Award for Encouragement of Research in IUMRS-ICA2014 is intended to honor young researchers who have delivered excellent presentations (oral or poster presentation) in IUMRS-ICA2014 for encouragement of future progress of the award winners.

分子認識能を有する高分子ナノ粒子の開発

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

Thermoelectric conversion of low temperature, delocalized, and abundant thermal sources is crucial for the development of the Internet of Things (IoT) and/or a carbon-free society. Thermocells are of great interest in thermoelectric conversion of low-temperature heat due to the low cost and flexibility of components. However, significant improvement of the conversion efficiency is required for the practical use of the cells. Here, we report thermo-electrochemical cells driven by volume phase transition (VPT) of hydrogel nanoparticles (NPs). Entropically driven VPT of poly(N-isopropylacrylamide) NPs containing carboxylic acids and amines generates a pH gradient of up to 0.049 and −0.053 pH K–1, respectively, around physiological temperature. The pH gradient triggers the proton-coupled electron transfer (PCET) reactions of quinhydrone on the electrodes, resulting in the highly efficient thermoelectric conversion with a Seebeck coefficient (Se) of −6.7 and +6.1 mV K–1. Thermocells driven by phase transition of hydrogels provide a nontoxic, flexible, and inexpensive charger that harvests carbon-free energy from abundant energy sources such as solar, body and waste heat.

DOI： doi.org/10.1021/jacs.0c08600

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

Sepsis is a life-threatening condition caused by the extreme release of inflammatory mediators into the blood in response to infection (e.g., bacterial infection, COVID-19), resulting in the dysfunction of multiple organs. Currently, there is no direct treatment for sepsis. Here we report an abiotic hydrogel nanoparticle (HNP) as a potential therapeutic agent for late-stage sepsis. The HNP captures and neutralizes all variants of histones, a major inflammatory mediator released during sepsis. The highly optimized HNP has high capacity and long-term circulation capability for the selective sequestration and neutralization of histones. Intravenous injection of the HNP protects mice against a lethal dose of histones through the inhibition of platelet aggregation and migration into the lungs. In vivo administration in murine sepsis model mice results in near complete survival. These results establish the potential for synthetic, nonbiological polymer hydrogel sequestrants as a new intervention strategy for sepsis therapy and adds to our understanding of the importance of histones to this condition.

DOI： 10.1038/s41467-021-25847-2

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DOI： doi.org/10.1039/d0tb00849d

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DOI： 10.1038/s41467-020-17285-3

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DOI： doi.org/10.1039/DoMA00149J

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DOI： doi.org/10.1021/acsabm.0c00390

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DOI： 10.1039/D0LC00080A

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DOI： doi.org/10.1039/DoRA02803G

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DOI： doi.org/10.1021/acsapm.9b00940

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： doi.org/10.1002/anie.201910558

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

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DOI： 10.1021/acs.analchem.9b01007

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DOI： 10.1021/acs.biomac.8b01820

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DOI： 10.1021/acs.bioconjchem.9b00134

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DOI： 10.1016/j.jconrel.2018.12.033

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DOI： Doi: 10.1016/j.jconrel.2018.12.033

Other Link： doi.org/10.1016/j.jconrel.2018.12.033

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

DOI： 10.1126/sciadv.aau0241

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

A fundamental challenge of biology is to understand the vast heterogeneity of cells, particularly how cellular composition, structure, and morphology are linked to cellular physiology. Unfortunately, conventional technologies are limited in uncovering these relations. We present a machine-intelligence technology based on a radically different architecture that realizes real-time image-based intelligent cell sorting at an unprecedented rate. This technology, which we refer to as intelligent image-activated cell sorting, integrates high-throughput cell microscopy, focusing, and sorting on a hybrid software-hardware data-management infrastructure, enabling real-time automated operation for data acquisition, data processing, decision-making, and actuation. We use it to demonstrate real-time sorting of microalgal and blood cells based on intracellular protein localization and cell-cell interaction from large heterogeneous populations for studying photosynthesis and
atherothrombosis, respectively. The technology is highly versatile and expected to enable machinebased scientific discovery in biological, pharmaceutical, and medical sciences.

DOI： 10.1016/j.cell.2018.08.028

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DOI： 10.1021/acsami.8b11397

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DOI： 10.1038/s41596-019-0183-1

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DOI： 10.1016/j.jconrel.2017.10.028

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DOI： 10.1002/cbic.201700314

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DOI： 10.1038/nchem.2749

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DOI： 10.1002/macp.201600570

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DOI： 10.1039/c7tb02107k

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DOI： 10.1021/jacs.5b12600

Other Link： http://pubs.acs.org/doi/abs/10.1021/jacs.5b12600

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DOI： 10.1021/jacs.5b05259

Other Link： http://pubs.acs.org/doi/abs/10.1021/jacs.5b05259

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DOI： 10.1039/C5SC01978H

Other Link： http://pubs.rsc.org/en/Content/ArticleLanding/2015/SC/C5SC01978H#!divAbstract

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DOI： 10.1038/nprot.2015.032

Other Link： http://www.nature.com/nprot/journal/v10/n4/abs/nprot.2015.032.html

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DOI： 10.1038/pj.2014.101

Other Link： http://www.nature.com/pj/journal/v47/n2/full/pj2014101a.html

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DOI： 10.1021/bm501671r

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DOI： 10.1039/C4TB01967A

Other Link： http://pubs.rsc.org/en/content/articlehtml/2015/tb/c4tb01967a

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DOI： 10.1021/bm500666j

Other Link： http://pubs.acs.org/doi/abs/10.1021/bm500666j

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DOI： 10.1002/adma.201305957

Other Link： http://onlinelibrary.wiley.com/doi/10.1002/adma.201305957/full

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DOI： 10.1021/ja410817p

Other Link： http://pubs.acs.org/doi/abs/10.1021/ja410817p

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DOI： 10.1002/ange.201309758

Other Link： http://onlinelibrary.wiley.com/doi/10.1002/ange.201309758/abstract

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DOI： 10.1021/bm401536v

Other Link： http://pubs.acs.org/doi/abs/10.1021/bm401536v

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DOI： 10.1021/am302404q

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DOI： 10.1021/ja3080192

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DOI： 10.1021/ja306053s

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DOI： 10.1021/ja303612d

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DOI： 10.1021/bm300986j

Other Link： http://pubs.acs.org/doi/abs/10.1021/bm300986j

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DOI： 10.1002/anie.201107797

Other Link： http://onlinelibrary.wiley.com/doi/10.1002/anie.201107797/full

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DOI： 10.1073/pnas.1112828109

Other Link： http://www.pnas.org/content/109/1/33.short

Repository Public URL： http://hdl.handle.net/2324/27289

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Other Link： http://pubs.rsc.org/en/content/articlelanding/2011/jm/c0jm03122d

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DOI： 10.1021/ja1058982

Other Link： http://pubs.acs.org/doi/abs/10.1021/ja1058982

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DOI： 10.1021/ja102148f

Other Link： http://pubs.acs.org/doi/abs/10.1021/ja102148f

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DOI： 10.1021/nn901256s

Other Link： http://pubs.acs.org/doi/abs/10.1021/nn901256s

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DOI： 10.1002/smll.200900186

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DOI： 10.1021/ja8062875

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DOI： 10.1021/bm050738e

Other Link： http://pubs.acs.org/doi/abs/10.1021/bm050738e

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DOI： 10.1002/1521-3927(20020301)23:4

Other Link： http://onlinelibrary.wiley.com/doi/10.1002/1521-3927(20020301)23:4%3C253::AID-MARC253%3E3.0.CO;2-H/abstract

Language：English   Publisher：Chemical Communications  

A quantitative understanding of thermodynamic effects of avidity in biomolecular interactions is important. Herein, we synthesized discrete glycooligomers and evaluated their interactions with a model protein using isothermal titration calorimetry. The dimeric glycooligomer exhibited higher binding constants compared to the glycomonomer, attributed to the reduced conformational entropy loss through local presentation of multiple carbohydrate units. Conversely, divalent glycoligands with polyethylene glycol linkers, aiming for multivalent binding, showed enhanced interactions through increased enthalpy. These findings emphasize the importance of distinguishing between the “local avidity” and the “multipoint avidity”.

DOI： 10.1039/d4cc02409e

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Language：English   Publisher：Inorganic Chemistry  

The utilization of aluminum, an abundant and inexpensive element, for the synthesis of novel functional complexes is extremely important, but the design and control of photofunctionality are still unexplored. In this study, we focused on our previously developed dinuclear triple-stranded helicates incorporating two aluminum ions (ALPHY) to synthesize both homoleptic and heteroleptic complexes with bromine atoms at the 3-position of the pyrrole moiety in the Schiff base ligands. The brominated Schiff base ligands were reacted with AlCl3 to synthesize homoleptic complexes, while different ligands were mixed to prepare heteroleptic complexes. Single-crystal X-ray structural analysis revealed the structures of these novel complexes. We found that increasing the degree of bromination resulted in a tunable emission color, shifting progressively from 550 (yellow) to 566 nm (orange). Optical resolution of the complexes facilitated the observation of mirror-image circular dichroism and circularly polarized luminescence. Furthermore, employing ultrafast spectroscopy techniques, we have elucidated that the optical properties are governed by the interligand charge transfer (ILCT) among the three ligands. The formation of heteroleptic complexes induces the ILCT state even in nonpolar environments, thereby accelerating nonradiative decay and intersystem crossing. These findings mark significant advancements in photofunctional materials based on multinuclear complexes.

DOI： 10.1021/acs.inorgchem.4c01214

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Language：English   Publisher：Dalton Transactions  

The construction of novel complexes can lead to the manifestation of unexpected structures and properties, thereby making chemical exploration in experiments a potential source for novel discoveries. In this study, by reacting 6,6′-dihydrazineyl-2,2′-bipyridine with acyl chlorides and subsequently coordinating with boron trifluoride, two different boron-tetradentate ligand complexes were simultaneously generated. One of these complexes exhibited a unique structure in which tetra-BF2 moieties coordinated to all four coordination sites of the ligand molecule, forming a flag-hinged structure around the bipyridine part. The second complex featured a helical structure formed by the hybridization of two BF2 and one B-O-B moieties, representing a highly unusual form of the complex. The structures of these two boron complexes were consistently observed when various substituted acyl chlorides were employed. Furthermore, it was found that enhancing electron-donor properties could induce a redshift in emissions. Utilizing the dimethylamino group as the proton receptor promoted a yellow-to-blue fluorescence switch in the tetra-BF2 complex and an OFF/ON fluorescence in the B-O-B bridged complex upon protonation. The helical chirality observed in the latter complex resulted in stable (P)/(M)-enantiomers after optical resolution. This complex exhibited circular dichroism with a |gabs| of up to 1.2 × 10−2 and circularly polarized luminescence with a |glum| on the order of 10−3 in solution and polymer film.

DOI： 10.1039/d4dt01172d

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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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Publisher：Polymer Journal  

Capturing CO2 from various sources, such as postcombustion exhaust gases and the atmosphere, is essential for a sustainable human society. Effective CO2 separation materials such as adsorbents and membranes are of utmost importance in efficient CO2 capture. This short review is focused on CO2 separation materials consisting of hydrogel particles. The first chapter introduces stimuli-responsive micro- and nanogel particles that reversibly absorb CO2 in response to thermal stimuli. The development of temperature-responsive hydrogel films comprising gel particles for reversible CO2 capture is introduced. The importance of choosing amines with optimal pK a values for efficient CO2 capture from various sources is explained in detail. The assembly of CO2 separation membranes consisting of amine-containing hydrogel particles is introduced in the final chapter. The paper highlights the promise of separation materials consisting of hydrogel particles for efficient CO2 capture from postcombustion gases and air and the prospects for further advances in this area.

DOI： 10.1038/s41428-023-00850-0

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

This study explored the development of functional dyes using aluminum, focusing on aluminum-based dinuclear triple-stranded helicates, and examined the effects of substituent variations on their structural and optical properties. Key findings revealed that the modification of methyl groups to the pyrrole positions significantly extended the conjugation system, resulting in a red shift in the absorption and emission spectra. Conversely, the modification of methyl groups at the methine positions due to steric hindrances increased the torsion angle of the ligands, leading to a blue shift in the absorption and emission spectra. A common feature across all complexes was that in the excited state, one of the three ligands underwent significant structural relaxation. This led to a pronounced Stokes shift and minimal spectra overlap with high photoluminescence behaviors. Moreover, our research extended to the optical resolution of the newly synthesized complexes by analyzing the chiroptical properties of the resulting enantiomers, including their circular dichroism and circularly polarized luminescence. These insights offer valuable contributions to the design and application of novel aluminum-based functional dyes, potentially influencing a range of fields, from materials science to optoelectronics.

DOI： 10.1021/acs.inorgchem.4c00045

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

Cyclic polymers, which are found in the field of biopolymers, exhibit unique physical properties such as suppressed molecular mobility. Considering thermodynamics, the suppressed molecular mobility of cyclic polymers is expected to prevent unfavorable entropy loss in molecular interactions. In this study, we synthesized cyclic glycopolymers carrying galactose units and investigated the effects of their molecular mobility on the interactions with a lectin (peanut agglutinin). The synthesized cyclic glycopolymers exhibited delayed elution time on size exclusion chromatography and a short spin–spin relaxation time, indicating typical characteristics of cyclic polymers, including smaller hydrodynamic size and suppressed molecular mobility. The hemagglutination inhibition assay revealed that the cyclic glycopolymers exhibited weakened interactions with PNA compared to the linear counterparts, attributable to the suppressed molecular mobility. Although the results are contrary to our expectations, the impact of polymer topology on molecular recognition remains intriguing, particularly in the context of protein repellent activity in the biomedical field.

DOI： 10.1002/cplu.202400136

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

Materials exhibiting room temperature phosphorescence (RTP) have recently emerged as a subject of significant interest. In this study, we successfully created inclusion crystals by introducing halobenzenes as guests into a host molecule combining benzophenone with naphthalene diimide. This approach led to the creation of fascinating fluorescence and RTP properties dependent on the guest molecules. Notably, crystals containing chlorobenzene showed cyan fluorescence, while those with iodobenzene displayed red RTP. This difference highlights the impact of the guest molecule on the luminescent properties, with the significant external heavy-atom effect of iodobenzene playing a key role in promoting efficient intersystem crossing between the excited singlet and triplet states. Crystals with bromobenzene exhibited a unique blend of fluorescence and RTP, both from benzophenone and naphthalene diimide, highlighting the moderate heavy-atom effect. These findings reveal composite materials with remarkably diverse and interesting optical characteristics.

DOI： 10.1002/asia.202301114

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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

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Language：Others   Publishing type：Research paper (scientific journal)   Publisher：Chemistry Letters  

Three structural isomers of naphthalene diimides were synthesized. In all compounds, the electron-withdrawing diimide group exhibits a stable two-step reduction behavior under electrochemical conditions, and it was revealed that their reduction potentials vary significantly depending on the position of the diimide group relative to the naphthalene ring.

DOI： 10.1093/chemle/upad022

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Language：Japanese   Publisher：THE JAPAN SOCIETY OF DRUG DELIVERY SYSTEM  

In this review chalenges for the development of plastic antibodies are summarized.

DOI： 10.2745/dds.39.42

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Advanced Optical Materials  

Advanced organoboron dyes, incorporating tetra-boron difluoride (tetra-BF2) moieties, are developed, demonstrating efficient electrochemiluminescence (ECL) emissions in the green to orange regions through direct ion annihilation. By introducing diverse alkyl modifications in the molecules, luminescence color tuning is achieved via alterations in conjugation and bending angle. A photoluminescence quantum yield of 100% in dilute solutions is successfully achieved. Notably, the introduction of alkyl groups to the methine side stabilizes the radical ionic state, resulting in a high ECL efficiency of 74% through an efficient radical-ion annihilation pathway. The key factor is that the energy of the annihilation reaction exceeds the S1 energy required for luminescence. Spin density calculations further elucidate the substituent effects on the radical ions of complexes. Moreover, the lasing properties of these materials in the solution-processed blend films are investigated, revealing a low amplified spontaneous emission (ASE) threshold (Eth) of 6.40 ± 0.24 µJ cm−2, which is notably lower among organic laser materials. This is attributed to their large Stokes shifts and high quantum yield. The excellent ECL and ASE performances establish these materials as a valuable addition to the existing library of organoboron dyes, offering fresh insights into the development of organic solid-state lasers.

DOI： 10.1002/adom.202302803

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

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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 PPh3 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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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Journal of the American Chemical Society  

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： 10.1021/jacs.3c06799

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Journal of Controlled Release  

Temperature-responsive polymers are often characterized by an abrupt change in the degree of swelling brought about by small changes in temperature. Polymers with a lower critical solution temperature (LCST) in particular, are important as drug and gene delivery vehicles. Drug molecules are taken up by the polymer in their solvent swollen state below their LCST. Increasing the temperature above the LCST, typically physiological temperatures, results in desolvation of polymer chains and microstructure collapse. The trapped drug is released slowly by passive diffusion through the collapsed polymer network. Since diffusion is dependent on many variables, localizing and control of the drug delivery rate can be challenging. Here, we report a fundamentally different approach for the rapid (seconds) tumor-specific delivery of a biomacromolecular drug. A copolymer nanoparticle (NP) was engineered with affinity for melittin, a peptide with potent anti-cancer activity, at physiological temperature. Intravenous injection of the NP-melittin complex results in its accumulation in organs and at the tumor. We demonstrate that by local cooling of the tumor the melittin is rapidly released from the NP-melittin complex. The release occurs only at the cooled tumor site. Importantly, tumor growth was significantly suppressed using this technique demonstrating therapeutically useful quantities of the drug can be delivered. This work reports the first example of an in vivo site-specific release of a macromolecular drug by local cooling for cancer therapy. In view of the increasing number of cryotherapeutic devices for in vivo applications, this work has the potential to stimulate cryotherapy for in vivo drug delivery.

DOI： 10.1016/j.jconrel.2023.02.020

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

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

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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Publisher：医歯薬出版  

DOI： 10.32118/ayu28209809

CiNii Research

Language：English   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

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PubMed

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

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

Improving polyhydroxyalkanoate (PHA, a biodegradable plastic) production under photoautotrophic cultivation is challenging for sustainable bioproduction. In this study, we demonstrated the use of engineered nanogel particles to enhance PHA accumulation in the marine photosynthetic bacterium Rhodovulum sulfidophilum under photoautotrophic culture. We screened the effect of 13 engineered nanogel particles on the cell growth and PHA accumulation of R. sulfidophilum. The addition of anionic nanogel particles significantly enhanced PHA accumulation in R. sulfidophilum up to 157-fold compared to that without nanogel particles. By performing 13C tracer experiments and gas chromatography-mass spectrometry analysis, we confirmed that HCO3- was assimilated throughout the central carbon metabolism and that the accumulated PHA was indeed incorporated from HCO3-. Our results indicate successful PHA production with the supplementation of engineered nanogel particles under photoautotrophic cultivation in R. sulfidophilum. Furthermore, the strategy of using engineered nanoparticles demonstrated in this study may be applicable to other microbial cell factories to produce other commodity metabolites.

DOI： 10.1021/acssuschemeng.1c07252

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Language：English   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.

CiNii Research

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

DOI： 10.1246/cl.210740

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

DOI： 10.1246/cl.210740

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

DOI： 10.1021/acs.biomac.1c01483

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

The carbohydrate–carbohydrate interaction was demonstrated by glyco-cluster with glycopolymers and could be measured quantitatively.

DOI： 10.1039/D1TB02344F

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

DOI： 10.1021/acs.biomac.1c01483

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

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

Sepsis is a life-threatening condition caused by the extreme release of inflammatory mediators into the blood in response to infection (e.g., bacterial infection, COVID-19), resulting in the dysfunction of multiple organs. Currently, there is no direct treatment for sepsis. Here we report an abiotic hydrogel nanoparticle (HNP) as a potential therapeutic agent for late-stage sepsis. The HNP captures and neutralizes all variants of histones, a major inflammatory mediator released during sepsis. The highly optimized HNP has high capacity and long-term circulation capability for the selective sequestration and neutralization of histones. Intravenous injection of the HNP protects mice against a lethal dose of histones through the inhibition of platelet aggregation and migration into the lungs. In vivo administration in murine sepsis model mice results in near complete survival. These results establish the potential for synthetic, nonbiological polymer hydrogel sequestrants as a new intervention strategy for sepsis therapy and adds to our understanding of the importance of histones to this condition.

DOI： 10.1038/s41467-021-25847-2

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

DOI： 10.1016/j.bbrc.2021.05.005

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

DOI： 10.1021/acsami.1c07266

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

DOI： 10.1021/acs.biomac.1c00553

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

DOI： 10.1016/j.bbrc.2021.05.005

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

DOI： 10.1039/D1BM00515D

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

DOI： 10.1021/acs.biomac.1c00553

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

DOI： 10.2116/analsci.20P388

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

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

DOI： doi.org/10.1016/j.cej.2020.126059

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

© 2020 Elsevier B.V. In this work, we report a proof-of-concept study on CO2 adsorbents synthesized by a thermally initiated free-radical copolymerization and then coated onto carbon paper and poly tetra fluoroethylene via a spray coating approach. A milli-channel reactor was employed to support the obtained materials for efficient CO2 capture with wet conditions, short cooling and heating cycles (303–348 K). CO2 uptake and release performance of the materials were measured and compared with that of the polyamine-based materials prepared by other methods. CO2 adsorption and desorption kinetics can be greatly enhanced when using the spray coating approach, especially for carbon paper as supporter. The CO2 adsorption capacity of the spray-coated carbon paper reaches 80% of its maximum value in only 4.37 ± 0.7 min. Moreover, its adsorption rate (114.6 mg/(g∙min) at 303 K) and desorption rate (239.9 mg/(g∙min) at 348 K) were 81.2% and 81.5% higher than those of the polyamine-impregnated carbon paper, respectively (12% CO2 at atmospheric pressure). Their largest increases of 71% and 67% were achieved by adjusting the concentration of polyamine nanogel particles deposited on the carbon paper surface. The prepared material also presents stable recyclability over 10 wet adsorption–desorption cycles and the aging experiments. The results obtained in this study indicate that the synthesized materials can serve as promising energy-efficient solid adsorbents for CO2 capture.

DOI： 10.1016/j.cej.2020.126059

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

DOI： 10.1016/j.eurpolymj.2020.110044

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

DOI： doi.org/10.1039/DoTB02093A

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

Thermoelectric conversion of low temperature, delocalized, and abundant thermal sources is crucial for the development of the Internet of Things (IoT) and/or a carbon-free society. Thermocells are of great interest in thermoelectric conversion of low-temperature heat due to the low cost and flexibility of components. However, significant improvement of the conversion efficiency is required for the practical use of the cells. Here, we report thermo-electrochemical cells driven by volume phase transition (VPT) of hydrogel nanoparticles (NPs). Entropically driven VPT of poly(N-isopropylacrylamide) NPs containing carboxylic acids and amines generates a pH gradient of up to 0.049 and -0.053 pH K-1, respectively, around physiological temperature. The pH gradient triggers the proton-coupled electron transfer (PCET) reactions of quinhydrone on the electrodes, resulting in the highly efficient thermoelectric conversion with a Seebeck coefficient (Se) of -6.7 and +6.1 mV K-1. Thermocells driven by phase transition of hydrogels provide a nontoxic, flexible, and inexpensive charger that harvests carbon-free energy from abundant energy sources such as solar, body and waste heat.

DOI： 10.1021/jacs.0c08600

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

DOI： 10.1038/s41428-020-00407-5

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

Immobilized transition metals for continuous-flow catalyses are greatly in demand to achieve automation, scale-up, facile separation, regeneration, and energy-saving production with high level of sustainability and efficiency. Here, we report a tertiary phosphine immobilized on a macroporous monolith (M-PS-TPP) for the challenging Pd-catalyzed cross-coupling reaction of aryl chloride in a continuous-flow system. The monolithic and macroporous structure of M-PS-TPP was fabricated by bulk polymerization in the presence of a high internal phase emulsion (HIPE) template. Owing to the large pore size and high porosity, the M-PS-TPP showed high permeability against continuous flow of the mobile phase. The continuous-flow Suzuki-Miyaura cross-coupling reaction was realized by permeation of organic/aqueous media containing inorganic salt through a Pd-loaded monolith (M-PS-TPP-Pd) column without serious clogging. Controlling coordination chemistry and hydrodynamics of M-PS-TPP-Pd boosted highly active phosphine-metal complex formation and fast mass transfer of reactants. Indeed, the M-PS-TPP-Pd column showed surprisingly higher yields (similar to 93%) and turnover numbers (2704) under continuous-flow conditions than that under batch conditions (similar to 6%).

DOI： 10.1021/acs.iecr.0c02404

Language：English   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 ofM-PS-TPPwas fabricated via polymerization-induced phase separation using porogenic solvent. Moreover, theM-PS-TPPwas synthesized using different feed ratios of divinylbenzene (DVB) for site-isolation and mono-P-ligating behavior of PPh3.P-31 CP/MAS NMR analysis revealed that the different selectivity ofM-PS-TPPs was obtained in formation of mono-P-ligation toward Pd-II. The macroporous properties and controlled mono-P-ligating behavior ofM-PS-TPPfacilitated the challenging Pd-catalyzed Suzuki-Miyaura cross-coupling reaction of chloroarenes.

DOI： 10.1002/cctc.202000651

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

DOI： doi.org/10.1021/acs.iecr.0c02404

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

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

The advent of image-activated cell sorting and imaging-based cell picking has advanced our knowledge and exploitation of biological systems in the last decade. Unfortunately, they generally rely on fluorescent labeling for cellular phenotyping, an indirect measure of the molecular landscape in the cell, which has critical limitations. Here we demonstrate Raman image-activated cell sorting by directly probing chemically specific intracellular molecular vibrations via ultrafast multicolor stimulated Raman scattering (SRS) microscopy for cellular phenotyping. Specifically, the technology enables real-time SRS-image-based sorting of single live cells with a throughput of up to ~100 events per second without the need for fluorescent labeling. To show the broad utility of the technology, we show its applicability to diverse cell types and sizes. The technology is highly versatile and holds promise for numerous applications that are previously difficult or undesirable with fluorescence-based technologies.

DOI： 10.1038/s41467-020-17285-3

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

DOI： 10.1021/acsabm.0c00390

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

The advent of intelligent image-activated cell sorting (iIACS) has enabled high-throughput intelligent image-based sorting of single live cells from heterogeneous populations. iIACS is an on-chip microfluidic technology that builds on a seamless integration of a high-throughput fluorescence microscope, cell focuser, cell sorter, and deep neural network on a hybrid software-hardware data management architecture, thereby providing the combined merits of optical microscopy, fluorescence-activated cell sorting (FACS), and deep learning. Here we report an iIACS machine that far surpasses the state-of-the-art iIACS machine in system performance in order to expand the range of applications and discoveries enabled by the technology. Specifically, it provides a high throughput of ∼2000 events per second and a high sensitivity of ∼50 molecules of equivalent soluble fluorophores (MESFs), both of which are 20 times superior to those achieved in previous reports. This is made possible by employing (i) an image-sensor-based optomechanical flow imaging method known as virtual-freezing fluorescence imaging and (ii) a real-time intelligent image processor on an 8-PC server equipped with 8 multi-core CPUs and GPUs for intelligent decision-making, in order to significantly boost the imaging performance and computational power of the iIACS machine. We characterize the iIACS machine with fluorescent particles and various cell types and show that the performance of the iIACS machine is close to its achievable design specification. Equipped with the improved capabilities, this new generation of the iIACS technology holds promise for diverse applications in immunology, microbiology, stem cell biology, cancer biology, pathology, and synthetic biology.

DOI： 10.1039/d0lc00080a

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

DOI： doi.org/10.1002/cctc.202000651

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

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

DOI： 10.1038/s41428-019-0298-9

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

© 2019 Elsevier B.V. Amine-containing nanogel particles as promising absorbents have been developed to reversibly uptake and release CO2 at a low regeneration temperature (75 °C), which is an efficient way to limit the degradation and volatility of amine. It is extremely important to explore a suitable CO2 capture process for further scale-up and industrial application. Herein, a temperature vacuum swing adsorption process for post-combustion CO2 capture from flue gas, using honeycomb-carbon-fiber-supported amine-containing nanogel particles in a rotating column was proposed. The corresponding models for CO2 adsorption and recovery were established and developed based on CO2 adsorption equilibrium experimental data. Two different process configurations were compared and optimized for a specified CO2 purity, recovery, productivity, and energy consumption. The effect of the feed gas CO2 concentration on the aforementioned performance indicators was investigated independently. Simulated results indicate that the cycling of concentrated CO2 in the desorption section can be used to improve the CO2 purity, which is almost independent of the feed gas CO2 concentration. However, it would be decreased when the purge gas combined with concentrated CO2 was recycled in the desorption section, especially for lower CO2 concentration of the feed gas. The performance indicators for 12% CO2 in terms of CO2 purity, productivity, recovery, and energy consumption were optimized to be 99.5%, 0.622 kg/(kg·h), 93.4%, and 567 kJ/kg CO2, respectively, indicating that the rotating honeycomb column with the temperature vacuum swing adsorption process can be a promising post-combustion CO2 capture technology.

DOI： 10.1016/j.cej.2019.123123

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

DOI： 10.1002/ange.201910558

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：Others   Publishing type：Research paper (scientific journal)  

DOI： 10.1038/s41428-019-0244-x

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)  

DOI： 10.1021/acsomega.9b02877

Language：English  

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

DOI： 10.1038/s41596-019-0252-5

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

© 2019 Elsevier Ltd Amine-containing nanogel particles with a lower cooling and heating cycles (303–348 K), which is beneficial to limit the degradation and volatile of amine, has been developed as promising absorbents for CO2 capture. It is extremely important to understand the CO2 capture kinetics and mechanisms for design and operation of corresponding processes. In present work, poly tetra fluoroethylene and carbon paper were used to support the GPs by filtering and loading method. The CO2 uptake and release performance of poly tetra fluoroethylene and carbon paper supported nanogel particles was measured. It was found that carbon paper as supporter shows higher CO2 capacity and desorption rate. A comparison of three different kinetic models shows that carbon paper as supporter gives a more enhanced kinetic behavior. Avrami's fractional order model presents the best fit to experimental data. To further investigate the mechanism of CO2 uptake on absorbents, interparticle diffusion model, intraparticle diffusion model and Boyd's film diffusion model were also applied. Film diffusion resistance governed the mass transfer rate of CO2 uptake on studied absorbents at the initial CO2 uptake stages. In the following stages, intra-particle diffusion resistance plays a major role until the equilibrium is reached. The sensible heat of carbon paper as supporter is about 25% lower than that of poly tetra fluoroethylene as supporter. The desorption activation energy obtained from the Arrhenius equation is 18 kJ/mol for carbon paper as supporter, which is 84% lower than that of the typical aqueous MEA solvent.

DOI： 10.1016/j.apenergy.2019.113567

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

DOI： 10.1039/C9FD00018F

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

The affinity of a synthetic polymer nanoparticle (NP) to a target biomacromolecule is determined by the association and dissociation rate constants (kon, koff) of the interaction. The individual rates and their sensitivity to local environmental influences are important factors for the on-demand capture and release a target biomacromolecule. Positively charged NPs for small interfering RNA (siRNA) delivery is a case in point. The knockdown efficacy of siRNA can be strongly influenced by the binding kinetics to the NP. Here, we show that kon and koff of siRNA to NPs can be individually engineered by tuning the chemical structure and composition of the NP. N-Isopropylacrylamide-based NPs functionalized with hydrophobic and amine monomers were used. koff decreased by increasing the amount of amine groups in the NP, whereas kon did not change. Importantly, NPs showing a low koff at pH 5.5 together with a high koff at pH 7.4 showed high knockdown efficiency when NP/siRNA complexes were packaged in lipid nanoparticles. These results provide direct evidence for the premise that the efficacy of an siRNA delivery vector is linked with the strong affinity to the siRNA in the endosome and low affinity in the cytoplasm.

DOI： 10.1021/acs.biomac.9b00611

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

DOI： 10.1021/acs.biomac.9b00611

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

DOI： 10.1246/cl.190293

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

Time-course analysis of single cells is important to characterize heterogeneous activities of individual cells such as the metabolic response to their environment. Single-cell isolation is an essential step prior to time-course analysis of individual cells by collecting, culturing, and identifying multiple single-cell targets. Although single-cell isolation has been performed by various methods previously, a glass microfluidic device with semiclosed microchannels dramatically improved this process with its simple operation and easy transfer for time-course analysis of identified single cells. This study demonstrates isolating single cells of the highly motile microalgae, Euglena gracilis, by semiclosed microchannels with liquid flow only. The isolated single cells were identified in isolating channels and continuously cultured to track, by Raman microscopy, for the formation of subcellular granules composed of polysaccharide paramylon, a unique metabolite of E. gracilis, generated through photosynthesis. Through low-temperature glass bonding, a thin glass interface was incorporated to the microfluidic device. Thus, the device could perform the direct measurements of cultured single cells at high magnification by Raman microscopy with low background noise. In this study, the first demonstration of sequential monitoring of paramylon biogenesis in a single identified E. gracilis cell is shown.

DOI： 10.1021/acs.analchem.9b01007

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

Synthetic glyco-ligands are promising candidates for effective nanomedicines against pathogens. Glycopolymers bearing sialyl-oligosaccharides interact with hemagglutinin present on the surface of influenza viruses. In designing new glycopolymers that further enhance the interaction with viruses, both static and dynamic properties of the glycopolymers should be considered. In this report, we evaluated the correlation between dynamic properties of glycopolymers and their interaction with the influenza virus. Glycopolymers with pendant sialyllactoses and various linker structures were synthesized, and their molecular mobility was determined by proton spin-spin relaxation time measurements. The molecular mobility of the glycounits increased as the length of the linker structures increased. Interestingly, glycopolymers with the medium-length linker structure exhibited the strongest interaction with the influenza virus, suggesting that optimal molecular mobility is required for maximizing multivalent interactions with the target.

DOI： 10.1021/acs.biomac.9b00515

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

DOI： doi.org/10.1021/acs.biomac.9b00515

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

DOI： doi.org/10.1016/j.cej.2019.123123

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)  

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

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

DOI： 10.1002/pola.29344

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

Glycopolymers mimicking GM1 gangliosides were synthesized by incorporating multiple types of carbohydrates into the polymer backbone. The glycopolymers were immobilized onto gold surfaces, and the interactions with the cholera toxin B subunit (CTB) were analyzed using surface plasmon resonance imaging. The glycopolymer containing both galactose and neuraminic acid showed enhanced recognition of CTB. The interaction was enhanced mainly because of an improvement in the dissociation process by the binding of the neuraminic acid group in the GM1 binding pocket. This cooperativity of galactose and neuraminic acid was achieved by incorporation into the same flexible polymer backbone, and the importance of the close placement of galactose and neuraminic acid groups was revealed. These results will be valuable in medical fields and also for the development of biofunctional materials.

DOI： 10.1002/asia.201900053

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

Synthetic polymers are of interest as stable and cost-effective biomolecule-affinity reagents, since these polymers interact with target biomolecules both in vitro and in the bloodstream. However, little has been reported about orally administered polymers capable of capturing a target molecule and inhibiting its intestinal absorption. Here, we describe the design of synthetic polymer nanoparticles (NPs) specifically capturing indole, a major factor exacerbating chronic kidney disease, in the intestine. N-isopropylacrylamide-based NPs were prepared with various hydrophobic monomers. The amounts of indole captured by NPs depended on the structures and feed ratios of the hydrophobic monomers and the polymer density but not on the particle size. The combination of hydrophobic and quadrupole interaction was effective to enhance the affinity and specificity of NPs for indole. The optimized NPs specifically inhibited intestinal absorption of orally administered indole in mice. These results showed the potential of synthetic polymer NPs for inhibiting the intestinal absorption of a target molecule.

DOI： 10.1021/acs.biomac.8b01820

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

DOI： 10.1002/asia.201900255

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)  

DOI： doi.org/10.1038/s41428-019-0244-x

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

Protein affinity reagents (PARs), frequently antibodies, are essential tools for basic research, diagnostics, separations and for clinical applications. However, there is growing concern about the reproducibility, quality and cost of recombinant and animal-derived antibodies. This has prompted the development of alternatives that could offer economic, and time-saving advantages without the use of living organisms. Synthetic copolymer nanoparticles (NPs), engineered with affinity for specific protein targets, are potential alternatives to PARs. Although there are now a number of examples of abiotic protein affinity reagents (APARs), most have been evaluated in vitro limiting a realistic assessment of their potential for more demanding, practical in vivo applications. We demonstrate for the first time that an abiotic copolymer hydrogel nanoparticle (NP1) engineered to bind a key signaling protein, vascular endothelial growth factor (VEGF165), functions in vivo to suppress tumor growth by regulating angiogenesis. Lightly cross-linked N-isopropylacrylamide based NPs that incorporate both sulfated N-acetylglucosamine and hydrophobic monomers were optimized by dynamic chemical evolution for VEGF165 affinity. NP1 efficacy in vivo was evaluated by systemic administration to tumor-bearing mice. The study found that NP1 suppresses tumor growth and reduces tumor vasculature density. Combination therapy with doxorubicin resulted in increased doxorubicin concentration in the tumor and dramatic inhibition of tumor growth. NP1 treatment did not show off target anti-coagulant activity. In addition, >97% of injected NPs are rapidly excreted from the body following IV injection. These results establish the use of APARs as inhibitors of protein-protein interactions in vivo and may point the way to their broader use as abiotic, cost effective protein affinity reagents for the treatment of certain cancers and more broadly for regulating signal transduction.

DOI： 10.1016/j.jconrel.2018.12.033

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

<jats:p>Flow cytometry is an indispensable tool in biology for counting and analyzing single cells in large heterogeneous populations. However, it predominantly relies on fluorescent labeling to differentiate cells and, hence, comes with several fundamental drawbacks. Here, we present a high-throughput Raman flow cytometer on a microfluidic chip that chemically probes single live cells in a label-free manner. It is based on a rapid-scan Fourier-transform coherent anti-Stokes Raman scattering spectrometer as an optical interrogator, enabling us to obtain the broadband molecular vibrational spectrum of every single cell in the fingerprint region (400 to 1600 cm<jats:sup>−1</jats:sup>) with a record-high throughput of ~2000 events/s. As a practical application of the method not feasible with conventional flow cytometry, we demonstrate high-throughput label-free single-cell analysis of the astaxanthin productivity and photosynthetic dynamics of <jats:italic>Haematococcus lacustris</jats:italic>.</jats:p>

DOI： 10.1126/sciadv.aau0241

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

DOI： 10.1038/s41428-018-0102-2

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

DOI： 10.1038/s41428-018-0102-2

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

A fundamental challenge of biology is to understand the vast heterogeneity of cells, particularly how cellular composition, structure, and morphology are linked to cellular physiology. Unfortunately, conventional technologies are limited in uncovering these relations. We present a machine-intelligence technology based on a radically different architecture that realizes real-time image-based intelligent cell sorting at an unprecedented rate. This technology, which we refer to as intelligent image-activated cell sorting, integrates high-throughput cell microscopy, focusing, and sorting on a hybrid software-hardware data-management infrastructure, enabling real-time automated operation for data acquisition, data processing, decision-making, and actuation. We use it to demonstrate real-time sorting of microalgal and blood cells based on intracellular protein localization and cell-cell interaction from large heterogeneous populations for studying photosynthesis and atherothrombosis, respectively. The technology is highly versatile and expected to enable machine-based scientific discovery in biological, pharmaceutical, and medical sciences.

DOI： 10.1016/j.cell.2018.08.028

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

The acid dissociation constants (p Ka values) of Brønsted acids at the active sites of proteins are reversibly modulated by intramolecular electrostatic interactions with neighboring ions in a reaction cycle. The resulting p Ka shift is crucial for the proteins to capture, transfer, and release target ions. On the other hand, reversible p Ka modulation through electrostatic interactions in synthetic polymer materials has seldom been realized because the interactions are strongly shielded by solvation water molecules in aqueous media. Here, we prepared hydrogel nanoparticles (NPs) bearing carboxylic acid groups whose p Ka values can be reversibly modulated by electrostatic interactions with counterions in the particles. We found that the deprotonated states of the acids were stabilized by electrostatic interactions with countercations only when the acids and cations were both imprinted in hydrophobic microdomains in the NPs during polymerization. Cationic monomers, like primary amine- and guanidium group-containing monomers, which interacted strongly with growing NPs showed greater p Ka modulation than monomers that did not interact with the NPs, such as quaternary ammonium group-containing monomers. Modulation was enhanced when the guanidium moieties were protected with hydrophobic groups during polymerization, so that the guanidium ions were imprinted in the hydrophobic microdomains; the lowest p Ka of ∼4.0 was achieved as a result. The p Ka modulation of the acids could be reversibly removed by inducing a temperature-dependent volume phase transition of the gel NPs. These design principles are applicable to other stimuli-responsive materials and integral to the development of synthetic materials that can be used to capture, transport, and separate target ions.

DOI： 10.1021/acsami.8b11397

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

DOI： 10.1021/acsami.8b07757

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

DOI： 10.1021/acs.langmuir.8b01527

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

DOI： 10.1021/acs.langmuir.8b01527

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

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

DOI： 10.1016/j.colsurfb.2017.09.038

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

pK(a) tuning of Bronsted 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 pK(a) 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 pK(a) 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 pK(a) shifts in the tuned pK(a) range and demonstrate applications of the NPs. pK(a) 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 pK(a) values could be used for the reversible and selective protonation of target molecules which have specific pK(a) 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

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

Many of macromolecular toxins induce cell death by directly interacting with cells or induction of inflammatory cytokines. Abiotic polymer ligands (PLs) composed of functional monomers are able to bind and neutralize toxins in vivo and are of great interest for efficient antidotes. However, little has been reported about recognition and neutralization of target molecules in the bloodstream because of readily elimination from the bloodstream. Here, we report a rational design of PLs-decorated lipid nanoparticles (PL-NPs) for neutralizing a target toxin in vivo. PL that decorated on the NPs would cooperatively interacts with target biomacromolecules since the lipid molecules in NPs have a high degree of freedom. In the present study, N-isopropylacrylamide based PLs interacting with histones, major mediators of sepsis, were synthesized. Affinity between PL-NPs and histones depends on monomer composition and polymer length. The optimized PL-NP showed little affinity for plasma proteins. The PL-NPs inhibited the toxicity of histones both in vitro and in vivo, suggesting that PLs on the NPs cooperatively bound to histones and neutralized their toxicity. In addition, circulation time of optimized PL was significantly prolonged by the modification onto NPs. These results provide a platform for designing antidote nanoparticles neutralizing toxic biomacromolecules.

DOI： 10.1016/j.jconrel.2017.10.028

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

DOI： 10.1021/acsomega.7b00909

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

DOI： 10.1021/acs.biomac.7b01426

Language：English  

DOI： 10.1007/978-3-319-65587-1_10

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)  

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 (similar to 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 similar to 65 degrees 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 degrees 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： 10.1038/pj.2017.28

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

DOI： 10.1246/cl.170360

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

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

Glycopolymers consisting of mannose and acrylamide with different mannose incorporation ratios (10 and 100%) were synthesized by reversible addition fragmentation chain transfer (RAFT) polymerization, and the polymer layers were prepared on a gold substrate. The detailed polymer layer structure and molecular recognition properties were analyzed by the surface plasmon resonance (SPR) technique. The glycopolymers formed pancake-like thin layers with thicknesses of similar to 2 nm in air and were swollen in the aqueous solution. The molecular recognition against concanavalin A (ConA) was also analyzed by SPR. Binding constants between glycopolymers and ConA were large enough to suggest multivalent effects. Binding rate constants of ConA to glycopolymers were in the same order; however, the dissociation rate constant was lower in the glycopolymer with a mannose ratio of 100% because of the high local mannose density near the binding point of ConA.

DOI： 10.1038/pj.2016.99

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

DOI： 10.1039/c7cc07107h

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

DOI： 10.1021/acsomega.7b00909

Language：Others  

DOI： 10.1021/bk-2017-1253.ch003

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

Macroporous monoliths, composed of thermoresponsive, tertiary-aminated, and crosslinking monomers, were prepared for continuous-flow separation of palladium(II) ions. N-Isopropylacrylamide was required to form the porous structure in the monoliths, indicating that the mechanism of porous structure formation involved polymerization-induced phase separation of the poly(N-isopropylacrylamide) gel. Tertiary-aminated monoliths showed adsorption selectivity for palladium(II) ions in hydrochloric media, compared with copper(II) ions. The maximum capacities of the monoliths with tertiary amine contents of 10, 20, 30, and 70 mol % for palladium(II) ions were 0.6, 1.1, 1.3, and 2.3 mmol/g, respectively. Darcy's permeabilities of water through the macroporous monolith were 10(-14) to 10(-13) m(2), and those were comparable to that through a commercially available membrane filter with a pore size of several micrometers. In the continuous-flow process, the macroporous monolith with tertiary amine selectively adsorbed palladium(II) ions in the coexistence of copper(II) ions with 10 times higher concentration than the palladium(II) ions. The palladium(II) ions were eluted from the macroporous monolith, and the concentration of palladium(II) ions in the eluate was up to 45 times of that in the feed solution. The average enrichment factor and total recovery percentage of palladium(II) ions were 8.7 times and 95%, respectively. (c) 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44385.

DOI： 10.1002/app.44385

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

The catalytic activities of basic and thermoresponsive microgel particles for the Knoevenagel condensation reaction in water at ambient temperature were evaluated. The gel particles (GPs) were incorporated with primary-amino, tertiary-amino, imidazole or pyridyl groups. In the Knoevenagel condensation between benzaldehyde and ethyl cyanoacetate, the GPs that had no basic group did not exhibit any catalytic activity. The GPs that had primary-amino, tertiary-amino and imidazole groups exhibited catalytic activity. The catalytic activity of the basic GPs depended on their base strength. The tertiary-aminated microgel particles had quadruple and double the activities of tertiary-aminated silica gel and trimethylamine, respectively. The higher catalytic activity may be attributable to the local enrichment effect of ethyl cyanoacetate. In terms of gel geometry, the activity of the tertiary amines in the microgel particles was higher than that in the bulk gel. The geometry of the microgel particles allowed the rapid uptake of the substrates. Because the base strength of the tertiary amines in the microgel particles decreased with increasing temperature, the catalysts and residual active methylene substrates were separated by dialysis at 80 degrees C. The recovered microgel particle catalysts were recyclable for an additional Knoevenagel condensation.

DOI： 10.1038/pj.2016.44

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

DOI： 10.1038/pj.2016.14

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

DOI： 10.1021/acsbiomaterials.5b00349

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：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1021/acs.chemrev.5b00247

Language：English  

Language：English  

Language：English  

DOI： 10.1021/acs.chemrev.5b00247

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

DOI： 10.1038/pj.2015.110

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

The pH response of lower critical solution temperature (LCST) of N-isopropylacrylamide (NIPAAm)/N-[3-(dimethylamino)propyl] methacrylamide (DMAPM) copolymers was switched by combination with porous CaCO3 microbeads. Although LCST of the simple copolymer hydrogels increases with decreasing pH, the critical value of the copolymers trapped in the porous framework decreases with the pH drop. The inversion of the pH response is ascribed to change of the effect of DMAPM by the presence of an ionic inorganic surface.

DOI： 10.1246/cl.150676

Language：Others  

Minimization of Synthetic Polymer Ligands for Specific Recognition and Neutralization of a Toxic Peptide

DOI： 10.1021/jacs.5b05259

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

DOI： 10.2116/analsci.31.173

Other Link： https://www.jstage.jst.go.jp/article/analsci/31/3/31_173/_article

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

Synthetic polymer nanoparticles (NPs) with intrinsic affinity for target biomacromolecules hold great promise in the development of novel tools for biological and biomedical research. We recently reported the design and synthesis of abiotic, synthetic polymer NPs with high intrinsic affinity for a peptide toxin melittin. The NP was selected by screening a small library of NPs (similar to 100 nm) composed of various ratios of monomers that contain functional groups complementary to the peptide melittin. The selected polymer NP, a co-polymer of acrylic acid (AAc), N-tert-butylacrylamide (TBAm), N-isopropylacrylamide (NIPAm) and N, N'-methylenebisacrylamide (BIS), effectively captures and neutralizes the toxicity of the peptide through a combination of electrostatic and hydrophobic interactions. This protocol describes a step-by-step procedure for the preparation and evaluation of synthetic polymer NPs for sequestration and neutralization of the target peptide toxin. The polymer NPs can be synthesized in a one-step polymerization reaction using commercially available reagents. The polymerization reaction for the synthesis of polymer NPs takes several hours, and the total protocol including subsequent purification and characterization by dynamic light scattering, NMR and toxicity neutralization assays takes 1-2 weeks in total.

DOI： 10.1038/nprot.2015.032

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

We describe the preparation and evaluation of nanogel-immobilized porous gel beads (GB) for application as a protein purification medium. Nanogel particles (NP) that bind with the Fc fragment of immunoglobulin G (IgG) were immobilized on the pore surface of macroporous hard GB containing quaternary ammonium cations on the surface via multipoint electrostatic interactions. The amount of NPs that were irreversibly immobilized in 1ml of GB slurry was determined to be similar to 30mg using fluorescent-labeled NPs. Images obtained via scanning electron microscopy established that the NPs were uniformly immobilized on the surface of the pores without blocking the macropores. The model target protein (IgG) was reversibly captured by the NP-immobilized GBs through NP-IgG interactions. NP-immobilized GBs have potential applications as novel affinity purification media for proteins, combining inexpensive and stable ligands with high-performance supports.

DOI： 10.1038/pj.2014.101

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

Poly(N-isopropylacrylamide) microgel (NMG) has been developed by adding various functional groups to control surface charges, hydrophobicity, pK(a) and protein adsorption capacity. Here, we developed and optimized NMG anchored with three types of functional groups as a polymeric catalyst to hydrolyze amide bonds under optimized mild conditions. Various optimization strategies were evaluated for efficient hydrolysis activity on a p-nitroaniline-based substrate by using a colorimetric assay. Based on the results, we propose a mechanism to hydrolyze amide bonds and determine the theoretical average distance, using NMG bearing functional group of 1-vinylimidazole as the study model. The hydrolysis of amide bonds was inhibited by a transition-state protease inhibitor, which also confirmed the proposed reaction model for NMG. These results provide an insight into the strategies developed to functionalize hydrogels through an enzyme-mimic approach for future robust bio- and chemical conversions as well as therapeutic utilities.

DOI： 10.1021/bm501671r

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

DOI： 10.1038/pj.2014.33

Other Link： http://www.nature.com/pj/journal/v46/n9/full/pj201433a.html#close

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

A catalytic membrane reactor, which was immobilized with palladium-loaded nanogel particles (NPs), was developed for continuous-flow Suzuki coupling reaction. Palladium-loaded membranes were prepared by immobilization of NPs, adsorption of palladium ions, and reduction into palladium(0). The presence of palladium in the membrane was confirmed by the scanning electron microscopy; palladium aggregation was not observed. The catalytic activity of the membrane reactor in continuous-flow Suzuki coupling reaction was approximately double that of a comparable reactor in which palladium ions were directly adsorbed onto an aminated membrane. This was attributed to the formation of small palladium particles. The reusability in the continuous-flow system was higher than that in a batch system, and the palladium-loaded membrane reactor had high long-term stability. (c) 2014 American Institute of Chemical Engineers AIChE J, 61: 582-589, 2015

DOI： 10.1002/aic.14653

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

DOI： 10.1002/aic.14653

Other Link： http://onlinelibrary.wiley.com/doi/10.1002/aic.14653/full

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

DOI： 10.1021/am503003v

Other Link： http://pubs.acs.org/doi/abs/10.1021/am503003v

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

Biosensors for the detection of proteins and bacteria have been developed using glycopolymer-immobilized metal mesh devices. The trimethoxysilane-containing glycopolymer was immobilized onto a metal mesh device using the silane coupling reaction. The surface shape and transmittance properties of the original metal mesh device were maintained following the immobilization of the glycopolymer. The mannose-binding protein (concanavalin A) could be detected at concentrations in the range of 10(-9) to 10(-6) mol L-1 using the glycopolymer-immobilized metal mesh device sensor, whereas another protein (bovine serum albumin) was not detected. A detection limit of 1 ng mm(-2) was achieved for the amount of adsorbed concanavalin A. The glycopolymer-immobilized metal mesh device sensor could also detect bacteria as well as protein. The mannose-binding strain of Escherichia coli was specifically detected by the glycopolymer-immobilized metal mesh device sensor. The glycopolymer-immobilized metal mesh device could therefore be used as a label-free biosensor showing high levels of selectivity and sensitivity toward proteins and bacteria.

DOI： 10.1021/am503003v

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

This article provides a brief review of the literature on the interaction between synthetic particles and biomacromolecules. Understanding the nonspecific interactions between biomacromolecules and synthetic particles is of great importance for using materials in vitro and in vivo. The interaction between functionalized polymer particles and proteins has been studied extensively to identify the main factor that governs the interaction in vitro. Recently, the composition and properties of the protein corona that forms on the surface of nanoparticles (NPs) in biofluids have been studied in the context of the function and distribution of the particles in vivo. In the meantime, NPs that recognize specific biomacromolecules have also been designed by tuning the combination and distribution of functional groups on gold NPs and dendrimers. It has also been shown that nano-gel particles that recognize target molecules can be achieved by (A) optimizing the combination and amount of functional groups in the particles and (B) molecular imprinting polymerization, in combination with (C) affinity purification. Some of these particles are capable of recognizing target molecules and neutralizing their function, even in the bloodstream of living animals, as 'plastic antibodies.'

DOI： 10.1038/pj.2014.33

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

A novel technique for detection of particulate matter in air using metal mesh devices is proposed. A 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   Publishing type：Research paper (scientific journal)  

Temperature-responsive nanogel particles with acids exhibiting large and reversible pK (a) shift are prepared by an ion-imprinting polymerization of stimuli responsive monomers, cross-linkers, and acidic monomers using protons as a template. The principles employed here should be broadly applicable to other stimuli-responsive materials and will be an integral step in the production of active proton transporter.

DOI： 10.1002/adma.201305957

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

DOI： 10.1039/C4TB00028E

Other Link： http://pubs.rsc.org/en/Content/ArticleLanding/2014/TB/c4tb00028e#!divAbstract

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

DOI： 10.1002/anie.201401095

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

Innenrücktitelbild: Temperature-Responsive Microgel Films as Reversible Carbon Dioxide Absorbents in Wet Environment (Angew. Chem. 10/2014)

DOI： 10.1002/ange.201401095

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

We describe a novel epitope discovery strategy for creating an affinity agent/peptide tag pair. A synthetic polymer nanoparticle (NP) was used as the "bait" to catch an affinity peptide tag. Biotinylated peptide tag candidates of varied sequence and length were attached to an avidin platform and screened for affinity against the polymer NP. NP affinity for the avidin/peptide tag complexes was used to provide insight into factors that contribute NP/tag binding. The identified epitope sequence with an optimized length (tMel-tag) was fused to two recombinant proteins. The tagged proteins exhibited higher NP affinity than proteins without tags. The results establish that a fusion peptide tag consisting of optimized 15 amino acid residues can provide strong affinity to an abiotic polymer NP. The affinity and selectivity of NP/tMel-tag interactions were exploited for protein purification in conjunction with immobilized metal ion/His6-tag interactions to prepare highly purified recombinant proteins. This strategy makes available inexpensive, abiotic synthetic polymers as affinity agents for peptide tags and provides alternatives for important applications where more costly affinity agents are used.

DOI： 10.1021/ja410817p

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 1.7mmolg(-1). Although the dried films did not show significant absorption, the reversible absorption capacity dramatically increased by adding a small amount of water (1mLg(-1)). The absorption capacity was independent of the amount of added water beyond 1mLg(-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 200-300m (maximum capacity of about 2Lm(-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/anie.201309758

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

DOI： 10.1002/ange.201309758

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

DOI： 10.1016/j.bmcl.2013.09.057

Other Link： http://www.sciencedirect.com/science/article/pii/S0960894X13011311

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

DOI： 10.1246/cl.131040

Other Link： https://www.jstage.jst.go.jp/article/cl/43/4/43_131040/_article

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

DOI： 10.1039/C3PY01001E

Other Link： http://pubs.rsc.org/en/content/articlehtml/2014/py/c3py01001e

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

DOI： 10.1021/la401068n

Other Link： http://pubs.acs.org/doi/abs/10.1021/la401068n

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

DOI： 10.3390/membranes3030169

Other Link： http://www.mdpi.com/2077-0375/3/3/169/pdf

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

DOI： 10.1246/cl.2013.301

Other Link： http://www.jstage.jst.go.jp/article/cl/38/6/38_538/_article

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

Preparation of Palladium-loaded Polymer Nanoparticles with Catalytic Activity for Hydrogenation and Suzuki Coupling Reactions
Palladium-loaded polymer nanoparticles with basic functional groups were prepared. When palladium ions were adsorbed on the polymer nanoparticles, the maximum loading capacity on the nanoparticles depended on the basic functional groups in the particles. The reduced palladium had a nanoscale average diameter. The palladium-loaded polymer nanoparticles exhibited catalytic activity for hydrogenation and Suzuki coupling reactions. The catalytic activity of the nanosized palladium-loaded nanoparticles was higher than that of bulk palladium.

DOI： 10.1246/cl.2013.301

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

DOI： 10.1021/am301637q

Other Link： http://pubs.acs.org/doi/abs/10.1021/am301637q

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

Language：Japanese  

Development of "Plastic Antibodies" : Synthetic Nanoparticles that are capable of Recognizing Proteins and Peptides

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

DOI： 10.1021/am2014713

Other Link： http://pubs.acs.org/doi/abs/10.1021/am2014713

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

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

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

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

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

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

分子インプリント法により抗体と同様の大きさ、分子認識能力を有するプラスチック抗体を合成できることを示した論文。

Other Link： http://medchem.pod.ne.jp/docs/medchemnews_19_03.pdf

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

Designed polymer nanoparticles (NPs) capable of binding and neutralizing a biomacromolecular toxin are prepared. A library of copolymer NPs is synthesized from combinations of functional monomers. The binding capacity and affinity of the NPs are individually analyzed. NPs with optimized composition are capable of neutralizing the toxin even in a complex biological milieu. It is anticipated that this strategy will be a starting point for the design of synthetic alternatives to antibodies.

DOI： 10.1002/smll.200900186

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

DOI： 10.1246/cl.2009.538

Other Link： http://www.jstage.jst.go.jp/article/cl/38/6/38_538/_article

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

DOI： 10.1246/cl.2005.1602

Other Link： http://www.jstage.jst.go.jp/article/cl/34/12/34_1602/_article

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

Communication: Strong films were prepared from an RNA/lipid complex by casting from organic solutions. RNA (mainly tRNA) was extracted from yeasts, followed by a replacement of the sodium counterions of the tRNA phosphate units by cationic amphiphiles. RNA units in the RNA/lipid film could be aligned in one direction by stretching due to the presence of inter-molecular hydrogen bonds. The film showed physical strength and was biodegradable.

DOI： 10.1002/1521-3927(20020301)23:4<253::AID-MARC253>3.0.CO;2-H

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

DOI： 10.1093/nass/1.1.61

Other Link： http://www.ncbi.nlm.nih.gov/pubmed/12836264

Event date： 2018.3

Language：Japanese   Presentation type：Symposium, workshop panel (public)  

Venue：関西大学（大阪府吹田市）   Country：Japan  

Event date： 2017.12

Language：English   Presentation type：Oral presentation (general)  

Venue：北九州私立大学　ひびきのキャンパス（北九州市）   Country：Japan  

Event date： 2017.12

Language：English   Presentation type：Oral presentation (general)  

Venue：北九州私立大学　ひびきのキャンパス（北九州市）   Country：Japan  

Event date： 2017.12

Language：English   Presentation type：Oral presentation (general)  

Venue：北九州私立大学　ひびきのキャンパス（北九州市）   Country：Japan  

Event date： 2017.11

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：大分大学（大分市）   Country：Japan  

Event date： 2017.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：松山   Country：Japan  

Event date： 2017.6

Language：English   Presentation type：Oral presentation (general)  

Venue：PARIS   Country：France  

Synthetic materials that alter their binding affinity to target molecules in response to　external stimuli have gained considerable attention as substitutes for protein based　ligands. Recently, we revealed that pNIPAm-based NPs that show large and　reversible pKa shifts can be prepared by the “proton imprinting” and　“microenvironment imprinting” strategy. The pKa variation range of　carboxylic acids in the NPs can further be tuned by designing structure of monomers　containing Brønsted acids and tuning cross-linking density and size of NPs. The pKa　variation range can be lowered/raised to be 4-9 by stabilizing/destabilizing carboxylate　anions by modifying the acids with electron withdrawing/donating group. The pKa of　acids can also be lowered dramatically by imprinting cationic functional group such as　guanidium group around the carboxylate anions.
Our results provide a guide for designing stable and inexpensive materials for many　biological and chemical applications as temperature-dependent affinity media and pH　modifiers.

Event date： 2017.5

Language：English   Presentation type：Oral presentation (general)  

Venue：Kyoto University   Country：Japan  

Event date： 2017.5

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：千葉   Country：Japan  

Event date： 2017.5

Language：Japanese   Presentation type：Symposium, workshop panel (public)  

Venue：千葉   Country：Japan  

Event date： 2017.4

Language：English   Presentation type：Oral presentation (general)  

Venue：San Francisco   Country：United States  

Event date： 2017.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：慶應義塾大学   Country：Japan  

Event date： 2017.3

Language：English   Presentation type：Oral presentation (general)  

Venue：Nihon University   Country：Japan  

Event date： 2017.3

Language：English   Presentation type：Oral presentation (general)  

Venue：Keio University   Country：Japan  

Event date： 2014.8

Language：English   Presentation type：Oral presentation (general)  

Venue：Fukuoka   Country：Japan  

Event date： 2014.8

Language：English  

Venue：Fukuoka   Country：Japan  

Event date： 2014.7

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：東京工業大学   Country：Japan  

Event date： 2013.12

Language：English  

Venue：Boston   Country：United States  

Event date： 2013.4

Language：English   Presentation type：Oral presentation (general)  

Venue：New Orleans, Louisiana   Country：United States  

Event date： 2013.4

Language：English   Presentation type：Oral presentation (general)  

Venue：New Orleans, Louisiana   Country：United States  

Event date： 2013.4

Language：English   Presentation type：Oral presentation (general)  

Venue：New Orleans, Louisiana   Country：United States  

Event date： 2013.4

Language：English   Presentation type：Oral presentation (general)  

Venue：New Orleans, Louisiana   Country：United States  

Event date： 2013.3

Language：English  

Venue：Fukuoka   Country：Japan  

Event date： 2013.3

Language：English  

Venue：Fukuoka   Country：Japan  

Event date： 2013.1

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：京都国際会館   Country：Japan  

Event date： 2012.3 - 2012.5

Presentation type：Oral presentation (general)  

Venue：San Diego, California   Country：United States  

Event date： 2011.3

Presentation type：Oral presentation (general)  

Venue：Anaheim, CA   Country：United States  

Event date： 2011.3

Presentation type：Oral presentation (general)  

Venue：Anaheim, CA   Country：United States  

Event date： 2011.3

Presentation type：Oral presentation (general)  

Venue：Anaheim, CA   Country：United States  

Event date： 2011.3

Presentation type：Oral presentation (general)  

Venue：Anaheim, CA   Country：United States  

Event date： 2011.3

Presentation type：Oral presentation (general)  

Venue：Anaheim, CA   Country：United States  

Event date： 2010.8

Presentation type：Oral presentation (general)  

Venue：New Orleans   Country：United States  

Event date： 2010.3

Presentation type：Oral presentation (general)  

Venue：San Francisco、CA   Country：United States  

Event date： 2010.3

Presentation type：Oral presentation (general)  

Venue：San Francisco, CA   Country：United States  

Event date： 2009.8

Presentation type：Oral presentation (general)  

Venue：Washington DC   Country：United States  

Event date： 2009.5

Presentation type：Oral presentation (general)  

Venue：Kobe   Country：Japan  

Event date： 2009.5

Presentation type：Oral presentation (general)  

Venue：Kobe   Country：Japan  

Event date： 2005.12

Presentation type：Oral presentation (general)  

Venue：Honolulu Hawai   Country：United States  

Event date： 2003.12

Presentation type：Oral presentation (general)  

Venue：Awaji   Country：Japan  

Event date： 2001.11

Presentation type：Oral presentation (general)  

Venue：Yokohama   Country：Japan  

Event date： 2024.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：大阪公立大学   Country：Japan  

Event date： 2023.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：熊本城ホール   Country：Japan  

Event date： 2023.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：福岡大学   Country：Japan  

Event date： 2023.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：広島   Country：Japan  

Event date： 2023.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：西新プラザ   Country：Japan  

Event date： 2023.8 - 2023.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：久留米   Country：Japan  

Event date： 2022.7

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2022.6

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2022.6

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2022.6

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：九州工業大学   Country：Japan  

Event date： 2022.4

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2022.1

Language：English   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2021.12

Language：English   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：United States  

Event date： 2021.12

Language：English   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：United States  

Event date： 2021.12

Language：English   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：United States  

Event date： 2021.12

Language：English   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：United States  

Event date： 2021.12

Language：English   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：United States  

Event date： 2021.11

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2021.10

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2021.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2021.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2021.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2021.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2021.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2021.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2021.8

Language：Japanese   Presentation type：Public lecture, seminar, tutorial, course, or other speech  

Venue：オンライン   Country：Japan  

Event date： 2021.7

Language：English   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：United States  

Event date： 2021.7

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2021.5

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2021.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2021.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2021.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2021.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2021.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2020.12

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2020.12

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2020.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2020.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2020.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2020.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2020.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2020.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2020.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2020.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2020.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2020.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2020.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2020.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2020.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2020.7

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2020.7

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2020.5

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：福岡国際会議場   Country：Japan  

Event date： 2020.5

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：福岡国際会議場   Country：Japan  

Event date： 2020.5

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：福岡国際会議場   Country：Japan  

Event date： 2020.5

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：福岡国際会議場   Country：Japan  

Event date： 2020.5

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：福岡国際会議場   Country：Japan  

Event date： 2020.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：関西大学　千里山キャンパス（吹田市）   Country：Japan  

Event date： 2020.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：関西大学　千里山キャンパス（吹田市）   Country：Japan  

Event date： 2020.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：関西大学　千里山キャンパス（吹田市）   Country：Japan  

Event date： 2020.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：関西大学　千里山キャンパス（吹田市）   Country：Japan  

Event date： 2020.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：関西大学　千里山キャンパス（吹田市）   Country：Japan  

Event date： 2020.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：関西大学　千里山キャンパス（吹田市）   Country：Japan  

Event date： 2020.3

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：上智大学　四谷キャンパス（千代田区）   Country：Japan  

Event date： 2019.11

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：TKP ガーデンシティ鹿児島中央（鹿児島市）   Country：Japan  

Event date： 2019.11

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：TKP ガーデンシティ鹿児島中央（鹿児島市）   Country：Japan  

Event date： 2019.11

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：TKP ガーデンシティ鹿児島中央（鹿児島市）   Country：Japan  

Event date： 2019.11

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：TKP ガーデンシティ鹿児島中央（鹿児島市）   Country：Japan  

Event date： 2019.10

Language：English   Presentation type：Oral presentation (general)  

Venue：Pusan National University   Country：Korea, Republic of  

Event date： 2019.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：福井大学　文京キャンパス（福井市）   Country：Japan  

Event date： 2019.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：福井大学　文京キャンパス（吹田市）   Country：Japan  

Event date： 2019.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：福井大学　文京キャンパス（福井市）   Country：Japan  

Event date： 2019.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：福井大学　文京キャンパス（福井市）   Country：Japan  

Event date： 2019.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：福井大学　文京キャンパス（福井市）   Country：Japan  

Event date： 2019.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：福井大学　文京キャンパス（福井市）   Country：Japan  

Event date： 2019.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：福井大学　文京キャンパス（福井市）   Country：Japan  

Event date： 2019.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：福井大学　文京キャンパス（福井市）   Country：Japan  

Event date： 2019.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：福井大学　文京キャンパス（福井市）   Country：Japan  

Event date： 2019.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：福井大学　文京キャンパス（福井市）   Country：Japan  

Event date： 2019.9

Language：English   Presentation type：Oral presentation (general)  

Venue：札幌コンベンションセンター（札幌）   Country：Japan  

Event date： 2019.7

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：北九州国際会議場（北九州市）   Country：Japan  

Event date： 2019.7

Language：Japanese   Presentation type：Oral presentation (general)