記述言語：日本語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Biomacromolecules  

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

DOI： 10.1021/acs.biomac.1c01483

Web of Science

Scopus

PubMed

リポジトリ公開URL： https://hdl.handle.net/2324/4793641

記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： doi.org/10.1039/D1CC04394C

リポジトリ公開URL： http://hdl.handle.net/2324/4706206

記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： doi.org/10.1021/acs.biomac.1c00553

リポジトリ公開URL： http://hdl.handle.net/2324/4706207

記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acs.biomac.9b00515

記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： org/10.1021/acs.bioconjchem.9b00134

リポジトリ公開URL： http://hdl.handle.net/2324/2320611

記述言語：日本語   掲載種別：研究論文（学術雑誌）  

Multiblock glycopolymers have gathered attention because of their potential use as effective ligands for sugar‐binding proteins. The authors report the quantitative preparation of multiblock glycopolymers by reversible addition‐fragmentation chain transfer polymerization. The optimized polymerization condition enabled the complete monomer incorporation into the elongating polymer chains at each polymerization step. The structure of the heptablock glycopolymer was well‐defined (polydispersity index <1.35), and their molecular recognition against lectins was evaluated.

DOI： 10.1002/pola.29344

記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： doi.org/10.1021/acsabm.8b00096

記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acs.biomac.7b01426

記述言語：日本語   掲載種別：研究論文（学術雑誌）  

This paper reports the synthesis and application of acrylamide-type neoglycoconjugates interacting with practical targets. Polymer backbones with acrylamide and acrylamide derivatives bearing alkyne groups were prepared using living radical polymerization. Oligosaccharides were introduced into the backbones using copper-catalysed azide–alkyne cycloaddition “post-click” chemistry.

DOI： doi.org/10.1039/C6PY00904B

記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： doi.org/10.1038/pj.2016.14

DOI： 10.1080/00219592.2024.2384402

Web of Science

担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/d4lp00135d

記述言語：英語   出版者・発行元：Biomacromolecules  

Polymer self-assemblies driven by enthalpic interactions, such as hydrogen bonding and electrostatic interactions, exhibit distinct properties compared to those driven by hydrophobic interactions. Carbohydrate-carbohydrate interactions, which are observed in physiological phenomena, also fall under enthalpic interactions. Our group previously reported on self-assemblies of methacrylate-type glycopolymers carrying mannose units in the presence of calcium ions; however, a detailed study of these interactions was lacking. In this work, we investigated the interactions between glycopolymers using the quartz crystal microbalance (QCM) method. Our quantitative analysis revealed that the interactions between the glycopolymers were influenced by the carbohydrate structures in the side chains, the types of divalent metal ions, and the structures of the polymer main chains. Notably, the strongest interaction was observed in the combination of methacrylate-type glycopolymers carrying mannose units and calcium ions, demonstrating their potential as a driving force for polymer self-assembly.

DOI： 10.1021/acs.biomac.4c00493

Web of Science

Scopus

PubMed

出版者・発行元：Polymer Journal  

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

DOI： 10.1038/s41428-024-00923-8

Web of Science

Scopus

記述言語：英語   出版者・発行元：ChemPlusChem  

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 peanut agglutinin 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

Web of Science

Scopus

PubMed

記述言語：英語   出版者・発行元：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

Web of Science

Scopus

PubMed

記述言語：英語   出版者・発行元：Nanoscale  

The optimal structure of synthetic glycopolymers for GM1 mimetics was determined through Bayesian optimization. The interactions of glycopolymers carrying galactose and neuraminic acid units in different compositions with cholera toxin B subunit (CTB) were assessed by an enzyme-linked immunosorbent assay (ELISA). Gaussian process regression, using the ELISA results, predicted the composition of glycopolymers that would exhibit stronger interactions with CTB. Following five cycles of optimization, the glycopolymers carrying 60 mol% galactose and 25 mol% neuraminic acid demonstrated an IC50 value of 75 μM for CTB, representing the lowest value among the synthesized glycopolymers.

DOI： 10.1039/d4nr00915k

Web of Science

Scopus

PubMed

出版者・発行元：Chemistry Letters  

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

DOI： 10.1093/chemle/upad012

Scopus

記述言語：英語  

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

CiNii Research

記述言語：日本語   出版者・発行元：公益社団法人 高分子学会  

<p>糖を高分子の側鎖に結合させた高分子、糖鎖高分子は、糖をベースにし、合成高分子と融合した構造をもち、精密重合などの高分子化学の技術を用いて調製可能である。この高分子は水溶性、両親媒性などの物理化学的な性質を発揮し、なおかつ糖鎖が集積した構造に基づく生体分子認識能を有する。糖鎖高分子の概要と近年の研究について紹介する。</p>

DOI： 10.1295/kobunshi.73.4_147

CiNii Research

記述言語：英語   出版者・発行元：Chemistry - An Asian Journal  

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

DOI： 10.1002/asia.202300643

Web of Science

Scopus

PubMed

記述言語：英語  

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

CiNii Research

記述言語：日本語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Materials Advances  

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

DOI： 10.1039/D3MA00251A

Web of Science

Scopus

リポジトリ公開URL： https://hdl.handle.net/2324/7160862

記述言語：英語  

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

CiNii Research

記述言語：英語   出版者・発行元：公益財団法人 旭硝子財団  

DOI： 10.50867/afreport.2023_042

CiNii Research

記述言語：日本語   掲載種別：研究論文（学術雑誌）   出版者・発行元：MDPI  

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

DOI： 10.3390/polym14235123

Web of Science

Scopus

PubMed

CiNii Research

記述言語：英語   出版者・発行元：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

Web of Science

Scopus

PubMed

記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/ange.202206456

記述言語：日本語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society  

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

DOI： 10.1021/acsomega.2c00719

Web of Science

Scopus

PubMed

CiNii Research

リポジトリ公開URL： https://hdl.handle.net/2324/7160860

記述言語：英語  

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

記述言語：英語   出版者・発行元：The Chemistry Society of Japan  

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

DOI： 10.1246/cl.210740

Web of Science

Scopus

CiNii Research

記述言語：日本語   掲載種別：研究論文（学術雑誌）  

記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/D1TB02344F

Web of Science

PubMed

記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/D1RE00386K

記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/D1RE00386K

記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： org/10.1016/j.eurpolymj.2020.110044

リポジトリ公開URL： http://hdl.handle.net/2324/4479609

記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： doi.org/10.1021/acs.langmuir.8b01527

記述言語：日本語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c7cc07107h

開催年月日： 2023年5月

記述言語：日本語   会議種別：口頭発表（一般）  

国名：日本国  

開催年月日： 2022年10月 - 2023年11月

記述言語：英語   会議種別：口頭発表（一般）  

国名：カナダ  

開催年月日： 2022年9月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：北海道大学   国名：日本国  

開催年月日： 2022年9月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：オンライン   国名：日本国  

開催年月日： 2022年9月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：東京工業大学　大岡山キャンパス   国名：日本国  

開催年月日： 2021年10月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：鹿児島県民交流センター   国名：日本国  

開催年月日： 2021年9月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：オンライン   国名：日本国  

開催年月日： 2021年6月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：オンライン   国名：日本国  

開催年月日： 2023年9月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：高野山大学   国名：日本国  

開催年月日： 2023年3月

記述言語：日本語  

開催地：東京農工大学　小金井キャンパス   国名：日本国  

開催年月日： 2022年9月

記述言語：英語   会議種別：口頭発表（一般）  

国名：日本国  

開催年月日： 2022年9月

記述言語：日本語   会議種別：口頭発表（一般）  

国名：日本国  

開催年月日： 2022年4月

記述言語：日本語  

開催地：オンライン   国名：日本国  

開催年月日： 2021年5月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：オンライン   国名：日本国