2023/07/19 更新

写真a

クサカ シンペイ
日下 心平
KUSAKA Shinpei
所属
大学院工学研究科 応用物質化学専攻 固体化学 助教
大学院担当
大学院工学研究科
学部担当
工学部 化学生命工学科
職名
助教

学位 1

  1. 博士(理学) ( 2013年3月   東京大学 ) 

研究分野 2

  1. ナノテク・材料 / 無機・錯体化学

  2. ナノテク・材料 / 無機・錯体化学

経歴 2

  1. 名古屋大学   大学院工学研究科 応用物質化学専攻 固体化学   助教

    2020年8月 - 現在

  2. 名古屋大学   大学院工学研究科 応用物質化学専攻 固体化学   特任助教

    2018年4月 - 2020年7月

 

論文 35

  1. Heterobilayer membranes from isostructural metal-organic frameworks for efficient CO2 separation

    Wang Xiaoguang, Kusaka Shinpei, Hori Akihiro, Sen Susan, Matsuda Ryotaro

    MICROPOROUS AND MESOPOROUS MATERIALS   338 巻   2022年6月

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    出版者・発行元:Microporous and Mesoporous Materials  

    Metal-organic frameworks (MOFs) are promising candidates for membrane gas separation because of their high porosity and structural tunability. Although the appropriate size of the pore aperture of MOFs is required depending on the target molecules to separate, pore size control of MOFs occasionally influences crystal growth, preventing the fabrication of dense membranes. In this study, we present a heterobilayer membrane strategy using two isostructural MOFs. First, a MOF Kgm-OPr with fast nucleation rate was fabricated as a seed layer on an Al2O3 substrate, then the layer of Kgm-OMe or Kgm-H, which is isostructural to Kgm-OPr, was prepared on the Kgm-OPr seed layer through secondary growth. In this way, the high-quality membranes which selectively permeate CO2 over N2, CH4, and C2H4 were obtained, although all three MOFs did not form dense membranes when they were used alone. Our result would contribute to the expansion of the family of MOFs applicable to membranes for molecular separation.

    DOI: 10.1016/j.micromeso.2022.111950

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  2. Design of a MOF based on octa-nuclear zinc clusters realizing both thermal stability and structural flexibility 査読有り 国際共著

    Ma Yunsheng, Tang Xiaoyan, Chen Ming, Mishima Akio, Li Liangchun, Hori Akihiro, Wu Xiaoyu, Ding Lifeng, Kusaka Shinpei, Matsuda Ryotaro

    CHEMICAL COMMUNICATIONS   58 巻 ( 8 ) 頁: 1139 - 1142   2022年1月

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    記述言語:英語   出版者・発行元:Chemical Communications  

    An octa-nuclear zinc (Zn8) cluster-based two-fold interpenetrated metal-organic framework (MOF) of [(CH3)2NH2]2[Zn8O3(FDC)6]·7DMF (denoted as Zn8-as; H2FDC = 9H-fluorene-2,7-dicarboxylic acid; DMF = N,N-dimethylformamide) was synthesized by the reaction of a hard base of a curved dicarboxylate ligand (H2FDC) with the borderline acid of Zn(ii) under solvothermal conditions. Zn8-as shows significant crystal volume shrinkage upon heating, yielding a solvate-free framework of [(CH3)2NH2]2[Zn8O3(FDC)6] (Zn8-de). Zn8-de displays gated adsorption for C2H2 and type-I adsorption for CO2, attributed to the framework flexibility and the different interactions between the gas molecules and the host framework.

    DOI: 10.1039/d1cc05893b

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  3. Selective Photochemical Reaction by Fixing Reactant as a MOF Building Block 査読有り

    Ono Katsuya, Kusaka Shinpei, Matsuda Ryotaro

    CHEMISTRY LETTERS   50 巻 ( 12 ) 頁: 1987 - 1989   2021年12月

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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:Chemistry Letters  

    We demonstrate selective photo-reactions observed between the two different chemical species bearing carbon-carbon double bonds in MOF 1. 1,2-Bis(4-pyridyl)ethylene (bpe) was fixed in 1 as the organic linker, which reacted with tetramethylethylene (TME) as the guest molecule. As a result, a specific product from the radical reaction was selectively generated, whereas various side products were observed when reacted in solution. Our strategy to realize selective reactions would contribute to enforce the applicability of solid-phase reactions in synthetic chemistry.

    DOI: 10.1246/cl.210525

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  4. Stabilization of radical active species in a MOF nanospace to exploit unique reaction pathways 査読有り 国際共著

    Harada Yuki, Kusaka Shinpei, Nakajo Toshinobu, Kumagai Jun, Kim Cho Rong, Shim Joo Young, Hori Akihiro, Ma Yunsheng, Matsuda Ryotaro

    CHEMICAL COMMUNICATIONS   57 巻 ( 91 ) 頁: 12115 - 12118   2021年11月

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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:Chemical Communications  

    We synthesized a metal-organic framework (MOF) using a ligand bearing haloalkoxy chains as a radical precursor. The radicals generated in the MOF upon photoirradiation were stable even at 250 K or under an O2 atmosphere, despite radicals generated from the ligand decomposing at 200 K; thus, the regular arrangement of radicals effectively stabilized them. Moreover, a unique photoproduct was obtained only in the MOF, indicating that the confinement effect in the nanospace enabled a specific reaction that did not occur in the bulk state. We propose a new platform for exploring chemical reactions and materials based on reactive species. This journal is

    DOI: 10.1039/d1cc04267j

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  5. Fabrication of a Kagome-type MOF Membrane by Seeded Growth on Amino-functionalized Porous Al2O3 Substrate 査読有り

    Wang Xiaoguang, Kusaka Shinpei, Hori Akihiro, Matsuda Ryotaro

    CHEMISTRY-AN ASIAN JOURNAL   16 巻 ( 15 ) 頁: 2018 - 2021   2021年8月

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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:Chemistry - An Asian Journal  

    In this study, we report an efficient fabrication method for the membrane of a metal-organic framework (MOF) (Kgm−OEt) which is one kind of kagomé-type MOF with a two-dimensional (2D) sheet structure having one-dimensional (1D) channels suitable for separation of H2 from other larger gases. The Kgm−OEt seed layer was created on an Al2O3 substrate using layer-by-layer (LBL) growth, then a membrane was fabricated by secondary growth. The membrane on a 3-aminopropyltriethoxysilane (APTEs)-treated substrate obtained in this method was continuous and defect-free with the crystal orientation suitable for gas transportation, while the membrane grown on an unmodified substrate was loosely packed with unfavorable crystal orientation.

    DOI: 10.1002/asia.202100507

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  6. Triplet Carbene with Highly Enhanced Thermal Stability in the Nanospace of a Metal-Organic Framework 査読有り

    Nakajo Toshinobu, Kumagai Jun, Kusaka Shinpei, Hori Akihiro, Hijikata Yuh, Pirillo Jenny, Ma Yunsheng, Matsuda Ryotaro

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   143 巻 ( 21 ) 頁: 8129 - 8136   2021年6月

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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  

    Triplet carbenes (TCs) are of great interest due to their magnetic properties and reactivity, which descend from TCs' unique electronic state. However, the reactivity and stability of TCs are usually a trade-off, and it is difficult to achieve both at the same time. In this work, we were able to enhance the thermal stability of a TC species while maintaining its reactivity by confining them in the nanospace of a metal-organic framework (MOF). We synthesized a new MOF using a TC precursor; subsequently, TCs were generated by photostimulation. The TCs generated in the MOF nanospace were detectable up to 170 K, whereas their non-MOF-confined counterparts (bare ligand) could not be detected above 100 K. In addition, the reactivity of TC generated in MOF with O2 was drastically improved compared to that of bare ligand. Our approach is generally applicable to the stabilization of highly reactive species, whose reactivity needs to be preserved.

    DOI: 10.1021/jacs.1c02430

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  7. Trapping and Releasing of Oxygen in Liquid by Metal-Organic Framework with Light and Heat 招待有り 査読有り 国際誌

    Fujimura Masashi, Kusaka Shinpei, Masuda Ayaka, Hori Akihiro, Hijikata Yuh, Pirillo Jenny, Ma Yunsheng, Matsuda Ryotaro

    SMALL   17 巻 ( 22 ) 頁: e2004351 - 2004351   2021年6月

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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:Small  

    Nanoporous materials can adsorb small molecules into their nanospaces. However, the trapping of light gas molecules dissolved in solvents suffers from low concentration and poor adsorption affinity. Here, the reversible trapping and releasing of dissolved oxygen are shown through integrating photosensitization and chemical capturing abilities into a metal–organic framework (MOF), MOMF-1. 9,10-Di(4-pyridyl)anthracene (dpa) ligands in MOMF-1 generates singlet oxygen from triplet oxygen under photoirradiation without additional photosensitizers, and successively reacts with it to produce anthracene endoperoxide, forming MOMF-2, which is proved crystallographically. The reverse reaction also proceeds quantitatively by heating MOMF-2. Moreover, MOMF-1 exhibits excellent water resistance, and completely removes oxygen of ppm order concentrations in water. The new material shown in this report allows controlling of the amount of dissolved oxygen, which can be applicable in various fields relating to numerous oxidation phenomena.

    DOI: 10.1002/smll.202004351

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    その他リンク: https://onlinelibrary.wiley.com/doi/full-xml/10.1002/smll.202004351

  8. Modulation of Self-Assembly Enhances the Catalytic Activity of Iron Porphyrin for CO2 Reduction 査読有り

    Tasaki Masahiro, Okabe Yuki, Iwami Hikaru, Akatsuka Chiharu, Kosugi Kento, Negita Kohei, Kusaka Sinpei, Matsuda Ryotaro, Kondo Mio, Masaoka Shigeyuki

    SMALL   17 巻 ( 22 )   2021年6月

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    記述言語:英語   出版者・発行元:Small  

    Electrochemical reduction of CO2 in aqueous media is an important reaction to produce value-added carbon products in an environmentally and economically friendly manner. Various molecule-based catalytic systems for the reaction have been reported thus far. The key features of state-of-the-art catalytic systems in this field can be summarized as follows: 1) an iron-porphyrin-based scaffold as a catalytic center, 2) a dinuclear active center for the efficient activation of a CO2 molecule, and 3) a hydrophobic channel for the accumulation of CO2. This article reports a novel approach to construct a catalytic system for CO2 reduction with the aforementioned three key substructures. The self-assembly of a newly designed iron-porphyrin complex bearing bulky substituents with noncovalent interaction ability forms a highly ordered crystalline solid with adjacent catalytically active sites and hydrophobic pores. The obtained crystalline solid serves as an electrocatalyst for CO2 reduction in aqueous media. Note that a relevant iron-porphyrin complex without bulky substituents cannot form a porous structure with adjacent active sites, and the catalytic performance of the crystals of this relevant iron-porphyrin complex is substantially lower than that of the newly developed catalytic system. The present study provides a novel strategy for constructing porous crystalline solids for small-molecule conversions.

    DOI: 10.1002/smll.202006150

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  9. Enhanced CO2 Adsorption by Insertion Reaction in the Nanospace of a Porphyrin-based MOF 査読有り

    Morita Masashi, Kusaka Shinpei, Yonezu Akira, Ohara Yuki, Sakamoto Hirotoshi, Matsuda Ryotaro

    CHEMISTRY LETTERS   50 巻 ( 4 ) 頁: 640 - 643   2021年4月

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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:Chemistry Letters  

    Here we report enhanced CO2 molecular recognition ability by incorporating insertion reaction into a metal porphyrin complex in a metal-organic framework (MOF). PCN-222(Cu)-INA was synthesized by the reaction of PCN-222(Cu) [Zr6O8(H2O)8- (Cu-TCPP)2], where Cu-TCPP = Cu(II) tetrakis(4-carboxyphenyl) porphyrin, and isonicotinic acid (INA). PCN-222(Cu)-INA exhibited a 1.5 times larger CO2 adsorption amount than PCN- 222(Cu) at 298K and 1 bar. The mechanism involving insertion reaction of CO2 into CuN bonds enhanced the adsorption, which was revealed by in situ IR spectroscopy and theoretical calculations.

    DOI: 10.1246/cl.200785

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  10. An Open-shell, Luminescent, Two-Dimensional Coordination Polymer with a Honeycomb Lattice and Triangular Organic Radical 査読有り

    Kimura Shun, Uejima Motoyuki, Ota Wataru, Sato Tohru, Kusaka Shinpei, Matsuda Ryotaro, Nishihara Hiroshi, Kusamoto Tetsuro

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   143 巻 ( 11 ) 頁: 4329 - 4338   2021年3月

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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  

    The use of organic radicals as building blocks is an effective approach to the production of open-shell coordination polymers (CPs). Two-dimensional (2D) CPs with honeycomb spin-lattices have attracted attention because of the unique electronic structures and physical properties afforded by their structural topology. However, radical-based CPs with honeycomb spin-lattices tend to have low chemical stability or poor crystallinity, and thus novel systems with high crystallinity and persistence are in strong demand. In this study, a novel triangular organic radical possessing three pyridyl groups, tris(3,5-dichloro-4-pyridyl)methyl radical (trisPyM) was prepared. It exhibits luminescence, high photostability, and a coordination ability, allowing formation of defined and persistent 2D CPs. Optical measurements confirmed the luminescence of trisPyM both in solution and in the solid state, with emission wavelengths, λem, of 665 and 700 nm, respectively. trisPyM exhibits better chemical stability under photoirradiation than other luminescent radicals: the half-life of trisPyM in CH2Cl2 was 10 »000 times that of the tris(2,4,6-trichlorophenyl)methyl radical (TTM), a conventional luminescent radical. Complexation between trisPyM and ZnII(hfac)2 yielded a single crystal of a 2D CP trisZn, possessing a honeycomb lattice with graphene-like spin topology. The coordination structure of trisZn is stable under evacuation at 60 °C. Moreover, trisZn exhibits luminescence at 79 K, with λem = 695 nm, and is a rare example of a luminescent material among 2D radical-based CPs. Our results indicate that trisPyM may be a promising building block in the construction of a new class of 2D honeycomb CPs with novel properties, including luminescence.

    DOI: 10.1021/jacs.0c13310

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  11. Molecular motion in the nanospace of MOFs upon gas adsorption investigated by in situ Raman spectroscopy 査読有り 国際誌

    Kusaka Shinpei, Nakajima Yasuaki, Hori Akihiro, Yonezu Akira, Kikushima Kenta, Kosaka Wataru, Ma Yunsheng, Matsuda Ryotaro

    FARADAY DISCUSSIONS   225 巻 ( 0 ) 頁: 70 - 83   2021年2月

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    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)   出版者・発行元:Faraday Discussions  

    Molecular motions taking place in the nanospace of metal-organic frameworks (MOFs) are an interesting research subject, although not yet fully investigated. In this work, we utilized in situ Raman spectroscopy in the ultralow-frequency region to investigate the libration motion (including the rotational motion of phenylene rings) of MOFs, in particular [Cu2(bdc)2(dabco)] (Cu-JAST-1), where bdc = 1,4-benzenedicarboxylate and dabco = 1,4-diazabicyclo[2.2.2]octane. The libration mode of Cu-JAST-1 was found to be significantly suppressed by the adsorption of various guest molecules, such as CO2, Ar, and N2. In addition, an appreciable correlation between the libration mode and adsorption equilibrium time was identified, which provides useful novel tools in the design of MOFs acting as molecular adsorption and separation materials.

    DOI: 10.1039/d0fd00002g

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  12. Hysteresis in the gas sorption isotherms of metal-organic cages accompanied by subtle changes in molecular packing. 査読有り

    Craig GA, Larpent P, Urabe H, Legrand A, Bonneau M, Kusaka S, Furukawa S

    Chemical communications (Cambridge, England)   56 巻 ( 25 ) 頁: 3689 - 3692   2020年3月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)  

    DOI: 10.1039/d0cc00932f

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  13. Direct observation of dimethyl sulfide trapped by MOF proving efficient removal of sulfur impurities 査読有り

    Morita Masashi, Yonezu Akira, Kusaka Shinpei, Hori Akihiro, Ma Yunsheng, Matsuda Ryotaro

    RSC ADVANCES   10 巻 ( 8 ) 頁: 4710 - 4714   2020年1月

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    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:RSC Advances  

    Here, we report the adsorptive removal of trace amounts of dimethyl sulfide (DMS) using metal-organic frameworks (MOFs). Cu2+-based MOFs with open metal sites (OMSs), [Cu3(btc)2] (HKUST-1), where btc = 1,3,5-benzenetricarboxylate, and without OMSs, [Cu2(bdc)2(dabco)] (Cu-JAST-1), where bdc = 1,4-benzenedicarboxylate and dabco = 1,4-diazabicyclo[2.2.2]octane, were investigated for the removal of DMS to compare their performance with that of Ag-Y zeolite, which is currently widely used in industry. HKUST-1 exhibited a considerably higher adsorption capacity for DMS than the other adsorbents, which was confirmed by breakthrough measurements. The adsorption state of DMS with HKUST-1 was directly revealed by single-crystal X-ray diffraction (SXRD) analysis and in situ Raman spectroscopy. In addition, it was shown that DMS can be removed by HKUST-1 even under humid conditions.

    DOI: 10.1039/c9ra09702c

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  14. Molecular motion in the nanospace of MOFs upon gas adsorption investigated by in situ Raman spectroscopy 査読有り

    日下 心平

    Faraday Discussions   - 巻   2020年

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  15. Dynamic Topochemical Reaction Tuned by Guest Molecules in the Nanospace of a Metal-Organic Framework 査読有り

    Kusaka Shinpei, Kiyose Atsushi, Sato Hiroshi, Hijikata Yuh, Hori Akihiro, Ma Yunsheng, Matsuda Ryotaro

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   141 巻 ( 40 ) 頁: 15742 - 15746   2019年10月

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    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)   出版者・発行元:Journal of the American Chemical Society  

    Reaction in well-designed solids allows yielding products with high selectivity and unique compounds that cannot be obtained in solution. However, the precise tuning of the arrangement of reactants in solids for the versatile application of solid-phase reactions remains a challenging subject. Here, a [2 + 2] photocyclization reaction at different positions of the carbon-carbon bonds is described in which the spatial arrangement of 4-styrylpyridines (4-spy) is changed by guest molecules in a flexible metal-organic framework. The 4-spy molecules undergo photodimerization between two carbon-carbon double bonds in the guest-free framework, whereas a reaction between olefinic and aromatic carbon-carbon bonds or the absence of reaction takes place in the solvent-incorporated form. This reactivity, which can be termed as "dynamic topochemistry" contributes to enforce the applicability of solid-phase reactions in synthetic chemistry.

    DOI: 10.1021/jacs.9b07682

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  16. Reversible low-temperature redox activity and selective oxidation catalysis derived from the concerted activation of multiple metal species on Cr and Rh-incorporated ceria catalysts 査読有り 国際誌

    Ikemoto Satoru, Huang Xiubing, Muratsugu Satoshi, Nagase Shoko, Koitaya Takanori, Matsui Hirosuke, Yokota Gen-ichi, Sudoh Takatoshi, Hashimoto Ayako, Tan Yuanyuan, Yamamoto Susumu, Tang Jiayi, Matsuda Iwao, Yoshinobu Jun, Yokoyama Toshihiko, Kusaka Shinpei, Matsuda Ryotaro, Tada Mizuki

    PHYSICAL CHEMISTRY CHEMICAL PHYSICS   21 巻 ( 37 ) 頁: 20868 - 20877   2019年10月

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    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:Physical Chemistry Chemical Physics  

    The ceria-based catalyst incorporated with Cr and a trace amount of Rh (Cr0.19Rh0.06CeOz) was prepared and the reversible redox performances and oxidation catalysis of CO and alcohol derivatives with O2 at low temperatures (<373 K) were investigated. In situ X-ray absorption fine structure (XAFS), ambient-pressure X-ray photoelectron spectroscopy (AP-XPS), high angle annular dark-field scanning transmission electron microscopy (HAADF-STEM)-EDS/EELS and temperature-programmed reduction/oxidation (TPR/TPO) revealed the structures and redox mechanisms of three metals in Cr0.19Rh0.06CeOz: dispersed Rh3+δ species (<1 nm) and Cr6-γO3-x nanoparticles (∼1 nm) supported on CeO2 in Cr0.19Rh0.06CeOz were transformed to Rh nanoclusters, Cr(OH)3 species and CeO2-x with two Ce3+-oxide layers at the surface in a concerted activation manner of the three metal species with H2

    DOI: 10.1039/c9cp04625a

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  17. One-Step Synthesis of an Adaptive Nanographene MOF: Adsorbed Gas-Dependent Geometrical Diversity 査読有り

    Suginome Shun, Sato Hiroshi, Hori Akihiro, Mishima Akio, Harada Yuki, Kusaka Shinpei, Matsuda Ryotaro, Pirillo Jenny, Hijikata Yuh, Aida Takuzo

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   141 巻 ( 39 ) 頁: 15649 - 15655   2019年10月

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    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:Journal of the American Chemical Society  

    A layered metal-organic framework (MOF) comprising extra-large nanographene sheets, HBCMOF, was successfully synthesized using a dicarboxylic acid derivative of hexa-peri-hexabenzocoronene (HBCLH2), and its structure was characterized by single-crystal X-ray diffraction analysis. The crystal structure shows that 2D layers composed of a dinuclear Zn2+ complex unit and HBCL are located on top of each other through multiple weak interlayer bonds, affording HBCMOF, having three dimensionally connected nanopores with large nanographene surfaces. The HBC-based nanographene sheets are anchored to the MOF framework via two zinc carboxylate linkages and therefore have an axial rotational freedom. The sorption isotherms of gaseous molecules such as carbon dioxide and hydrocarbons (acetylene, propane, propylene, benzene, and cyclohexane) on HBCMOF all displayed a hysteretic profile with reversible structural changes, as observed by in situ powder X-ray diffraction studies.

    DOI: 10.1021/jacs.9b07732

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  18. Microwave-Assisted Hydrothermal Synthesis of [Al(OH)(1,4-NDC)] Membranes with Superior Separation Performances 査読有り 国際誌

    Liu Yi, Hori Akihiro, Kusaka Shinpei, Hosono Nobuhiko, Li Mingrun, Guo Ang, Du Dongying, Li Yanshuo, Yang Weishen, Ma Yunsheng, Matsuda Ryotaro

    CHEMISTRY-AN ASIAN JOURNAL   14 巻 ( 12 ) 頁: 2072 - 2076   2019年6月

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    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:Chemistry - An Asian Journal  

    In this study, we report a facile ligand-assisted in situ hydrothermal approach for preparation of compact [Al(OH)(1,4-NDC)] (1,4-NDC=1,4-naphthalenedicarboxylate) MOF membranes on porous γ-Al2O3 substrates, which also served as the Al3+ source of MOF membranes. Simultaneously, it was observed that the heating mode exerted significant influence on the final microstructure and separation performance of [Al(OH)(1,4-NDC)] membranes. Compared with the conventional hydrothermal method, the employment of microwave heating led to the formation of [Al(OH)(1,4-NDC)] membranes composed of closely packed nanorods with superior H2/CH4 selectivity.

    DOI: 10.1002/asia.201900152

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  19. Creation of MOFs with open metal sites by partial replacement of metal ions with different coordination numbers 査読有り 国際誌

    Harada Yuki, Hijikata Yuh, Kusaka Shinpei, Hori Akihiro, Ma Yunsheng, Matsuda Ryotaro

    DALTON TRANSACTIONS   48 巻 ( 8 ) 頁: 2545 - 2548   2019年2月

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    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:Dalton Transactions  

    Herein, we developed isostructural metal-organic frameworks (MOFs) [Cu 1-x Pd x (SiF 6 )(bpy) 2 ] (bpy: 4,4′-bipyridine) (SIFSIX-1-CuPd-3, -5 and -10) containing open metal sites using a partial metal-replacement approach. Starting from the SIFSIX-1-Cu-type MOF, some of the Cu 2+ ions having octahedral geometry were successfully replaced with Pd 2+ ions having square planar geometry in different ratios, while the framework structure was maintained. The results showed that gas adsorption properties of SIFSIX-1-Cu-type MOFs can be tuned via partial metal replacement.

    DOI: 10.1039/c8dt04218g

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  20. Highly responsive nature of porous coordination polymer surfaces imaged by in situ atomic force microscopy 査読有り 国際誌

    Hosono Nobuhiko, Terashima Aya, Kusaka Shinpei, Matsuda Ryotaro, Kitagawa Susumu

    NATURE CHEMISTRY   11 巻 ( 2 ) 頁: 109 - 116   2019年2月

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    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:Nature Chemistry  

    The ability of porous coordination polymers to undergo reversible structural transformations in response to the presence of guest molecules has been intensively investigated for applications such as molecular separation, storage, sensing and signalling processes. Here we report on the direct observation of the highly guest-responsive nature of the surface of a single-crystalline porous coordination polymer, which consists of paddlewheel zinc clusters and two types of ligand, by in situ liquid-phase atomic force microscopy. Observations were carried out in solution at constant temperature (28 °C) by high-speed atomic force microscopy with lattice resolution. A sharp and reversible response to the presence or absence of biphenyl guest molecules was observed, under conditions that can scarcely induce the transformation of the bulk crystal. Additionally, by modulating the surface coordination equilibrium, layer-by-layer delamination events were captured in real time at every ~13 s per frame.

    DOI: 10.1038/s41557-018-0170-0

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  21. Design and control of gas diffusion process in a nanoporous soft crystal 査読有り 国際誌

    Gu Cheng, Hosono Nobuhiko, Zheng Jia-Jia, Sato Yohei, Kusaka Shinpei, Sakaki Shigeyoshi, Kitagawa Susumu

    SCIENCE   363 巻 ( 6425 ) 頁: 387 - +   2019年1月

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    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:Science  

    Design of the gas-diffusion process in a porous material is challenging because a contracted pore aperture is a prerequisite, whereas the channel traffic of guest molecules is regulated by the flexible and dynamic motions of nanochannels. Here, we present the rational design of a diffusion-regulatory system in a porous coordination polymer (PCP) in which flip-flop molecular motions within the framework structure provide kinetic gate functions that enable efficient gas separation and storage. The PCP shows substantial temperature-responsive adsorption in which the adsorbate molecules are differentiated by each gate-admission temperature, facilitating kinetics-based gas separations of oxygen/argon and ethylene/ethane with high selectivities of ∼350 and ∼75, respectively. Additionally, we demonstrate the long-lasting physical encapsulation of ethylene at ambient conditions, owing to strongly impeded diffusion in distinctive nanochannels.

    DOI: 10.1126/science.aar6833

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  22. Insights into inorganic buffer layer-assisted in situ fabrication of MOF films with controlled microstructures 査読有り 国際誌

    Liu Yi, Matsuda Ryotaro, Kusaka Shinpei, Hori Akihiro, Ma Yunsheng, Kitagawa Susumu

    CRYSTENGCOMM   20 巻 ( 43 ) 頁: 6995 - 7000   2018年11月

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    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:CrystEngComm  

    In this study, it was demonstrated that the introduction of Co-Al/Mg-Al hydrotalcite-like compound buffer layers on porous α-Al2O3 substrates enabled effective manipulation of the microstructure of ZIF-7 films so that metal ions located in the inorganic buffer layers were not necessarily identical with those residing in the MOF crystals. Moreover, zinc sources were found to exert a significant influence on the final microstructure of the prepared ZIF-7 films. In addition to ZIF-7, well-intergrown ZIF-8 and HKUST-1 films could also be in situ grown on diverse HTlc buffer layer-modified α-Al2O3 substrates, which convincingly demonstrated the generality of this strategy for the facile preparation of qualified MOF films/membranes.

    DOI: 10.1039/c8ce01681j

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  23. Theoretical Insight into Gate-Opening Adsorption Mechanism and Sigmoidal Adsorption Isotherm into Porous Coordination Polymer 査読有り 国際誌

    Zheng Jia-Jia, Kusaka Shinpei, Matsuda Ryotaro, Kitagawa Susumu, Sakaki Shigeyoshi

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   140 巻 ( 42 ) 頁: 13958 - 13969   2018年10月

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    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:Journal of the American Chemical Society  

    The gate-opening adsorption mechanism and sigmoidal adsorption isotherm were theoretically investigated taking CO2 adsorption into porous coordination polymers, [Fe(ppt)2]n (PCP-N, Hppt = 3-(2-pyrazinyl)-5-(4-pyridyl)-1,2,4-triazole) and [Fe(dpt)2]n (PCP-C, Hdpt = 3-(2-pyridinyl)-5-(4-pyridyl)-1,2,4-triazole) as examples, where the hybrid method consisting of dispersion-corrected DFT for infinite PCP and a post-Hartree-Fock (SCS-MP2 and CCSD(T)) method for the cluster model was employed. PCP-N has site I (one-dimensional channel), site II (small aperture to site I), and site III (small pore) useful for CO2 adsorption. CO2 adsorption at site I occurs in a one by one manner with a Langmuir adsorption isotherm. CO2 adsorption at sites II and III occurs through a gate-opening adsorption mechanism, because the crystal deformation energy (EDEF) at these sites is induced largely by the first CO2 adsorption but induced much less by the subsequent CO2 adsorption. Interestingly, nine CO2 molecules are adsorbed simultaneously at these sites because a large EDEF cannot be overcome by adsorption of one CO2 molecule but can be by simultaneous adsorption of nine CO2 molecules. For such CO2 adsorption, the Langmuir-Freundlich sigmoidal adsorption isotherm was derived from the equilibrium equation for CO2 adsorption. A very complicated CO2 adsorption isotherm, experimentally observed, is reproduced by combination of the Langmuir and Langmuir-Freundlich adsorption isotherms. In PCP-C, CO2 adsorption occurs only at site I with the Langmuir adsorption isotherm. Sites II and III of PCP-C cannot be used for CO2 adsorption because a very large EDEF cannot be overcome by simultaneous adsorption of nine CO2 molecules. Factors necessary for gate-opening adsorption mechanism are discussed on the basis of differences between PCP-N and PCP-C.

    DOI: 10.1021/jacs.8b09358

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  24. Switchable gate-opening effect in metal-organic polyhedra assemblies through solution processing 査読有り 国際誌

    Craig Gavin A., Larpent Patrick, Kusaka Shinpei, Matsuda Ryotaro, Kitagawa Susumu, Furukawa Shuhei

    CHEMICAL SCIENCE   9 巻 ( 31 ) 頁: 6463 - 6469   2018年8月

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    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:Chemical Science  

    Gate-opening gas sorption is known for metal-organic frameworks, and is associated with structural flexibility and advantageous properties for sensing and gas uptake. Here, we show that gate-opening is also possible for metal-organic polyhedra (MOPs), and depends on the molecular organisation in the lattice. Thanks to the solubility of MOPs, several interchangeable solvatomorphs of a lantern-type MOP were synthesised via treatment with different solvents. One phase obtained through use of methanol induced a gate-opening effect in the lattice in response to carbon dioxide uptake. The sorption process was thoroughly investigated with in situ powder X-ray diffraction and simultaneous adsorption experiments. Meanwhile, solution processing of this flexible phase using THF led to a permanently porous phase without a gate-opening effect. Furthermore, we find that we can change the metallic composition of the MOP, and yet retain flexibility. By showing that gate-opening can be switched on and off depending on the solvent of crystallisation, these findings have implications for the solution-based processing of MOPs.

    DOI: 10.1039/c8sc02263a

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  25. Reversible Switching between Highly Porous and Nonporous Phases of an Interpenetrated Diamondoid Coordination Network That Exhibits Gate-Opening at Methane Storage Pressures. 査読有り 国際誌

    Yang QY, Lama P, Sen S, Lusi M, Chen KJ, Gao WY, Shivanna M, Pham T, Hosono N, Kusaka S, Perry JJ 4th, Ma S, Space B, Barbour LJ, Kitagawa S, Zaworotko MJ

    Angewandte Chemie (International ed. in English)   57 巻 ( 20 ) 頁: 5684 - 5689   2018年5月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)  

    DOI: 10.1002/anie.201800820

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  26. Generation of thiyl radicals in a zinc(II) porous coordination polymer by light-induced post-synthetic deprotection 査読有り 国際誌

    Kusaka Shinpei, Matsuda Ryotaro, Kitagawa Susumu

    CHEMICAL COMMUNICATIONS   54 巻 ( 38 ) 頁: 4782 - 4785   2018年5月

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    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:Chemical Communications  

    Kinetic stabilisation of unstable chemical species in nanospace is of potential importance in the field of materials and synthetic chemistry, and porous coordination polymers (PCPs) represent a facile platform to provide such reaction fields. Thiyl radicals are important reactive substances that often play a leading role in organic and bioorganic chemistry. However, their generation in nanospace has been barely investigated due to synthetic difficulties. Here, we report a facile methodology for the functionalisation of active thiyl substituents on PCP pore surfaces using a post-synthetic protection and deprotection technique. The thiyl radicals were generated inside a zinc(ii)-based PCP upon the deprotection of asymmetric disulfides, which were used as the protecting groups by ultraviolet light irradiation.

    DOI: 10.1039/c8cc01837e

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  27. Finely Controlled Stepwise Engineering of Pore Environments and Mechanistic Elucidation of Water-Stable, Flexible 2D Porous Coordination Polymers. 査読有り 国際誌

    Wang H, Cao H, Zheng JJ, Mathew S, Hosono N, Zhou B, Lyu H, Kusaka S, Jin W, Kitagawa S, Duan J

    Chemistry (Weinheim an der Bergstrasse, Germany)   24 巻 ( 24 ) 頁: 6412 - 6417   2018年4月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)  

    DOI: 10.1002/chem.201705858

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  28. Readily accessible shape-memory effect in a porous interpenetrated coordination network. 査読有り 国際誌

    Shivanna M, Yang QY, Bajpai A, Sen S, Hosono N, Kusaka S, Pham T, Forrest KA, Space B, Kitagawa S, Zaworotko MJ

    Science advances   4 巻 ( 4 ) 頁: eaaq1636   2018年4月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)  

    DOI: 10.1126/sciadv.aaq1636

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  29. Cooperative Bond Scission in a Soft Porous Crystal Enables Discriminatory Gate Opening for Ethylene over Ethane 査読有り 国際誌

    Sen Susan, Hosono Nobuhiko, Zheng Jia-Jia, Kusaka Shinpei, Matsuda Ryotaro, Sakaki Shigeyoshi, Kitagawa Susumu

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   139 巻 ( 50 ) 頁: 18313 - 18321   2017年12月

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    記述言語:日本語   掲載種別:研究論文(学術雑誌)  

    DOI: 10.1021/jacs.7b10110

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  30. Development of a Porous Coordination Polymer with a High Gas Capacity Using a Thiophene-Based Bent Tetracarboxylate Ligand 査読有り 国際誌

    Wang Fei, Kusaka Shinpei, Hijikata Yuh, Hosono Nobuhiko, Kitagawa Susumu

    ACS APPLIED MATERIALS & INTERFACES   9 巻 ( 39 ) 頁: 33455 - 33460   2017年10月

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    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:ACS Applied Materials and Interfaces  

    A new porous coordination polymer (PCP) based on a ligand with a unique bent angle bearing a thiophene-bridged bent carboxylate ligand and the Cu2+ ion was synthesized and structurally characterized. The structure has a pillared-layer framework based on a kagomé-like layer with aromatic partition groups. It exhibits a high CO2 uptake of 180 mL(STP)/g at 1 bar, and 400 mL(STP)/g at 30 bar at 273 K. The uptakes of C2H2 and C2H4 reach 164 and 160 mL(STP)/g at 298 K and 1 bar, with good selectivity of C2H2 and C2H4 over CH4, both of which are among the highest levels of reported PCPs.

    DOI: 10.1021/acsami.7b01568

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  31. Characteristic Features of CO2 and CO Adsorptions to Paddle-Wheel type Porous Coordination Polymer 査読有り 国際誌

    Zheng Jia-Jia, Kusaka Shinpei, Matsuda Ryotaro, Kitagawa Susumu, Sakaki Shigeyoshi

    JOURNAL OF PHYSICAL CHEMISTRY C   121 巻 ( 35 ) 頁: 19129 - 19139   2017年9月

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    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:Journal of Physical Chemistry C  

    Adsorptions of CO, N2, NO, and CO2 in a paddle-wheel-type porous coordination polymer (PCP) [Cu(aip)]n (aip = 5-azidoisophthalate) were investigated with ONIOM[MP4(SDQ):ωB97XD] method using a model system consisting of two [Cu2(O2CC6H4-R)4] units (R = H and Me) and one [Cu2(O2CC6H4-R)4] unit, namely, dimer and monomer models. The experimental CO adsorption position was reproduced well by the present calculation with the dimer model. For adsorptions of CO, N2, NO, and CO2 in the dimer model, the position of gas molecule deviates from the normal one that is found in the monomer model and becomes more distant from the surrounding phenyl group(s) of the neighbor [Cu(aip)] unit. For all of these gas molecules, the calculated binding energy (BE) at the deviating adsorption position is larger than that at the normal one against our expectation that the normal position is the best for the gas adsorption. The deviation of gas adsorption position arises from the interaction between the organic linker (O2CC6H4-R moiety) and gas molecule. For all cases, the exchange repulsion with the organic linker decreases to a larger extent than the attractive electrostatic and dispersion interactions decrease when going from the normal position to the deviating one. To enhance the binding energy of gas molecule, the introduction of electron-donating substituent on phenyl moiety is computationally recommended for this PCP.

    DOI: 10.1021/acs.jpcc.7b02707

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  32. Fine-tuning optimal porous coordination polymers using functional alkyl groups for CH4 purification 査読有り 国際誌

    Fujun Cheng, Qianqian Li, Jingui Duan, Nobuhiko Hosono, Shin-ichiro Noro, Rajamani Krishna, Hongliang Lyu, Shinpei Kusaka, Wanqin Jin, Susumu Kitagawa

    JOURNAL OF MATERIALS CHEMISTRY A   5 巻 ( 34 ) 頁: 17874 - 17880   2017年9月

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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:ROYAL SOC CHEMISTRY  

    Nano-porous coordination polymers (nano-PCPs), as a new class of crystalline material, have become a lucrative topic in coordination chemistry due to the facile tunability of their functional pore environments. However, elucidating the pathways for the rational design and preparation of nano-PCPs with various integrated properties for feasible gas separation remains a great challenge. Here, we demonstrate a new route to achieve nano-PCPs with an integrated pore system and physical properties using a reticular chemistry strategy. By optimizing the position and length of the shortest two alkyl groups in the channels, unprecedented phenomena of improved surface area, gas uptake, gas selectivity, thermal stability and chemical stability were observed in the PCPs, especially in NTU-14, the structure with a pendant ethyl group. Furthermore, the high performance of adsorption-and membrane-based separation makes NTU-14 a promising medium for CH4 purification from a mixture at room temperature.

    DOI: 10.1039/c7ta02760e

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  33. Density Gradation of Open Metal Sites in the Mesospace of Porous Coordination Polymers. 査読有り 国際誌

    Duan J, Higuchi M, Zheng J, Noro SI, Chang IY, Hyeon-Deuk K, Mathew S, Kusaka S, Sivaniah E, Matsuda R, Sakaki S, Kitagawa S

    Journal of the American Chemical Society   139 巻 ( 33 ) 頁: 11576 - 11583   2017年8月

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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.7b05702

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  34. Photofunctionality in Porphyrin-Hybridized Bis(dipyrrinato)zinc(II) Complex Micro- and Nanosheets.

    Sakamoto R, Yagi T, Hoshiko K, Kusaka S, Matsuoka R, Maeda H, Liu Z, Liu Q, Wong WY, Nishihara H

    Angewandte Chemie (International ed. in English)   56 巻 ( 13 ) 頁: 3526 - 3530   2017年3月

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    記述言語:英語  

    DOI: 10.1002/anie.201611785

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  35. Photofunctionality in Porphyrin-Hybridized Bis(dipyrrinato)zinc(II) Complex Micro- and Nanosheets 査読有り 国際誌

    Ryota Sakamoto, Toshiki Yagi, Ken Hoshiko, Shinpei Kusaka, Ryota Matsuoka, Hiroaki Maeda, Zheng Liu, Qian Liu, Wai-Yeung Wong, Hiroshi Nishihara

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   56 巻 ( 13 ) 頁: 3526 - 3530   2017年3月

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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:WILEY-V C H VERLAG GMBH  

    New bis(dipyrrinato) zinc(II) complex micro- and nanosheets containing zinc(II) porphyrin (N2) are synthesized. A liquid/liquid interface method between dipyrrin porphyrin ligand L2 and zinc acetate produces N2 with a large domain size. N2 can be layered quantitatively onto a flat substrate by a modified Langmuir-Schafer method. N2 deposited on a SnO2 electrode functions as a photoanode for a photoelectric conversion system. The photoresponse of N2 covers the whole visible wavelength range (400-650 nm), with a maximum quantum efficiency of more than twice that of a bis(dipyrrinato) zinc(II) complex nanosheet without porphyrin.

    DOI: 10.1002/ange.201611785

    Web of Science

▼全件表示

書籍等出版物 1

  1. フロンティアナノ金属錯体化学

    山下 正廣, 小西 克明 , 秋吉 亮平, 芥川 智行, 有賀 克彦, 井口 弘章, 伊藤 肇 , 内田 さやか, 加藤 恵一, 川脇 徳久, 河野 慎一郎, 日下 心平, 米田 忠弘, 澤田 知久, 陳 旻究, 七分 勇勝, 鈴木 康介, 高石 慎也, 高野 慎二郎, 田所 誠, 田中 健太郎, 佃 達哉, 中西 亮, 中村 貴義

    三共出版  2022年  ( ISBN:9784782708019

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    記述言語:日本語

    CiNii Books

MISC 32

  1. Dynamic Topochemical Reaction Tuned by Guest Molecules in the Nanospace of a Metal–Organic Framework 査読有り

    Kusaka Shinpei, Kiyose Atsushi, Sato Hiroshi, Hijikata Yuh, Hori Akihiro, Ma Yunsheng, Matsuda Ryotaro  

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY141 巻 ( 40 ) 頁: 15742-15746   2019年10月

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    記述言語:英語  

    DOI: 10.1021/jacs.9b07682

    Web of Science

  2. Reversible low-temperature redox activity and selective oxidation catalysis derived from the concerted activation of multiple metal species on Cr and Rh-incorporated ceria catalysts 査読有り

    Ikemoto Satoru, Huang Xiubing, Muratsugu Satoshi, Nagase Shoko, Koitaya Takanori, Matsui Hirosuke, Yokota Gen-ichi, Sudoh Takatoshi, Hashimoto Ayako, Tan Yuanyuan, Yamamoto Susumu, Tang Jiayi, Matsuda Iwao, Yoshinobu Jun, Yokoyama Toshihiko, Kusaka Shinpei, Matsuda Ryotaro, Tada Mizuki  

    PHYSICAL CHEMISTRY CHEMICAL PHYSICS21 巻 ( 37 ) 頁: 20868-20877   2019年10月

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    記述言語:英語  

    DOI: 10.1039/c9cp04625a

    Web of Science

  3. One-Step Synthesis of an Adaptive Nanographene MOF: Adsorbed Gas-Dependent Geometrical Diversity 査読有り

    Suginome Shun, Sato Hiroshi, Hori Akihiro, Mishima Akio, Harada Yuki, Kusaka Shinpei, Matsuda Ryotaro, Pirillo Jenny, Hijikata Yuh, Aida Takuzo  

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY141 巻 ( 39 ) 頁: 15649-15655   2019年10月

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    記述言語:英語  

    DOI: 10.1021/jacs.9b07732

    Web of Science

  4. Microwave-Assisted Hydrothermal Synthesis of [Al(OH)(1,4-NDC)] Membranes with Superior Separation Performances 査読有り

    Liu Yi, Hori Akihiro, Kusaka Shinpei, Hosono Nobuhiko, Li Mingrun, Guo Ang, Du Dongying, Li Yanshuo, Yang Weishen, Ma Yunsheng, Matsuda Ryotaro  

    CHEMISTRY-AN ASIAN JOURNAL14 巻 ( 12 ) 頁: 2072-2076   2019年6月

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    記述言語:英語  

    DOI: 10.1002/asia.201900152

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  5. Highly responsive nature of porous coordination polymer surfaces imaged by in situ atomic force microscopy 査読有り

    Hosono Nobuhiko, Terashima Aya, Kusaka Shinpei, Matsuda Ryotaro, Kitagawa Susumu  

    NATURE CHEMISTRY11 巻 ( 2 ) 頁: 109-116   2019年2月

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    記述言語:英語  

    DOI: 10.1038/s41557-018-0170-0

    Web of Science

  6. Design and control of gas diffusion process in a nanoporous soft crystal 査読有り

    Gu Cheng, Hosono Nobuhiko, Zheng Jia-Jia, Sato Yohei, Kusaka Shinpei, Sakaki Shigeyoshi, Kitagawa Susumu  

    SCIENCE363 巻 ( 6425 ) 頁: 387-+   2019年1月

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    記述言語:英語  

    DOI: 10.1126/science.aar6833

    Web of Science

  7. Theoretical Insight into Gate-Opening Adsorption Mechanism and Sigmoidal Adsorption Isotherm into Porous Coordination Polymer 査読有り

    Zheng Jia-Jia, Kusaka Shinpei, Matsuda Ryotaro, Kitagawa Susumu, Sakaki Shigeyoshi  

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY140 巻 ( 42 ) 頁: 13958-13969   2018年10月

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    記述言語:英語  

    DOI: 10.1021/jacs.8b09358

    Web of Science

  8. Switchable gate-opening effect in metal-organic polyhedra assemblies through solution processing 査読有り

    Craig Gavin A., Larpent Patrick, Kusaka Shinpei, Matsuda Ryotaro, Kitagawa Susumu, Furukawa Shuhei  

    CHEMICAL SCIENCE9 巻 ( 31 )   2018年8月

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    記述言語:英語  

    DOI: 10.1039/c8sc02263a

    Web of Science

  9. Reversible Switching between Highly Porous and Nonporous Phases of an Interpenetrated Diamondoid Coordination Network That Exhibits Gate-Opening at Methane Storage Pressures 査読有り

    Yang Qing-Yuan, Lama Prem, Sen Susan, Lusi Matteo, Chen Kai-Jie, Gao Wen-Yang, Shivanna Mohana, Pham Tony, Hosono Nobuhiko, Kusaka Shinpei, Perry John J., Ma Shengqian, Space Brian, Barbour Leonard J., Kitagawa Susumu, Zaworotko Michael J.  

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION57 巻 ( 20 ) 頁: 5684-5689   2018年5月

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    記述言語:英語  

    DOI: 10.1002/anie.201800820

    Web of Science

  10. Generation of thiyl radicals in a zinc(II) porous coordination polymer by light-induced post-synthetic deprotection 査読有り

    Kusaka Shinpei, Matsuda Ryotaro, Kitagawa Susumu  

    CHEMICAL COMMUNICATIONS54 巻 ( 38 ) 頁: 4782-4785   2018年5月

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    記述言語:英語  

    DOI: 10.1039/c8cc01837e

    Web of Science

  11. Finely Controlled Stepwise Engineering of Pore Environments and Mechanistic Elucidation of Water-Stable, Flexible 2D Porous Coordination Polymers 査読有り

    Wang Haijun, Cao Haifei, Zheng Jia-jia, Mathew Simon, Hosono Nobuhiko, Zhou Bihang, Lyu Hongliang, Kusaka Shinpei, Jin Wanqin, Kitagawa Susumu, Duan Jingui  

    CHEMISTRY-A EUROPEAN JOURNAL24 巻 ( 24 ) 頁: 6412-6417   2018年4月

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    記述言語:英語  

    DOI: 10.1002/chem.201705858

    Web of Science

  12. Readily accessible shape-memory effect in a porous interpenetrated coordination network 査読有り

    Shivanna Mohana, Yang Qing-Yuan, Bajpai Alankriti, Sen Susan, Hosono Nobuhiko, Kusaka Shinpei, Pham Tony, Forrest Katherine A., Space Brian, Kitagawa Susumu, Zaworotko Michael J.  

    SCIENCE ADVANCES4 巻 ( 4 )   2018年4月

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    記述言語:英語  

    DOI: 10.1126/sciadv.aaq1636

    Web of Science

  13. 配位不飽和サイトを有するナノポーラス金属錯体による希薄ガスの吸着除去

    米津章, 森田将司, 森田将司, 日下心平, 堀彰宏, 馬運声, 松田亮太郎  

    日本吸着学会研究発表会講演要旨集32nd 巻   2018年

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  14. Development of a Porous Coordination Polymer with a High Gas Capacity Using a Thiophene-Based Bent Tetracarboxylate Ligand 査読有り

    Wang Fei, Kusaka Shinpei, Hijikata Yuh, Hosono Nobuhiko, Kitagawa Susumu  

    ACS APPLIED MATERIALS & INTERFACES9 巻 ( 39 ) 頁: 33455-33460   2017年10月

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    記述言語:英語  

    DOI: 10.1021/acsami.7b01568

    Web of Science

  15. Fine-tuning optimal porous coordination polymers using functional alkyl groups for CH4 purification 査読有り

    Cheng Fujun, Li Qianqian, Duan Jingui, Hosono Nobuhiko, Noro Shin-ichiro, Krishna Rajamani, Lyu Hongliang, Kusaka Shinpei, Jin Wanqin, Kitagawa Susumu  

    JOURNAL OF MATERIALS CHEMISTRY A5 巻 ( 34 ) 頁: 17874-17880   2017年9月

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    記述言語:英語  

    DOI: 10.1039/c7ta02760e

    Web of Science

  16. これまでの多孔質材料にない特徴をもつPCP/MOFの化学 : 孔径,孔表面性質の調製,吸着材料・触媒としての応用 (特集 新しい『多孔質材料』の作製とその応用)

    日下 心平, 北川 進  

    Material stage17 巻 ( 1 ) 頁: 48 - 54   2017年4月

     詳細を見る

    記述言語:日本語   出版者・発行元:技術情報協会  

    CiNii Books

  17. Photofunctionality in Porphyrin-Hybridized Bis(dipyrrinato)zinc(II) Complex Micro- and Nanosheets 査読有り

    Sakamoto Ryota, Yagi Toshiki, Hoshiko Ken, Kusaka Shinpei, Matsuoka Ryota, Maeda Hiroaki, Liu Zheng, Liu Qian, Wong Wai-Yeung, Nishihara Hiroshi  

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION56 巻 ( 13 ) 頁: 3526-3530   2017年3月

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    記述言語:英語  

    DOI: 10.1002/anie.201611785

    Web of Science

  18. Dissymmetric Bis(dipyrrinato)zinc(II) Complexes: Rich Variety and Bright Red to Near-Infrared Luminescence with a Large Pseudo-Stokes Shift 査読有り

    Sakamoto Ryota, Iwashima Toshiki, Koegel Julius F., Kusaka Shinpei, Tsuchiya Mizuho, Kitagawa Yasutaka, Nishihara Hiroshi  

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY138 巻 ( 17 ) 頁: 5666-5677   2016年5月

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    記述言語:英語  

    DOI: 10.1021/jacs.6b02128

    Web of Science

  19. Heteroleptic [Bis(oxazoline)](dipyrrinato)zinc(II) Complexes: Bright and Circularly Polarized Luminescence from an Originally Achiral Dipyrrinato Ligand 査読有り

    Koegel Julius F., Kusaka Shinpei, Sakamoto Ryota, Iwashima Toshiki, Tsuchiya Mizuho, Toyoda Ryojun, Matsuoka Ryota, Tsukamoto Takamasa, Yuasa Junpei, Kitagawa Yasutaka, Kawai Tsuyoshi, Nishihara Hiroshi  

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION55 巻 ( 4 ) 頁: 1377-1381   2016年1月

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    記述言語:英語  

    DOI: 10.1002/anie.201509411

    Web of Science

  20. A Convenient Strategy for Designing a Soft Nanospace: An Atomic Exchange in a Ligand with Isostructural Frameworks 査読有り

    Ma Yunsheng, Matsuda Ryotaro, Sato Hiroshi, Hijikata Yuh, Li Liangchun, Kusaka Shinpei, Foo Mawlin, Xue Fengfeng, Akiyama George, Yuan Rongxin, Kitagawa Susumu  

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY137 巻 ( 50 ) 頁: 15825-15832   2015年12月

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    記述言語:英語  

    DOI: 10.1021/jacs.5b09666

    Web of Science

  21. A photofunctional bottom-up bis(dipyrrinato)zinc(II) complex nanosheet 査読有り

    Sakamoto Ryota, Hoshiko Ken, Liu Qian, Yagi Toshiki, Nagayama Tatsuhiro, Kusaka Shinpei, Tsuchiya Mizuho, Kitagawa Yasutaka, Wong Wai-Yeung, Nishihara Hiroshi  

    NATURE COMMUNICATIONS6 巻   2015年4月

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    記述言語:英語  

    DOI: 10.1038/ncomms7713

    Web of Science

  22. New aspects in bis and tris(dipyrrinato) metal complexes: bright luminescence, self-assembled nanoarchitectures, and materials applications 査読有り

    Sakamoto Ryota, Iwashima Toshiki, Tsuchiya Mizuho, Toyoda Ryojun, Matsuoka Ryota, Koegel Julius F., Kusaka Shinpei, Hoshiko Ken, Yagi Toshiki, Nagayama Tatsuhiro, Nishihara Hiroshi  

    JOURNAL OF MATERIALS CHEMISTRY A3 巻 ( 30 ) 頁: 15357-15371   2015年

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    記述言語:英語  

    DOI: 10.1039/c5ta02040a

    Web of Science

  23. Luminescent Heteroleptic Tris(dipyrrinato)indium(III) Complexes 査読有り

    Kusaka Shinpei, Sakamoto Ryota, Nishihara Hiroshi  

    INORGANIC CHEMISTRY53 巻 ( 7 ) 頁: 3275-3277   2014年4月

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    記述言語:英語  

    DOI: 10.1021/ic500326u

    Web of Science

  24. Asymmetric dinuclear bis(dipyrrinato)zinc(II) complexes: broad absorption and unidirectional quantitative exciton transmission 査読有り

    Tsuchiya Mizuho, Sakamoto Ryota, Kusaka Shinpei, Kitagawa Yasutaka, Okumura Mitsutaka, Nishihara Hiroshi  

    CHEMICAL COMMUNICATIONS50 巻 ( 44 ) 頁: 5881-5883   2014年

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    記述言語:英語  

    DOI: 10.1039/c4cc01573h

    Web of Science

  25. Triarylamine-Conjugated Bis(dipyrrinato)zinc(II) Complexes: Impact of Triarylamine on Photochemical Property and Multi-Redox Reaction 査読有り

    Tsuchiya Mizuho, Sakamoto Ryota, Kusaka Shinpei, Kakinuma Junko, Nishihara Hiroshi  

    ELECTROCHEMISTRY81 巻 ( 5 ) 頁: 337-339   2013年5月

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  26. Coordination Programming of Photofunctional Molecules 査読有り

    Sakamoto Ryota, Kusaka Shinpei, Hayashi Mikihiro, Nishikawa Michihiro, Nishihara Hiroshi  

    MOLECULES18 巻 ( 4 ) 頁: 4091-4119   2013年4月

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    記述言語:英語  

    DOI: 10.3390/molecules18044091

    Web of Science

  27. meso-Alkynyl BODIPYs: Structure, Photoproperties, -Extension, and Manipulation of Frontier Orbitals 査読有り

    Kusaka Shinpei, Sakamoto Ryota, Kitagawa Yasutaka, Okumura Mitsutaka, Nishihara Hiroshi  

    CHEMISTRY-AN ASIAN JOURNAL8 巻 ( 4 ) 頁: 723-727   2013年4月

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    記述言語:英語  

    DOI: 10.1002/asia.201201176

    Web of Science

  28. An Extremely Bright Heteroleptic Bis(dipyrrinato)zinc(II) Complex 査読有り

    Kusaka Shinpei, Sakamoto Ryota, Kitagawa Yasutaka, Okumura Mitsutaka, Nishihara Hiroshi  

    CHEMISTRY-AN ASIAN JOURNAL7 巻 ( 5 ) 頁: 907-910   2012年5月

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    記述言語:英語  

    DOI: 10.1002/asia.201200131

    Web of Science

  29. Fluorescent azadipyrrinato zinc(II) complex: hybridisation with a dipyrrinato ligand 査読有り

    Sakamoto Ryota, Kusaka Shinpei, Kitagawa Yasutaka, Kishida Masa-aki, Hayashi Mikihiro, Takara Yusuke, Tsuchiya Mizuho, Kakinuma Junko, Takeda Takuma, Hirata Keisuke, Ogino Tomoya, Kawahara Keisuke, Yagi Toshiki, Ikehira Shu, Nakamura Tomoya, Isomura Mayuko, Toyama Mikoto, Ichikawa Saki, Okumura Mitsutaka, Nishihara Hiroshi  

    DALTON TRANSACTIONS41 巻 ( 46 ) 頁: 14035-14037   2012年

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    記述言語:英語  

    DOI: 10.1039/c2dt32039h

    Web of Science

  30. Elucidation of the Stereochemistry of Thiirane Formation from a 1 lambda(4),2-Dithietane Bearing Two Chiral Carbon Centers 査読有り

    Kusaka Shinpei, Kano Naokazu, Kawashima Takayuki  

    HETEROATOM CHEMISTRY21 巻 ( 6 ) 頁: 412-417   2010年

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    記述言語:英語  

    DOI: 10.1002/hc.20630

    Web of Science

  31. Insertion of platinum and palladium into a sulfur(IV)-sulfur(II) bond of a sulfur-substituted sulfurane 査読有り

    Kano Naokazu, Kusaka Shinpei, Kawashima Takayuki  

    DALTON TRANSACTIONS39 巻 ( 2 ) 頁: 456-460   2010年

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    記述言語:英語  

    DOI: 10.1039/b911566h

    Web of Science

  32. Structure and Properties of a Sulfur(IV)-Sulfur(II)-Bond Compound: Reversible Conversion of a Sulfur-Substituted Organosulfurane into a Thiol 査読有り

    Kano Naokazu, Itoh Yusuke, Watanabe Yuki, Kusaka Shinpei, Kawashima Takayuki  

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION47 巻 ( 49 ) 頁: 9430-9433   2008年

     詳細を見る

    記述言語:英語  

    DOI: 10.1002/anie.200803945

    Web of Science

▼全件表示

科研費 6

  1. 反応速度の転換を可能にする柔軟性MOFナノ空間反応場の創製と機能開拓

    研究課題/研究課題番号:22K05141  2022年4月 - 2025年3月

    科学研究費助成事業  基盤研究(C)

    日下 心平

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    担当区分:研究代表者 

    配分額:4160000円 ( 直接経費:3200000円 、 間接経費:960000円 )

    ナノメートルサイズの空間の中での反応は、空間と反応基質の立体相互作用により特異な生成物を与えるなど、化学反応の可能性を大きく拡げられると期待されている。とりわけmetal-organic framework(MOF)は、その構造設計性により新たな反応場としての応用が期待されている。しかしながら、これまでのナノ空間反応場における反応開発は、生成物に着目した研究が大半で、反応速度に着目した研究はほとんど行われてこなかった。本研究では、柔軟性MOFナノ空間を用いた、微小な反応条件の変化に応答して反応速度が劇的に増加する「反応速度転換機能」を有する反応場の実現を目指す。

  2. ナノポーラス錯体によるダイナミック熱スイッチ材料の創製

    研究課題/研究課題番号:20K20564  2020年7月 - 2023年3月

    日本学術振興会  科学研究費助成事業  挑戦的研究(開拓)

    松田 亮太郎, 日下 心平

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    担当区分:研究分担者 

    本研究では、多孔性金属錯体(MOF)を用いて、ナノ空間物質へのガス吸脱着現象を利用した全く新しい熱制御材料の開発に挑戦する。MOFの「吸着・脱着機能」と「熱スイッチ機能」を統合することで、まったく新しい「ダイナミック熱スイッチ機能」を有する物質を創製する。環境の圧力や温度を変化させることで自在に熱流量や伝熱方向の制御が可能な新物質により、「吸着化学」と「熱科学」を融合した新しい学問領域を開拓する。
    熱を特定の方向に流すことが可能な「熱スイッチ材料」は、熱制御において中核的な役割を果たすものである。しかし、熱伝導を能動的かつ任意に制御可能な材料はほとんど研究がない。本研究では、ナノ空間物質へのガス吸脱着現象を利用した全く新しい熱制御材料の開発に挑戦する。本研究では多孔性物質の一種である多孔性金属錯体(MOF)を熱制御材料として用いる。これまでのMOF研究のほとんどは、ガス吸着やガス分離に主眼がおかれている。その一方で、細孔への分子吸脱着によりMOF細孔内の密度が大きく変化するので、「吸着状態のMOF結晶」と、「脱着状態のMOF結晶」の熱物性は大きく異なっていると予想されるが、そのことに着目した研究はほとんど見当たらない。本研究課題ではMOFの「吸着・脱着機能」と「熱スイッチ機能」を統合することで、まったく新しい「ダイナミック熱スイッチ機能」を有する物質を創製し、外の環境温度や圧力の操作で、物質を変えることなく、熱良導体から熱不良導体へとスイッチ可能な全く新しい熱制御システムの開拓を行うことを目的としている。これをふまえ、当該年度は下記の実験を実施した。
    (1).熱スイッチ機能を志向した、MOF結晶の合成。
    (2).水および二酸化炭素を用いて、水および二酸化炭素を用いた、熱伝導度測定に影響すると想定される吸着熱の直接観察。
    (3).熱伝導度測定装置の立ち上げ
    その結果、(1)に関しては6種類の剛直および柔軟な構造特性を有するMOFの合成に成功した。また、(2)に関しては吸着熱の観察システムの高度化を達成し、精密に吸着熱を測定することが可能にした。これを用いて、吸着熱測定を(1)で合成したMOFに対して実施し、それぞれの吸着熱の挙動を明らかにした。
    本研究課題を実現するために必須の下記A、B、Cの課題を設定し、計画的に取り組んでいる。
    課題A:MOFへの気体分子の吸脱着を基盤とした熱スイッチ材料の開発
    課題B:高速熱伝導材料を志向した高速分子拡散が可能なMOFの開発
    課題C:超高速熱拡散率を有するMOFの構築
    当該年度は課題Aを中心に研究を実施した。その結果予定より多くのMOF結晶の合成に成功し、また吸着の際の熱の直接観察にも成功した。本成果は現在論文としてまとめており、本年度中に投稿できる段階にある。また、当初課題Bは2年度以降に実施することを考えていたが、計画を前倒しして、吸着熱測定とともに吸着速度測定を実施することができ、従来の物質よりも吸着速度が高速であるものを見出した。
    上述したように、本研究課題を実現するために必須の下記A、B、Cの課題を設定し、計画的に取り組んでいる。
    課題A:MOFへの気体分子の吸脱着を基盤とした熱スイッチ材料の開発
    課題B:高速熱伝導材料を志向した高速分子拡散が可能なMOFの開発
    課題C:超高速熱拡散率を有するMOFの構築
    今年度は課題Bを中心に推進し、昨年度に合成を実施したMOFの熱伝導に関する基本的知見を得るとともに、吸着下での熱物性と分子拡散特性についての検討を行っていく。

  3. 適応性空間の化学 / Chemistry of Adaptable Space

    研究課題/研究課題番号:18H05262  2018年6月 - 2023年3月

    日本学術振興会  科学研究費助成事業  基盤研究(S)

    北川 進, 細野 暢彦, 大竹 研一, Zheng Jiajia, 土方 優, 日下 心平

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    担当区分:研究分担者 

    生物は様々な環境の変化に対し自らを適応させる。この自発的適応機能を化学の視点で捉えれば、例えば分子シグナルの授受や細胞膜内外の物質移動といったナノレベルの多重な機能を協同的に連携作用させて応答を行う「流れ」の確立にある。その機能実現にはダイナミックなナノ空間が重要な役割をしている。本課題では、生物の受容、検出、移送、変換などの基本操作を材料化学的な空間素子として設計し、それらを連携させた空間にエンコードして多様な環境変化に応答する新しい概念の多孔性物質を創出することを目指す。そのためには、1.動的PCPの結晶界面の観察手法を開発し、PCPのゲストに対する振る舞いについての理解を深める、2.空間ドメインの接合および融合技術の開発、3.異なる細孔径を非対称的に有するアシンメトリックなPCP単結晶の合成法の確立が特に重要な課
    題となる。本研究では次の3つにテーマを分けて集中的に取り組んでいる。1. 動的ナノ空間および界面による情報の受容と変換、2. 空間ドメインの有機的複合・融合化、3. 計算化学による連携機能の統括的理解と設計
    本年度は、それぞれの課題について顕著な成果が複数得られた。特に動的PCPによるゲスト分子の高効率な変換(Nat. Commun. 2019)、高効率ケムレジスタセンシング(Angew.Chem.Int.Ed. 2020)といった本課題を遂行するにあたり柱となる動的空間の機能開拓に関する研究内容が大きく進展した。PCPドメインの融合技術については、高分子との複合化による物質分離膜や、PCP結晶上に別の結晶を成長させた階層構造材料や階層構造ナノシステムの構築を進めている。
    計算化学的な課題においては、PCPの局所的な構造変化に注目し、そのローカルな構造変
    化が細孔空間内の静電場に及ぼす影響に注目し理論計算を進めた。
    本年度は申請書で掲げた複数の技術的課題について順調に進展がみられている。特に動的PCPによるゲスト分子の高効率な変換(Nat. Commun. 2019)、高効率ケムレジスタセンシング(Angew.Chem.Int.Ed. 2020)といった本課題を遂行するにあたり柱となる動的空間の機能開拓に関する研究内容が大きく進展している。PCPドメインの融合技術については、高分子との複合化による物質分離膜や、PCP結晶上に別の結晶を成長させた階層構造材料や階層構造ナノシステムの構築を進めている。
    計算化学的な課題においては、PCPの局所的な構造変化に注目し、そのローカルな構造変
    化が細孔空間内の静電場に及ぼす影響に注目し理論計算を進めた。
    本年度に得られた技術的ブレークスルーを基礎に研究をさらに展開する。特に、物質の変換および計算化学によるメカニズム考察には力を入れる。PCP細孔内の物質移動、反応および変換に関して、X線構造解析と計算化学を駆使して本質的かつ基礎的な知見を得る予定である。また、申請書に掲げた溶融PCPの開発、および複数のPCPドメインからなる階層構造ナノシステムの構築と、それを利用した空間接合技術についての研究を加速する。

  4. 多孔錯体チャネルを有するガス分離変換膜の開発

    研究課題/研究課題番号:18H02072  2018年4月 - 2021年3月

    日本学術振興会  科学研究費助成事業  基盤研究(B)

    細野 暢彦, 山田 秀尚, 梶原 隆史, 日下 心平

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    担当区分:研究分担者 

    我々の社会生活を支えるガス分離膜の高機能化を目指し、多孔性金属錯体(MOF)および中空金属錯体(MOC)を分子を選別し変換するナノ空間チャネルとしてとらえ、それらを高分子材料と融合させることで全く新しいガス分離膜材料の合成を行った。結果、MOCと高分子を有機的に結合させ膜化する技術の開発に成功したほか、超高選択的ガス分離機能を発現するMOF、二酸化炭素を工業的に有用な有機物質へと変換するMOF触媒の合成も達成し、目指す分離変換膜の合成を実現させるための基盤技術群の開発に成功した。
    本研究は、ガス分離膜設計に対してこれまでとは大きく異なるコンセプトを与えるものであり、今後の高機能性膜開発へ向けた重要な足がかりとなる成果を生んだ。本研究においてガス分離素子、物質変換素子として開発した新しいMOF材料は、類を見ない超高選択的ガス分離機能や分子変換機能を示した。これらの成果は、我々の生活を支えるガス分離材料の性能向上に資するだけでなく、次世代の物質分離技術、触媒技術開発のエッセンスとなる重要なものである。

  5. ゲート型ナノシート積層ガス分離膜の開発

    研究課題/研究課題番号:18K14043  2018年4月 - 2020年3月

    日本学術振興会  科学研究費助成事業 若手研究  若手研究

    日下 心平

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    担当区分:研究代表者 

    配分額:4160000円 ( 直接経費:3200000円 、 間接経費:960000円 )

    分子サイズの穴を持つ結晶である多孔性配位高分子(PCP)を1ミクロン以下の薄さで隙間なく膜状にしたものは、分子が膜を通過する速度の差を利用した物質の分離精製に利用できることから盛んに研究されている。これまでのPCPを用いた膜はPCPの向きがランダムなものであったが、本研究ではPCPを剥離してナノシートとし、それを再積層させることで、PCPおよび穴の向きが一方方向に揃った膜を作成できた。さらに、環境によって穴の大きさを変えるPCPが、この成膜方法でその性質を保っていることを明らかにした。
    これまでガスの分離膜は一定の大きさの穴を持っており、分子のサイズの違いによってこの穴を通れるか否か、が分離の鍵となっていた。これに対して本研究では、環境により大きさを変化させられる穴を持つ新しい材料を用いた膜の作成を行った。この材料が、膜化しても元の性質を失わないことを示したことで、既存の膜では分離が困難であった物質の分離を可能にするための礎になると期待される。

  6. 空間融合による機能化学の新機軸

    研究課題/研究課題番号:18H03928  2018年4月 - 2019年3月

    日本学術振興会  科学研究費助成事業 基盤研究(A)  基盤研究(A)

    北川 進

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    担当区分:研究分担者 

    生物は細胞や膜といったように、機能をコンパートメントに分け、それらを有機的に連携させることで複雑な機能を生み出している。これは、例えば分子シグナルの授受や細胞膜内外の物質移動といったナノレベルの多重な機能を協同的に連携作用させて応答を行う「流れ(flow)」の確立にある。その実現には「ナノ空間の化学」が重要な役割をしている。
    本課題では、生物の受容、検出、移送、変換などの基本操作を材料化学的な空間素子として設計し、それらを連携させた空間を有機的に結合・融合させる「空間融合法」の開発を目指す。具体的には、機能開拓の舞台として動的なナノ空間機能を有する多孔性配位高分子(PCP)を主として用いる。異なる機能を有するPCPを「融合(fusion)」させる界面の化学を深化させ、例えば外部刺激・環境変化といったシグナルを増幅・伝搬するflowの創出に繋がる基盤技術の確立を目的とする。
    本年度は「空間融合」の学理の土台構築のために不可欠なPCP結晶の界面について理解を深めるため、PCP結晶表面の直接観察手法について検討した。PCPの結晶表面・界面は、その動的変形を最初に映し出すため、極めて重要な研究対象である。また、PCP結晶を融合・接合する上で、界面の理解は最も重要である。結果、原子間力顕微鏡を用い、PCP結晶表面を安定的に長時間観察するための条件の一部を決定することができた。基盤研究(S)の採択により、本課題は2018年6月11日付で廃止となった。
    平成30年度が最終年度であるため、記入しない。
    平成30年度が最終年度であるため、記入しない。

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担当経験のある科目 (本学) 2

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