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

DOI： 10.1021/acs.biomac.1c01483

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

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

DOI： doi.org/10.1039/D1CC04394C

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

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

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

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

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

DOI： 10.1021/acs.biomac.9b00515

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

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

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

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

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

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

DOI： doi.org/10.1021/acsabm.8b00096

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

DOI： 10.1021/acs.biomac.7b01426

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

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

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

DOI： doi.org/10.1038/pj.2016.14

DOI： 10.1080/00219592.2024.2384402

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Authorship：Corresponding author   Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1039/d4lp00135d

Language：English   Publisher：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

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Publisher：Polymer Journal  

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

DOI： 10.1038/s41428-024-00923-8

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Language：English   Publisher：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

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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：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

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Publisher：Chemistry Letters  

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

DOI： 10.1093/chemle/upad012

Scopus

Language：English  

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

Language：Japanese   Publisher：The Society of Polymer Science, Japan  

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

DOI： 10.1295/kobunshi.73.4_147

CiNii Research

Language：English   Publisher：Chemistry - An Asian Journal  

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

DOI： 10.1002/asia.202300643

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Language：English  

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

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

DOI： 10.1039/D3MA00251A

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Scopus

Repository Public URL： https://hdl.handle.net/2324/7160862

Language：English  

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

Language：English   Publisher：The Asahi Glass Foundation  

DOI： 10.50867/afreport.2023_042

CiNii Research

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

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

DOI： 10.1002/ange.202206456

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

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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CiNii Research

Repository Public URL： https://hdl.handle.net/2324/7160860

Language：English  

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  

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

DOI： 10.1246/cl.210740

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CiNii Research

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

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

DOI： 10.1039/D1TB02344F

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PubMed

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

DOI： 10.1039/D1RE00386K

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

DOI： 10.1039/D1RE00386K

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

DOI： org/10.1016/j.eurpolymj.2020.110044

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

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

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

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

DOI： 10.1039/c7cc07107h

Event date： 2023.5

Language：Japanese   Presentation type：Oral presentation (general)  

Country：Japan  

Event date： 2022.10 - 2023.11

Language：English   Presentation type：Oral presentation (general)  

Country：Canada  

Event date： 2022.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：北海道大学   Country：Japan  

Event date： 2022.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2022.9

Language：Japanese   Presentation type：Oral presentation (general)  

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

Event date： 2021.10

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：鹿児島県民交流センター   Country：Japan  

Event date： 2021.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2021.6

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：オンライン   Country：Japan  

Event date： 2023.9

Language：Japanese   Presentation type：Oral presentation (general)  

Venue：高野山大学   Country：Japan  

Event date： 2023.3

Language：Japanese  

Venue：東京農工大学　小金井キャンパス   Country：Japan  

Event date： 2022.9

Language：English   Presentation type：Oral presentation (general)  

Country：Japan  

Event date： 2022.9

Language：Japanese   Presentation type：Oral presentation (general)  

Country：Japan  

Event date： 2022.4

Language：Japanese  

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