受賞区分：国内学会・会議・シンポジウム等の賞  受賞国：日本国

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Bulletin of the Chemical Society of Japan  

Living cells and organisms are composed of numerous biomolecules and control their concentrations and spatial distribution in a spatiotemporal manner to exhibit intricate biological functions. Inspired by the extracellular matrix, synthetic multi-network hydrogels have attracted attention due to their remarkable properties like extremely high toughness. This account summarizes our research progress on one emerging class of the multi-network hydrogels, supramolecularpolymer composite hydrogel. Composite hydrogels can rationally integrate stimulus response of supramolecular gels and stiffness of polymer gels. Super-resolution microscopy visualizes four types of network patterns at the µm scale: an orthogonal and three interactive networks, which may influence the viscoelastic properties of composite hydrogels. We found a kind of composite hydrogel that shows autonomous network remodeling, enabling fracture-induced 3D gel patterning. Furthermore, we demonstrated that supramolecularpolymer composite hydrogels are applicable as a matrix for controlled release of protein biopharmaceuticals in response to antibodies through incorporation of functional molecules such as enzymes and their inhibitors. Supramolecularpolymer composite hydrogels hold promise as the next-generation smart and responsive soft materials for biomedical applications, including tissue engineering and regenerative medicine.

DOI： 10.1246/bcsj.20230129

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Journal of the American Chemical Society  

Coacervates, which are formed by liquid-liquid phase separation, have been extensively explored as models for synthetic cells and membraneless organelles, so their in-depth structural analysis is crucial. However, both the inner structure dynamics and formation mechanism of coacervates remain elusive. Herein, we demonstrate real-time confocal observation of a three-dimensional sponge-like network in a dipeptide-based coacervate. In situ generation of the dipeptide allowed us to capture the emergence of the sponge-like network via unprecedented membrane folding of vesicle-shaped intermediates. We also visualized dynamic fluctuation of the network, including reversible engagement/disengagement of cross-links and a stochastic network kissing event. Photoinduced transient formation of a multiphase coacervate was achieved with a thermally responsive phase transition. Our findings expand the fundamental understanding of synthetic coacervates and provide opportunities to manipulate their physicochemical properties by engineering the inner network for potential applications in development of artificial cells and life-like material fabrication.

DOI： 10.1021/jacs.3c03793

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Nature Communications  

Synthetic composite hydrogels comprising supramolecular fibers and covalent polymers have attracted considerable attention because their properties are similar to biological connective tissues. However, an in-depth analysis of the network structures has not been performed. In this study, we discovered the composite network can be categorized into four distinct patterns regarding morphology and colocalization of the components using in situ, real-time confocal imaging. Time-lapse imaging of the network formation process reveals that the patterns are governed by two factors, the order of the network formation and the interactions between the two different fibers. Additionally, the imaging studies revealed a unique composite hydrogel undergoing dynamic network remodeling on the scale of a hundred micrometers to more than one millimeter. Such dynamic properties allow for fracture-induced artificial patterning of a network three dimensionally. This study introduces a valuable guideline to the design of hierarchical composite soft materials.

DOI： 10.1038/s41467-023-37412-0

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その他リンク： https://www.nature.com/articles/s41467-023-37412-0

担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society ({ACS})  

The fate of living cells often depends on their processing of temporally modulated information, such as the frequency and duration of various signals. Synthetic stimulus-responsive systems have been intensely studied for >50 years, but it is still challenging for chemists to create artificial systems that can decode dynamically oscillating stimuli and alter the systems’ properties/functions because of the lack of sophisticated reaction networks that are comparable with biological signal transduction. Here, we report morphological differentiation of synthetic dipeptide-based coacervates in response to temporally distinct patterns of the light pulse. We designed a simple cationic diphenylalanine peptide derivative to enable the formation of coacervates. The coacervates concentrated an anionic methacrylate monomer and a photoinitiator, which provided a unique reaction environment and facilitated light-triggered radical polymerization-even in air. Pulsed light irradiation at 9.0 Hz (but not at 0.5 Hz) afforded anionic polymers. This dependence on the light pulse patterns is attributable to the competition of reactive radical intermediates between the methacrylate monomer and molecular oxygen. The temporal pulse pattern-dependent polymer formation enabled the coacervates to differentiate in terms of morphology and internal viscosity, with an ultrasensitive switch-like mode. Our achievements will facilitate the rational design of smart supramolecular soft materials and are insightful regarding the synthesis of sophisticated chemical cells.

DOI： 10.1021/jacs.2c05101

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Nature Communications  

Direct activation of cell-surface receptors is highly desirable for elucidating their physiological roles. A potential approach for cell-type-specific activation of a receptor subtype is chemogenetics, in which both point mutagenesis of the receptors and designed ligands are used. However, ligand-binding properties are affected in most cases. Here, we developed a chemogenetic method for direct activation of metabotropic glutamate receptor 1 (mGlu1), which plays essential roles in cerebellar functions in the brain. Our screening identified a mGlu1 mutant, mGlu1(N264H), that was activated directly by palladium complexes. A palladium complex showing low cytotoxicity successfully activated mGlu1 in mGlu1(N264H) knock-in mice, revealing that activation of endogenous mGlu1 is sufficient to evoke the critical cellular mechanism of synaptic plasticity, a basis of motor learning in the cerebellum. Moreover, cell-type-specific activation of mGlu1 was demonstrated successfully using adeno-associated viruses in mice, which shows the potential utility of this chemogenetics for clarifying the physiological roles of mGlu1 in a cell-type-specific manner.

DOI： 10.1038/s41467-022-30828-0

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society ({ACS})  

DOI： 10.26434/chemrxiv-2022-bp028

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Royal Society of Chemistry ({RSC})  

The synthesis of branched gold nanoparticles (AuNPs) with shape- and size-specific optical properties requires effective control of the particle formation mechanism using appropriate reducing agents and protective agents that prevent particle aggregation in solution. In this context, the heterogeneous synthesis of AuNPs using solid surfaces of graphene oxides and metal–organic frameworks has attracted much attention. These materials are characterized by their ability to immobilize and stabilize the particles grown on the surface without the need for additional protective agents. However, the shape- and size-selective synthesis of AuNPs using solid surfaces remains challenging. Herein, we report the shape-selective one-step synthesis of monodisperse branched AuNPs using a metal–macrocycle framework (MMF), a porous molecular crystal of PdII3-tris(phenylenediamine) macrocycle. Konpeito-Shaped branched AuNPs with uniform size were obtained on the surface of MMF by mixing HAuCl<inf>4</inf>·4H<inf>2</inf>O, l-ascorbic acid and MMF microcrystals. Spectroscopic and microscopic observations confirmed that MMF promoted the reduction of gold by its reductive activity as well as acted as a solid support to electrostatically immobilize the pseudo-seed particles for further growth on the crystal surface. In addition, the MMF also served as a substrate for in situ high-speed AFM imaging due to the effective immobilization of AuNPs on the surface, allowing direct visualization of the particle growth. Since the chemical structural features of MMF allow the growth of branched AuNPs via pseudo-seeding, this approach would provide new synthetic methods for obtaining a variety of gold nanostructures.

DOI： 10.1039/d1dt03973c

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jacs.1c09172

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

DOI： https://doi.org/10.1021/acs.chemrev.0c01334

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

DOI： https://doi.org/10.1246/cl.200513

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： https://doi.org/10.1038/s41467-020-17984-x

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

DOI： https://doi.org/10.1038/s41467-020-17698-0

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

DOI： https://doi.org/10.1038/s41467-020-17394-z

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： https://doi.org/10.1039/D0FD00019A

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： https://doi.org/10.1039/D0CE00120A

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

DOI： https://doi.org/10.1002/open.201900328

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： https://doi.org/10.1021/acsnano.9b05342

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

DOI： https://doi.org/10.1016/bs.mie.2019.02.033

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： https://doi.org/10.1021/jacs.9b00715

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： https://doi.org/10.1039/C8SC03086C

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

DOI： https://doi.org/10.1021/acscentsci.8b00390

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： https://doi.org/10.1021/acs.bioconjchem.8b00260

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： https://doi.org/10.1038/s41565-017-0026-6

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

DOI： https://doi.org/10.1038/nchem.2554

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： https://doi.org/10.1039/C6CC02621D

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： https://doi.org/10.1038/nchem.2526

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

DOI： https://doi.org/10.1039/C5SC04570C

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

DOI： https://doi.org/10.1039/C4CS00381K

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

DOI： https://doi.org/10.1038/nchem.2044

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： https://doi.org/10.1002/anie.201404179

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： https://doi.org/10.1039/C3DT51827B

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

DOI： https://doi.org/10.1080/10610278.2012.733394

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： https://doi.org/10.1021/ja209422m

開催年月日： 2026年1月

記述言語：日本語   会議種別：口頭発表（招待・特別）  

開催地：鳥取   国名：日本国  

開催年月日： 2025年12月

記述言語：英語   会議種別：口頭発表（招待・特別）  

開催地：Honolulu   国名：アメリカ合衆国  

非平衡な超分子化学に関する国際学会における招待講演

開催年月日： 2025年12月

記述言語：英語   会議種別：口頭発表（招待・特別）  

開催地：Honolulu   国名：アメリカ合衆国  

自己集合性ペプチドに関する国際学会における招待講演

開催年月日： 2025年12月

記述言語：日本語   会議種別：ポスター発表  

開催地：広島   国名：日本国  

開催年月日： 2025年5月

記述言語：英語   会議種別：口頭発表（招待・特別）  

開催地：Kyoto   国名：日本国  

超分子化学に関する国際学会における招待講演

開催年月日： 2025年5月

記述言語：日本語   会議種別：口頭発表（招待・特別）  

開催地：神奈川   国名：日本国