production is the fusion of complex chemical structures with polymeric properties. Multivalent interactions of the saccharides with specific biological targets, such as proteins, are an essential function of GAGs and other multivalent saccharides. In this review, methods for generating GAGs from glycopolymers are presented and research reports describing the functional characterization of the synthesized GAGs are outlined.

DOI： 10.1038/pj.2015.110

Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1038/pj.2015.110

Language：English  

The pathogenesis of Alzheimer’s disease is known to be related to the glycosaminoglycans that are associated with the deposition of amyloid beta (Aβ) peptides. We prepared heparin-mimicking multimeric saccharides and investigated their interactions with Aβ peptides in solution. The results showed that multimeric saccharides, especially the dimeric saccharide, strongly inhibited β-sheeted Aβ aggregation as assessed by the thioflavin-T (Th-T) assay, average zeta potential measurements and atomic force microscopy (AFM). This result suggested that the amyloidosis of Aβ (1-42) was affected by the multivalency of saccharides even in the solution.

DOI： 10.1246/cl.150633

Language：English  

Language：Japanese   Publishing type：Research paper (scientific journal)  

DOI： 10.1002/aic.14653

Language：English  

DOI： 10.1038/pj.2014.101

Language：English  

DOI： 10.1039/c4tb01967a

Language：English  

In this paper, a library of multi-functional linear poly-N-isopropylacrylamide (pNIPAm) polymers having a range of molecular weights and functional groups were synthesized and their interaction with the hemolytic peptide, melittin, was examined. The linear pNIPAm (LPs) containing both tert-butyl group and carboxylic acids bound with the peptide by a combination of hydrophobic and electrostatic interactions and neutralized its toxicity. The melittin binding capacity and affinity of each LP was quantified and further compared with cross-linked multi-functional nanogel particles (NPs) having same combination of functional groups. The binding capacity of the LPs (weight of captured melittin/weight of LP) was independent of their molecular weight and was three times higher than that of previously reported NPs. The binding constant depended on the molecular weight of the LPs, showing the highest value of 1.1 × 108 (M−1) for a ∼1000 mer linear polymer with 40% tert-butyl group and 20% carboxylic acid. Comparison of the interactions of the LPs and NPs suggested the importance of the flexibility of the polymer chain in order to achieve high binding capacity and affinity.

DOI： 10.1039/C4TB01967A

Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1021/bm501671

Language：Japanese  

DOI： 10.1021/mz500555x

Language：English  

DOI： 10.1038/pj.2014.33

Language：Japanese   Publishing type：Research paper (scientific journal)  

DOI： 10.1021/am503003v

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DOI： 10.1002/adma.201305957

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DOI： 10.1021/bm401536v

Language：Japanese   Publishing type：Research paper (scientific journal)  

DOI： 10.1039/C4TB00028E

Language：English   Publishing type：Research paper (scientific journal)  

Hydrogel films composed of temperature-responsive microgel particles (GPs) containing amine groups work as stimuli-responsive carbon dioxide absorbent with a high capacity of approximately 1.7 mmol g−1. Although the dried films did not show significant absorption, the reversible absorption capacity dramatically increased by adding a small amount of water (1 mL g−1). The absorption capacity was independent of the amount of added water beyond 1 mL g−1, demonstrating that the GP films can readily be used under wet conditions. The amount of CO2 absorbed by the GP films was proportional to their thickness up to 200–300 μm (maximum capacity of about 2 L m−2). Furthermore, the films consisting of GPs showed faster and greater absorption and desorption of CO2 than that of monolithic hydrogel films. These results indicated the importance of a fast stimulus response rate of the films that are composed of GPs in order to achieve long-range and fast diffusion of bicarbonate ions. Our study revealed the potential of stimuli-responsive GP films as energy-efficient absorbents to sequester CO2 from high-humidity exhaust gases.

DOI： 10.1002/ange.201309758

Language：Japanese   Publishing type：Research paper (scientific journal)  

DOI： 10.1016/j.bmcl.2013.09.057

Language：English   Publishing type：Research paper (scientific journal)  

A novel technique for detection of particulate matter in air using metal mesh devices is proposed. Metal mesh device with square apertures was used as membrane filter and as band-pass filter. Frequency shifts in transmittance spectra of the metal mesh device collected with particulate matter had a linear relationship to the particulate matter concentrations with a high coefficient of determination. When metal mesh devices with different opening lengths were stacked, particulate matter was fractionalized by size.

DOI： 10.1246/cl.131040

Language：English  

DOI： 10.1039/C3PY01001E

Language：English  

Porous membranes with glycopolymer brushes were prepared as biomaterials for affinity separation. Glycopolymer brushes contained acrylic acid and D-mannose or N-acetyl-D-glucosamine, and were formed on substrates by surface-initiated atom transfer radical polymerization. The presence of glycopolymer brush was confirmed by X-ray photoelectron spectroscopy, contact angle, and ellipsometry measurements. The interaction between lectin and the glycopolymer immobilized on glass slides was confirmed using fluorescent-labeled proteins. Glycopolymer-immobilized surfaces exhibited specific adsorption of the corresponding lectin, compared with bovine serum albumin. Lectins were continuously rejected by the glycopolymer-immobilized membranes. When the protein solution was permeated through the glycopolymer-immobilized membrane, bovine serum albumin was not adsorbed on the membrane surface. In contrast, concanavalin A and wheat germ agglutinin were rejected by membranes incorporating D-mannose or N-acetyl-D-glucosamine, respectively. The amounts of adsorbed concanavalin A and wheat germ agglutinin was increased five- and two-fold that of adsorbed bovine serum albumin, respectively.

DOI： 10.3390/membranes3030169

Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1021/la401068n

Language：English  

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Herein we report that an aqueous solution of temperature-responsive micro- and nanogel particles (GPs) consisting of N-isopropylacrylamide (NIPAm) and N-[3-(dimethylamino)propyl]methacrylamide (DMAPM) reversibly absorbs and desorbs CO2 via a phase transition induced by cooling and heating cycles (30–75 °C). Below the phase-transition temperature, most of the amines in the swollen GPs are capable of forming ion pairs with absorbed bicarbonate ions. However, above the phase-transition temperature, shrinkage of the GPs lowers the pKa and the number of amine groups exposed to water, thereby resulting in almost complete desorption of CO2. The GPs can reversibly absorb more than the DMAPM monomer and polymer without NIPAm, which indicates the importance of the temperature-responsive phase transition of polymers in determining the degree of absorption. The results show the potential of temperature-responsive polymer solutions as absorbents to sequester CO2 at a low energy cost.

Language：English   Publishing type：Research paper (scientific journal)  

DOI： doi:10.3390/molecules171011877

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DOI： DOI: 10.1021/ja306053s

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DOI： DOI: 10.1021/am301637q

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DOI： 10.1186/1556-276X-7-108

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6位硫酸化グルコサミンを結合させたポリロタキサン（PRX-6S-GlcNAc)を合成してアミロイドβ（１－４０）に対する凝集抑制効果について検討した。10％の糖鎖含有量を持つPRX-6S-GｌｃNAｃについては6位硫酸化グルコサミンの単体に比べて優れた凝集抑制能を示した。硫酸化糖修飾ポリロタキサンのアミロイド阻止機能については、糖鎖含有量やポリマーの添加量に依存があった。ポリロタキサンの糖鎖含有量が多くなると、アミロイド阻止機能は低下した。一方で、糖鎖修飾ポリロタキサンの量が増えるほど、アミロイド阻止機能は向上した。一方で、糖鎖修飾ポリロタキサンの量が増えるほどアミロイド阻止機能は向上した。ポリロタキサンの携帯はアミロイドβとの結合に必ずしも有利ではないが、一定のアミロイド阻止機能を発揮した。そして、PRX-6S-GlcNAｃによる、アミロイド化抑制については原子間力顕微鏡による、形態観察によっても明らかになった。

Publishing type：Research paper (scientific journal)  

糖鎖高分子という特殊な素材でコートした金微粒子を用いることにより、糖ータンパク質の相互作用を鋭敏に測定できることを明らかにした。糖とタンパク質の測定は極めて難しいことが知られており、ナノレベルで制御された微粒子と糖鎖多価化合物を使うことによってnM以下での鋭敏な測定を達成した。

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Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (scientific journal)  

Language：English   Publishing type：Research paper (bulletin of university, research institution)  

Language：English   Publishing type：Research paper (scientific journal)  

Language：Japanese   Book type：Scholarly book

Responsible for pages：PP99-105   Language：Japanese   Book type：Scholarly book

Responsible for pages：213-224   Language：English   Book type：Scholarly book

Responsible for pages：408-411　457-460   Language：Japanese   Book type：Scholarly book

Responsible for pages：257-267   Language：English   Book type：Scholarly book

Responsible for pages：Chapter 18, 455-480.   Language：Japanese   Book type：Scholarly book

Responsible for pages：Chapter 5, 85-100   Language：English   Book type：General book, introductory book for general audience

Responsible for pages：156-160   Language：Japanese   Book type：General book, introductory book for general audience

Responsible for pages：特殊形状高分子の項   Language：Japanese   Book type：General book, introductory book for general audience

Repository Public URL： http://hdl.handle.net/2324/1001431253

Responsible for pages：糖質材料を用いたアルツハイマー病へのアプローチ   Language：Japanese   Book type：General book, introductory book for general audience

Responsible for pages：バイオミメティックスを基盤とする生体材料設計   Language：Japanese   Book type：General book, introductory book for general audience

Language：Japanese   Book type：General book, introductory book for general audience

Responsible for pages：エコマテリアルハンドブック   Book type：General book, introductory book for general audience

Language：Japanese   Book type：General book, introductory book for general audience

Event date： 2018.5

Language：Japanese   Presentation type：Oral presentation (general)  

Country：Japan  

Event date： 2018.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：関西大学   Country：Japan  

Event date： 2018.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：関西大学   Country：Japan  

Event date： 2018.3

Language：Japanese   Presentation type：Oral presentation (general)  

Country：Japan  

Event date： 2012.3

Presentation type：Oral presentation (general)  

Venue：宇部高専   Country：Japan  

Event date： 2011.5

Venue：大阪   Country：Japan  

Event date： 2010.9

Venue：大阪大学   Country：Japan  

Event date： 2025.3

Language：Japanese  

Venue：東京理科大学   Country：Japan  

Event date： 2025.3

Language：Japanese   Presentation type：Poster presentation  

Venue：東京理科大学   Country：Japan  

Event date： 2025.3

Language：Japanese   Presentation type：Poster presentation  

Venue：東京理科大学   Country：Japan  

Event date： 2025.3

Language：Japanese  

Venue：東京理科大学   Country：Japan  

Event date： 2025.3

Language：Japanese  

Venue：東京理科大学   Country：Japan  

Event date： 2025.3

Language：Japanese  

Venue：東京理科大学   Country：Japan  

Event date： 2025.3

Language：Japanese  

Venue：東京理科大学   Country：Japan  

Event date： 2025.3

Language：Japanese  

Venue：東京理科大学   Country：Japan  

Event date： 2025.3

Language：Japanese  

Venue：東京理科大学   Country：Japan  

Event date： 2025.3

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Venue：東京理科大学   Country：Japan  

Event date： 2024.12

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Venue：横浜市開港記念会館   Country：Japan  

Event date： 2024.12

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Venue：横浜市開港記念会館   Country：Japan  

Event date： 2024.12

Language：Japanese  

Venue：別府 豊泉荘   Country：Japan  

Event date： 2024.12

Language：Japanese  

Venue：別府 豊泉荘   Country：Japan  

Event date： 2024.12

Language：Japanese  

Venue：別府 豊泉荘   Country：Japan  

Event date： 2024.12

Language：Japanese  

Venue：別府 豊泉荘   Country：Japan  

Event date： 2024.12

Language：Japanese  

Venue：別府 豊泉荘   Country：Japan  

Event date： 2024.11

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：福江文化会館   Country：Japan  

Event date： 2024.9

Language：Japanese  

Venue：新潟大学   Country：Japan  

Event date： 2024.9

Language：Japanese  

Venue：新潟大学   Country：Japan  

Event date： 2024.9

Language：Japanese  

Venue：新潟大学   Country：Japan  

Event date： 2024.9

Language：Japanese  

Venue：新潟大学   Country：Japan  

Event date： 2024.9

Language：Japanese  

Venue：新潟大学   Country：Japan  

Event date： 2024.9

Language：Japanese  

Venue：新潟大学   Country：Japan  

Event date： 2024.9

Language：Japanese  

Venue：新潟大学   Country：Japan  

Event date： 2024.9

Language：Japanese  

Venue：新潟大学   Country：Japan  

Event date： 2024.9

Language：Japanese  

Venue：新潟大学   Country：Japan  

Event date： 2024.9

Language：Japanese  

Venue：慶應義塾大学   Country：Japan  

Event date： 2024.9

Language：Japanese  

Venue：北海道大学   Country：Japan  

Event date： 2024.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：北海道大学   Country：Japan  

Event date： 2024.9

Language：Japanese  

Venue：北海道大学   Country：Japan  

Event date： 2024.9

Language：Japanese  

Venue：北海道大学   Country：Japan  

Event date： 2024.9

Language：Japanese  

Venue：北海道大学   Country：Japan  

Event date： 2024.8

Language：Japanese  

Venue：東京工業大学   Country：Japan  

Event date： 2024.8

Language：Japanese  

Venue：東京工業大学   Country：Japan  

Event date： 2024.8

Language：Japanese  

Venue：東京工業大学   Country：Japan  

Event date： 2024.7

Language：Japanese  

Venue：長崎ブリックホール   Country：Japan  

Event date： 2024.6

Language：Japanese  

Venue：北九州国際会議場   Country：Japan  

Event date： 2024.6

Language：Japanese  

Venue：北九州国際会議場   Country：Japan  

Event date： 2024.6

Language：Japanese  

Venue：北九州国際会議場   Country：Japan  

Event date： 2024.6

Language：Japanese  

Venue：北九州国際会議場   Country：Japan  

Event date： 2024.6

Language：Japanese  

Venue：九州工業大学   Country：Japan  

Event date： 2024.6

Language：Japanese  

Venue：九州工業大学   Country：Japan  

Event date： 2024.6

Language：Japanese  

Venue：九州工業大学   Country：Japan  

Event date： 2024.6

Language：Japanese  

Venue：九州工業大学   Country：Japan  

Event date： 2024.6

Language：Japanese  

Venue：仙台国際センター   Country：Japan  

Event date： 2024.6

Language：Japanese  

Venue：仙台国際センター   Country：Japan  

Event date： 2024.6

Language：Japanese  

Venue：仙台国際センター   Country：Japan  

Event date： 2024.6

Language：Japanese  

Venue：仙台国際センター   Country：Japan  

Event date： 2024.6

Language：Japanese  

Venue：仙台国際センター   Country：Japan  

Event date： 2024.3

Language：Japanese  

Venue：大阪公立大学   Country：Japan  

Event date： 2024.3

Language：Japanese  

Venue：大阪公立大学   Country：Japan  

Event date： 2024.3

Venue：大阪公立大学  

Event date： 2024.3

Language：Japanese  

Venue：大阪公立大学   Country：Japan  

Event date： 2023.12

Language：English  

Venue：Nanyang Technological University   Country：Singapore  

Event date： 2023.12

Language：English  

Venue：Nanyang Technological University   Country：Singapore  

Event date： 2023.12 - 2022.12

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：横浜　産業貿易センタービル   Country：Japan  

Event date： 2023.12

Language：English  

Venue：東京都立大学   Country：Japan  

Event date： 2023.11

Language：Japanese  

Venue：熊本城ホール   Country：Japan  

Event date： 2023.11

Language：Japanese  

Venue：熊本城ホール   Country：Japan  

Event date： 2023.11

Language：Japanese  

Venue：熊本城ホール   Country：Japan  

Event date： 2023.11

Language：Japanese  

Venue：熊本城ホール   Country：Japan  

Event date： 2023.11

Language：Japanese  

Venue：熊本城ホール   Country：Japan  

Event date： 2023.11

Language：Japanese  

Venue：熊本城ホール   Country：Japan  

Event date： 2023.11

Language：Japanese  

Event date： 2023.10

Language：English  

Venue：Calgary TELUS Convention Centre   Country：Canada  

Event date： 2023.9

Language：Japanese  

Venue：香川大学   Country：Japan  

Event date： 2023.9

Language：Japanese  

Venue：香川大学   Country：Japan  

Event date： 2023.9

Language：Japanese  

Venue：香川大学   Country：Japan  

Event date： 2023.9

Language：Japanese  

Venue：香川大学   Country：Japan  

Event date： 2023.9

Language：Japanese  

Venue：香川大学   Country：Japan  

Event date： 2023.9

Language：Japanese  

Venue：福岡大学   Country：Japan  

Event date： 2023.9

Language：Japanese  

Venue：福岡大学   Country：Japan  

Event date： 2023.9

Language：Japanese  

Venue：福岡大学   Country：Japan  

Event date： 2023.9

Language：Japanese  

Venue：福岡大学   Country：Japan  

Event date： 2023.9

Language：Japanese  

Venue：とりぎん文化会館   Country：Japan  

Event date： 2023.9

Language：English  

Venue：SMXコンベンションセンター   Country：Philippines  

Event date： 2023.9

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Venue：SMXコンベンションセンター   Country：Philippines  

Event date： 2023.7

Language：Japanese  

Venue：東京工業大学   Country：Japan  

Event date： 2023.7

Language：Japanese  

Venue：東京工業大学   Country：Japan  

Event date： 2023.7

Language：Japanese  

Venue：東京工業大学   Country：Japan  

Event date： 2023.7

Language：Japanese  

Venue：東京工業大学   Country：Japan  

Event date： 2023.7

Language：Japanese  

Venue：北九州国際会議場   Country：Japan  

Event date： 2023.7

Language：Japanese  

Venue：北九州国際会議場   Country：Japan  

Event date： 2023.7

Language：Japanese  

Venue：北九州国際会議場   Country：Japan  

Event date： 2023.5

Language：Japanese  

Venue：Gメッセ群馬   Country：Japan  

Event date： 2023.5

Language：Japanese  

Venue：Gメッセ群馬   Country：Japan  

Event date： 2023.5

Language：Japanese  

Venue：Gメッセ群馬   Country：Japan  

Event date： 2023.5

Language：Japanese  

Venue：Gメッセ群馬   Country：Japan  

Event date： 2023.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：東京理科大学   Country：Japan  

Event date： 2023.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：東京理科大学   Country：Japan  

Event date： 2023.3

Language：Japanese  

Venue：大阪公立大学   Country：Japan  

Event date： 2023.3

Language：Japanese  

Venue：大阪公立大学   Country：Japan  

Event date： 2023.3

Language：Japanese  

Venue：大阪公立大学   Country：Japan  

Event date： 2023.3

Language：Japanese  

Venue：大阪公立大学   Country：Japan  

Event date： 2023.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2023.3

Language：Japanese  

Venue：東京農工大学   Country：Japan  

Event date： 2023.3

Language：Japanese  

Venue：東京農工大学   Country：Japan  

Event date： 2023.3

Language：Japanese  

Venue：東京農工大学   Country：Japan  

Event date： 2023.3

Language：Japanese  

Venue：東京農工大学   Country：Japan  

Event date： 2023.3

Language：Japanese  

Venue：東京農工大学   Country：Japan  

Event date： 2023.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：大分大学   Country：Japan  

Event date： 2023.2

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2023.1

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2023.1

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：大阪大学   Country：Japan  

Event date： 2023.1

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：岡山市　杜の街グレース　オフィススクエア E,Fホール   Country：Japan  

Event date： 2022.12 - 2023.12

Language：English  

Venue：Brisbane Convention & Exhibition Center   Country：Australia  

Event date： 2022.12

Language：English  

Venue：Brisbane Convention ＆ Exhibition Center   Country：Australia  

Event date： 2022.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：信州大学   Country：Japan  

Event date： 2022.9

Language：Japanese  

Country：Japan  

Event date： 2022.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：北海道大学   Country：Japan  

Event date： 2022.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：北海道大学   Country：Japan  

Event date： 2022.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：北海道大学   Country：Japan  

Event date： 2022.9

Language：Japanese  

Venue：北海道大学   Country：Japan  

Event date： 2022.7

Language：Japanese   Presentation type：Oral presentation (general)  

Country：Japan  

Event date： 2022.7

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：東京工業大学大岡山キャンパス   Country：Japan  

Event date： 2022.7

Language：Japanese  

Venue：京工業大学(大岡山キャンパス)   Country：Japan  

Event date： 2022.7

Language：Japanese  

Venue：北九州国際会議場   Country：Japan  

Event date： 2022.7

Language：Japanese  

Venue：北九州国際会議場   Country：Japan  

Event date： 2022.5

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2022.5