黒子　弘道KUROSU Hiromichiクロス　ヒロミチ

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プロフィール情報

• 姓

  黒子, クロス

• 名

  弘道, ヒロミチ

学位

• 工学修士, 東京工業大学
• 工学博士, 東京工業大学

研究分野

• ライフサイエンス, 構造生物化学
• ナノテク・材料, 高分子材料
• 人文・社会, 家政学、生活科学

経歴

• 2012年04月, 奈良女子大学研究院生活環境科学系衣環境学領域領域・教授
• 2009年04月, 2012年03月, 奈良女子大学大学院人間文化研究科共生自然科学専攻・教授
• 2007年04月, 2009年03月, 奈良女子大学大学院人間文化研究科共生自然科学専攻・准教授
• 2007年04月, 2008年03月, 京都大学化学研究所客員准教授
• 2003年04月, 2007年03月, 奈良女子大学大学院人間文化研究科基盤生活科学講座・助教授
• 1999年04月, 2003年03月, 奈良女子大学大学院人間文化研究科人間環境基礎講座・助教授
• 1997年04月, 1999年03月, 奈良女子大学生活環境学部・助教授
• 1989年10月, 1997年03月, 東京工業大学工学部・助手
• 1991年10月, 1992年03月, 英国Surrey大学化学科・博士研究員

学歴

• 1987年, 東京工業大学, 理工学研究科, 高分子工学
• 1985年, 東京工業大学, 工学部, 高分子工学科

担当経験のある科目（授業）

• 生活工学マテリアルワーク, 奈良女子大学
• 生活工学特別研究（修士）, 奈良女子大学
• 繊維素材分子論演習, 奈良女子大学
• 繊維構造論演習, 奈良女子大学
• 生活工学材料解析論, 奈良女子大学
• 生活工学概論Ａ, 奈良女子大学
• 生活環境学原論, 奈良女子大学
• 繊維素材分子論, 奈良女子大学
• 繊維構造論, 奈良女子大学
• アパレル科学特論, 奈良女子大学
• 生活と科学, 奈良女子大学
• アパレル素材分子論演習, 奈良女子大学
• 繊維材料構造論演習, 奈良女子大学
• 繊維材料構造論, 奈良女子大学
• 繊維材料化学, 奈良女子大学
• 衣環境学実験Ⅰ（物理）, 奈良女子大学
• 高分子材料学, 奈良女子大学
• 衣環境学概論, 奈良女子大学
• アパレル素材分子論, 奈良女子大学
• 繊維状材料性能論, 奈良女子大学

所属学協会

• 日本核磁気共鳴学会
• 日本化学会
• 繊維学会
• 日本家政学会
• 高分子学会

Ⅱ．研究活動実績

論文

• 査読あり, 英語, Materials, Platinum Metallization of Polyethylene Terephthalate by Supercritical Carbon Dioxide Catalyzation and the Tensile Fracture Strength, 2023年, 16, 2377, https://doi.org/10.3390/ma16062377
• 査読あり, 英語, The Journal of Supercritical Fluids, Solid-State 13C NMR Spectroscopic Study of Supercritical CO2 Catalyzation Treated Polyethylene Terephthalate Textiles for Platinum Metallization, 2023年, 197, 105896, https://doi.org/10.1016/j.supflu.2023.105896
• 査読あり, 英語, Biotechnology Journal, Immobilization of Arg-Gly-Asp peptides on silk fibroin via Gly-Ala-Gly-Ala-Gly-Ser sequences, 2023年年2月, 18, 2200139, https://doi.org/10.1002/biot.202200139
• 査読あり, 英語, Micro and Nano Engineering, Supercritical Carbon Dioxide-Assisted Platinum Metallization of Polyethylene Terephthalate Textile toward Wearable Device, 2022年, 15, 100132, https://doi.org/10.1016/j.mne.2022.100132
• 査読あり, 英語, Macromolecules, Roles of Conformational Flexibility in the Crystallization of Stereo-Irregular Polymer, 2021年, 54, 5705, 5718, https://pubs.acs.org/doi/10.1021/acs.macromol.1c00888
• 英語, PeerJ Materials Science, PeerJ Journals, The influence of thermal treatments on the secondary structure of silk fibroin scaffolds and their interaction with fibroblasts, 2020年, 2:e8, 1, 18, https://doi.org/10.7717/peerj-matsci.8
• 査読あり, 英語, Microelectronic Engineering, Metallization of PET textile utilizing supercritical CO2 catalyzation, Kenichi Tokuoka; Chun Yi Chen; Tso Fu Mark Chang; Wan Ting Chiu; Hiromichi Kurosu; Masato Sone, © 2020 Elsevier B.V. Metallization of polyethylene terephthalate (PET) textiles was realized by conducting the catalyzation step in supercritical CO2 and using an organometallic compound, palladium bis-hexafluoracetylacetonate (Pd(hfa)2, as source of the palladium catalyst for the later Ni-P deposition step. Electrical resistance of the Ni-P/PET was evaluated before and after adhesion and high temperature incubation tests to reveal durability of the Ni-P/PET. Electrical resistances of the Ni-P/PET prepared at 343 K did not vary much after two cycles of the tape adhesion test when the deposition time was longer than 1.0 h. The Ni-P/PET metallized at 343 K for 2.0 h retained a low electrical resistance at 0.038 Ω after the high temperature incubation test at 414 K. The supercritical CO2 catalyzation was confirmed to be an effective method to metallize PET textile., 2020年02月15日, 223, 研究論文（学術雑誌）, 10.1016/j.mee.2020.111233

  DOI URLScopus URLScopus Citedby URL
• 査読あり, 英語, Electrochimica Acta, Ni–P and TiO2 codeposition on silk textile via supercritical CO2 promoted electroless plating for flexible and wearable photocatalytic devices, Wan Ting Chiu; Chun Yi Chen; Tso Fu Mark Chang; Tomoko Hashimoto; Hiromichi Kurosu; Masato Sone, © 2018 Elsevier Ltd This study reported integration of Ni–P/TiO2 incorporated structure on silk textiles to produce a flexible, highly reliable, and photocatalytic composite material toward applications in functional wearable devices. Supercritical carbon dioxide (Sc–CO2) promoted electroless plating was utilized to codeposit photocatalytic TiO2 and electrically conductive Ni–P metallization layer on silk textile. Silk was chosen as the substrate for its flexibility and stretchability. Ni–P was utilized due to its high corrosion resistance, electrical conductivity, and high wear resistance. TiO2 was selected for its photocatalytic activity and acting as a reinforcement filler to fulfill requirements for applications in wearable devices. Surface morphology, composition, crystal structure, electrical resistance, corrosion resistance, adhesive test, and photocatalytic activity assessments were conducted to evaluate the practicability for wearable photocatalytic devices. With the assistance of sc–CO2, palladium (II) acetylacetonate catalyst was successfully embedded into the silk substrate at around 330 nm in depth. The coatings on the silk were confirmed to be amorphous Ni–P phase and TiO2 anatase phase. Uniform Ni–P/TiO2 composite layer with strong adherence was successfully co–deposited on the silk textile. Ni–P/TiO2 composite layer deposited with 30 g/L of TiO2 (critical concentration) in the electrolyte showed higher corrosion resistance while comparing to those of TiO2–free specimen. The Ni–P/TiO2 composite layer deposited with the critical concentration of TiO2 in the electrolyte performed the highest photocatalytic activity., 2019年01月20日, 294, 68, 75, 研究論文（学術雑誌）, 10.1016/j.electacta.2018.10.076

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• 査読あり, 英語, Surface and Coatings Technology, Platinum coating on silk by a supercritical CO2 promoted metallization technique for applications of wearable devices, Wan Ting Chiu; Chun Yi Chen; Tso Fu Mark Chang; Yuma Tahara; Tomoko Hashimoto; Hiromichi Kurosu; Masato Sone, © 2018 Elsevier B.V. Highly reliable Pt coating on silk textile was practiced by supercritical carbon dioxide (sc-CO2) promoted electroless plating in this study. Electroless plating is a facile method to integrate polymeric and metallic materials, and sc-CO2 was introduced to the process to enhance the electroless plating characteristics. Firstly, the palladium organometallic complex was inlaid into the silk substrate without damaging the silk structure in the catalyzation step. Secondly, a smooth and compact Pt layer was realized in the metallization step. Mechanisms involved in the sc-CO2-assisted metallization step were focused and discussed in this study. The lowest electrical resistance was found at 50 mΩ in the sample metallized with the optimized conditions. The adhesive test showed robustness of the composite material. Corrosion resistance results revealed the applicability of this silk-Pt composite materials prepared by the sc-CO2-assisted electroless plating in wearable device technology., 2018年09月25日, 350, 1028, 1035, 研究論文（学術雑誌）, 10.1016/j.surfcoat.2018.02.070

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• 査読あり, 英語, ELECTROCHIMICA ACTA, Fabrication and Photocatalytic Performance of Au/ZnO Layered Structure on Silk Textile for Flexible Device Applications, Wan-Ting Chiu; Chun-Yi Chen; Tso-Fu Mark Chang; Yuma Tahara; Tomoko Hashimoto; Hiromichi Kurosu; Masato Sone, This study integrated ZnO/Au layered structure on silk textiles to realize a flexible photocatalytic composite material for wearable devices. Supercritical carbon dioxide promoted electroless plating and cathodic deposition were used to metallize and deposit photocatalytic metal oxides on silk textiles. Silk was used as the substrate for its flexibility and stretchability. Au was selected due to its high biocompatibility, electrical conductivity, and ductility. ZnO was chosen for its photocatalytic activity and biocompatibility to fulfill the application. Surface morphology, composition, crystal structure, electrical resistance and photocatalytic activity assessments were evaluated. With the assistance of supercritical carbon dioxide, smooth, strong adherence and uniform coverage of Au layer was successfully electroless plated on the silk. ZnO was homogeneously deposited on the Au metal layer. The coatings on the silk have been confirmed to be metallic Au phase and ZnO wurtzite phase. The ZnO modified specimen with 0.2 wt. % H2O2 in the electrolyte showed the highest crystallinity and performed 11.5 times enhancement in the photocurrent density when comparing to the H2O2-free one. (C) 2017 Elsevier Ltd. All rights reserved., 2017年11月, 253, 39, 46, 研究論文（学術雑誌）, 10.1016/j.electacta.2017.09.041

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• 査読あり, 英語, Ind. Eng. Chem. Res., Fundamental Property Assessments of Biocompatible Silk–Pt Composite Prepared by Supercritical Carbon Dioxide Promoted Electroless Plating, 黒子 弘道, This study reports preparation and characterization of biocompatible, conductive, and flexible silk-Pt composite materials for applications in wearable and medical devices. The distinct Pt and silk materials were integrated via supercritical carbon dioxide (sc-CO2) promoted electroless plating. Sc-CO2 was introduced into the catalyzation step, which is a critical step in electroless plating, to overcome the common difficulty of inlaying the catalyst into the textile substrate. High surface coverage and thick Pt layer were constructed as the metallization time extended. Metal ions released in a simulated body fluid in an immersion test were negligible when compared to the daily metal input and output of the human body. The composites showed high corrosion resistances in both 3.5 wt % NaCl and simulated body fluid solutions. The electrical conductivity and corrosion resistance persisted after the adhesion tests. The assessments revealed the applicability of this silk-Pt material to wearable and medical devices., 2017年08月, 56, 31, 8864, 8871, 研究論文（学術雑誌）, 10.1021/acs.iecr.7b01749

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• 査読あり, 英語, MICROELECTRONIC ENGINEERING, Silk-Pt composite integration by supercritical carbon dioxide assisted electroless plating for medical devices application, Wan-Ting Chiu; Yuma Tahara; Chun-Yi Chen; Tso-Fu Mark Chang; Tomoko Hashimoto; Hiromichi Kurosu; Masato Sone, This study successfully integrated flexible silk textiles and highly conductive platinum together by a supercritical CO2-assisted electroless plating process to achieve the materials for wearable medical devices. Pt and silk textiles were chosen for the composite material due to the request of high biocompatibility in the applications. Supercritical CO2 was introduced to the catalyzation step in the electroless plating process to promote the catalyst deposition. Surface morphology, composition, crystal structure, electrical resistance and biocompatibility assessments were evaluated. Coverage of the Pt layer increased as a function of the plating time. The thickness reached 0.91 pm when 200 min of the plating time was used. The lowest resistance at 86 ma was obtained when the plating time was extended to 160 min. The Pt ion releasing rate in the r-type simulated body fluid was negligible when comparing with the daily input and output of Pt in human body. (C) 2016 Elsevier B.V. All rights reserved., 2017年05月, 175, 34, 37, 研究論文（学術雑誌）, 10.1016/j.mee.2016.12.024

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• 査読あり, 英語, JOURNAL OF THE ELECTROCHEMICAL SOCIETY, A Supercritical CO2 Promoted Electroless Ni-P Plating on Silk and Their Fundamental Characteristics Investigations, Wan-Ting Chiu; Yuma Tahara; Chun-Yi Chen; Tso-Fu Mark Chang; Tomoko Hashimoto; Hiromichi Kurosu; Masato Sone, This study demonstrated a promising method to integrate flexible silk textiles and conductive Ni-P metal coatings for the increasing interest in wearable devices. Electroless plating with supercritical carbon dioxide (sc-CO2) was utilized to combine the two distinct materials together conformally. Ni-P was chosen for its electrical conductivity and high corrosion resistance while silk was chosen as the substrate for its flexibility. Sc-CO2 was used as a promoter in the catalyzation to enhance the compatibility between the Ni-P with the silk. This technique allows simplification of the electroless plating by excluding the pretreatments while the substrate remains undamaged after the catalyzation step. In addition, the sc-CO2 leads to an environmental friendly process by cutting down the usage of corrosive chemicals in the catalyzation step. This study therefore demonstrates a series of palladium (II) acetylacetonate catalyzation followed by Ni-P deposition on the silk. The lowest electrical resistance at 1.02 Omega was achieved at 4 min of the Ni-P plating time. Corrosion resistance of the Ni-P/silk in a solution simulating the human sweat was evaluated. Reliability of the Ni-P/silk composite material was revealed by comparing the electrical resistances and corrosion resistances before and after an adhesive test. (C) 2017 The Electrochemical Society. All rights reserved., 2017年, 164, 7, D406, D411, 研究論文（学術雑誌）, 10.1149/2.0551707jes

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• 査読あり, 英語, SURFACE & COATINGS TECHNOLOGY, Application of supercritical carbon dioxide in catalyzation and Ni-P electroless plating of nylon 6,6 textile, Mitsuo Sano; Yuma Tahara; Chun-Yi Chen; Tso-Fu Mark Chang; Tomoko Hashimoto; Hiromichi Kurosu; Tatsuo Sato; Masato Sone, In this study, an electroless deposition method including catalyzation in supercritical carbon dioxide (sc-CO2) and plating in sc-CO2 emulsified electrolyte was applied in metallization of Nylon 6,6 textile. In order to demonstrate the effects of the sc-CO2, the catalyzation was conducted either by the conventional method or the supercritical CO2 catalyzation (SCC) method with bis (2,4-pentandionato)-palladium. After the catalyzation process, either the conventional electroless plating or the electroless plating with supercritical CO2 emulsified electrolyte (ELP-SCE) was performed. Surface of the Ni-P coatings on the Nylon 6,6 was observed by an optical microscope and a scanning electron microscope. The Ni-P coating by the conventional catalyzation and the conventional electroless plating showed some cracks, nodules and rough structure. The Ni-P coating by the SCC and the conventional electroless plating showed smooth Ni-P coating on the surface of each fibers and had some peeled-off parts. On the other hand, uniform Ni-P coating on the surface of each fibers was obtained by the SCC and the ELP-SCE. These results demonstrated that the SCC is effective to impregnate Pd catalysts into the fibers, and the ELP-SCE can inhibit the nodule growth of the Ni-P. Thus, the proposed method can metallize the surface of each Nylon 6,6 fibers and has potential to give some functions on textiles. (C) 2016 Elsevier B.V. All rights reserved., 2016年09月, 302, 336, 343, 研究論文（学術雑誌）, 10.1016/j.surfcoat.2016.06.037

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• 査読あり, 英語, MICROELECTRONIC ENGINEERING, Metallization of textile by Pt catalyzation in supercritical carbon dioxide and Pt electroless plating for applications in wearable devise, Mitsuo Sano; Yuma Tahara; Tso-Fu Mark Chang; Chun-Yi Chen; Tomoko Hashimoto; Hiromichi Kurosu; Masato Sone, In this study, an electroless plating method involved Pt catalyzation in supercritical carbon dioxide (sc-CO2) and conventional Pt electroless plating was used for the metallization of polyamide 6,6 (PA66) textiles. The catalyzation was conducted either by conventional method at atmospheric pressure or in sc-CO2 with bis (2,4-pentandionato)-platinum. After the catalyzation process, the conventional Pt electroless plating method was performed for the Pt catalyzed PA66 textiles. Surface of the Pt coated PA66 was observed by an optical microscope and a scanning electron microscope. The Pt coating by the conventional catalyzation had a rough surface, and the surface did not show the textile outline because of the dissolution of the textile in the conventional catalyzation solution. The textile metallized by the sc-CO2 catalyzation showed a metallic bright coating, and the Pt coating was observed on the surface of each fiber. These results indicate that the sc-CO2 catalyzation is a promising method to catalyze the PA66 textile. (C) 2016 Elsevier B.V. All rights reserved., 2016年03月, 153, 92, 95, 研究論文（学術雑誌）, 10.1016/j.mee.2016.02.027

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• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, Solid-state C-13 NMR study of banana liquid crystals-3: Alkyl-tail-group packing environments of an acute-angle bent-core molecule in the hexagonal columnar and cubic phases, Kurosu, Hiromichi; Endo, Yumi; Kimura, Saori; Hashimoto, Tomoko; Harada, Motoi; Lee, Eun-Woo; Sone, Masato; Watanabe, Junji; Kang, Sungmin, Solid-state C-13 nuclear magnetic resonance (NMR) measurements were performed on the hexagonal columnar and cubic phases of an acute-angle banana-shaped molecule, N(1,7)-S30. In the hexagonal columnar phase, three peaks appear at the NMR chemical shifts assigned to the internal methylene carbons of alkyl tails, indicating that the two alkyl tails have different packing structures, and one of the tails has two different conformations within a single molecule. Combined cross-polarization/magic-angle spinning and pulse saturation transfer/magic-angle spinning measurements show that one of the alkyl chains is located inside and the other is located outside the columnar structure. In the cubic phase, pulse saturation transfer/magic-angle spinning measurement shows that only one peak appears at the NMR chemical shifts assigned to the internal methylene carbons of alkyl tails, indicating that both of the alkyl chains are located outside the cubic structure. (C) 2015 Elsevier B.V. All rights reserved., 2016年02月, 1105, 34, 40, 研究論文（学術雑誌）, 10.1016/j.molstruc.2015.10.030

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• 査読あり, 英語, Nuclear Magnetic Resonance, Synthetic macromolecules, Hiromichi Kurosu; Takeshi Yamanobe, In this chapter, the papers devoted to NMR application to study synthetic polymers over a period from June 2013 through May 2014 have been reviewed. It includes analysis of primary structure of polymers such as tacticity, regioregularity, end group, sequence distribution (Section 2), application of imaging, diffusion and solid-state NMR techniques to characterize the synthetic macromolecules (Sections 3 and 4). Finally in Section 5, papers devoted to dynamics of the synthetic macromolecules have been surveyed., 2015年, 44, 431, 455, 研究論文（学術雑誌）, 10.1039/9781782622758-00431

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• 査読あり, 英語, Nuclear Magnetic Resonance, Synthetic macromolecules, Hiromichi Kurosu; Takeshi Yamanobe, In this chapter, the papers devoted to NMR application to study synthetic polymers over a period from June 2012 through May 2013 have been reviewed. It includes analysis of primary structure of polymers such as tacticity, regioregularity, end group, sequence distribution (Section 2), application of imaging, diffusion and solid-state NMR techniques to characterize the synthetic macromolecules (Sections 3 and 4). Finally in Section 5, papers devoted to dynamics of the synthetic macromolecules have been surveyed., 2014年, 43, 423, 456, 研究論文（学術雑誌）, 10.1039/9781849738125-00423

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• 査読あり, 英語, JOURNAL OF MOLECULAR LIQUIDS, Sites of protonation and copper(II)-complexation in protic ionic liquids comprised of N-hexylethylenediaminium cation, Mayu Watanabe; Shinobu Takemura; Sayaka Kawakami; Emi Syouno; Hiromichi Kurosu; Masafumi Harada; Masayasu Iida, Protonation sites of a chelating mono-protic ionic liquid (PIL) comprising N-hexylethylenediaminium (= HHexen(+)) depending on the counter anion were studied by N-15 and C-13 NMR spectroscopy and DFT calculation. In the case of the bis(trifluoromethanesulfonyl) amide (=TFSA(-)) PIL, the protonation occurred almost at the secondary amine, whereas the protonation occurred preferentially at the primary amine in the trifluoroacetate (= TFA(-)) PIL The formation of a chelating copper(II) complex with the cationic unit of the PIL despite the electrostatic repulsion was revealed using the paramagnetic broadenings of the C-13 NMR spectra of the PILs. (C) 2013 Elsevier B.V. All rights reserved., 2013年07月, 183, 50, 58, 研究論文（学術雑誌）, 10.1016/j.molliq.2013.04.002

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• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, Solid-state C-13 NMR study of banana liquid crystals-2: Alkyl tail-group packing environments in the hexagonal columnar phase, Kurosu, Hiromichi; Endo, Yumi; Kimura, Saori; Hashimoto, Tomoko; Harada, Motoi; Lee, Eun-Woo; Sone, Masato; Watanabe, Junji; Kang, Sungmin, Solid-state C-13 nuclear magnetic resonance (NMR) measurements were performed in order to obtain the packing structure of alkyl tail in the hexagonal columnar phase of the banana-shaped N(1,7)-S16 molecule. In this phase, NMR chemical shifts assigned to the internal methylene carbons at an amorphous state appear as two peaks, indicating that the two alkyl tails are placed under two different chemical environments. From combined cross-polarization/magic-angle spinning and pulse saturation transfer/magical-angle spinning measurements, two alkyl tails were found to have the different mobility. Such two different environments are not unusual in conventional mesophases, but in the hexagonal columnar phase formed by cylindrical columns composed of enclosed smectic layers; one of the alkyl tails is located inside and the other is located outside the columnar structure. (C) 2013 Elsevier B.V. All rights reserved., 2013年05月, 1040, 117, 121, 研究論文（学術雑誌）, 10.1016/j.molstruc.2013.03.003

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• 査読あり, 英語, Experimental Methods in Polymer Science: Modern Methods in Polymer Research and Technology, NMR Spectroscopy in Polymer Science, I. Ando; M. Kobayashi; M. Kanekiyo; S. Kuroki; S. Ando; S. Matsukawa; H. Kurosu; H. Yasunaga; S. Amiya, 2012年12月02日, 261, 493, 論文集(書籍)内論文, 10.1016/B978-0-08-050612-8.50010-6

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• 査読あり, 英語, Nuclear Magnetic Resonance, A specialist periodical report on nuclear magnetic resonance (2011/8) synthetic macromolecules, Hiromichi Kurosu; Takeshi Yamanobe, 2012年, 41, 386, 428, 研究論文（学術雑誌）, 10.1039/9781849734851-00386

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• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, Solid-state C-13 NMR study of banana liquid crystals - 1: Two different alkyl tail-group packing environments in the B7 phase, Kurosu, Hiromichi; Nakanishi, Saki; Kimura, Saori; Kang, Sungmin; Li, Xiaodong; Sone, Masato; Watanabe, Junji, Solid-state C-13 nuclear magnetic resonance (NMR) measurements were performed for the B7 phase of the banana-shaped molecule P-8-O-PIMB(NO2). In this phase, NMR chemical shifts assigned to five methylene carbons on the alkyl tail appear as at least seven peaks, indicating that the two alkyl tails within a single molecule have different packing structures. Combined CP/MAS and PST/MAS measurements show that one of the alkyl tails has dense packing with low molecular mobility and the other has loose packing with high molecular mobility. Thus, it can be concluded that both the polar bent and molecular axes are tilted toward the layer in the B7 phase of P-8-O-PIMB(NO2), exhibiting molecular leaning. (C) 2011 Elsevier B.V. All rights reserved., 2012年01月, 1008, 49, 53, 研究論文（学術雑誌）, 10.1016/j.molstruc.2011.11.021

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• 査読あり, 英語, POLYMER, Crystalline structure of polyethylene containing vinylene units in the main chain, Naofumi Naga; Rika Arai; Genzo Kikuchi; Akinori Toyota; Keiichi Noguchi; Masato Sone; Fukiko Shirae; Tomoka Gotoh; Hiromichi Kurosu, Polyethylene containing trans- or cis-vinylene units in the main chain has been synthesized by means of partial hydrogenation of trans- or cis-polypentenamer (TP or CP), and trans-polyoctenamer (TO). Crystalline structure of the polymers has been investigated with wide-angle X-ray diffraction, FT-IR analyses, solid-state NMR measurements and quantum chemical calculations of the NMR chemical shifts. These results clear that the partially hydrogenated TP or CP samples having an average number of methylene units of 6.9-8.4 per vinylene unit forms not only orthorhombic crystal but hexagonal-like crystal. (C) 2011 Elsevier Ltd. All rights reserved., 2011年09月, 52, 21, 4857, 4866, 研究論文（学術雑誌）, 10.1016/j.polymer.2011.08.058

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• 査読あり, 英語, Journal of Molecular Structure, Precise side-chain conformation analysis of l-phenylalanine in α-helical polypeptide by quantum-chemical calculation and 13C CP-MAS NMR measurement, Subaru Niimura; Junya Suzuki; Hiromichi Kurosu; Takeshi Yamanobe; Akira Shoji, To clarify the positive role of side-chain conformation in the stability of protein secondary structure (main-chain conformation), we successfully calculated the optimization structure of a well-defined α-helical octadecapeptide composed of l-alanine (Ala) and l-phenylalanine (Phe) residues, H-(Ala)8-Phe-(Ala)9-OH, based on the molecular orbital calculation with density functional theory (DFT/B3LYP/6-31G(d)). From the total energy and the precise secondary structural parameters such as main-chain dihedral angles and hydrogen-bond parameters of the optimized structure, we confirmed that the conformational stability of an α-helix is affected dominantly by the side-chain conformation (χ1) of the Phe residue in this system: model A (T form: around 180° of χ1) is most stable in α-helix and model B (G+ form: around -60° of χ1) is next stable, but model C (G- form: around 60° of χ1) is less stable. In addition, we demonstrate that the stable conformation of poly(l-phenylalanine) is an α-helix with the side-chain T form, by comparison of the carbonyl 13C chemical shift measured by 13C CP-MAS NMR and the calculated one. © 2010 Elsevier B.V. All rights reserved., 2010年04月22日, 969, 1-3, 40, 47, 研究論文（学術雑誌）, 10.1016/j.molstruc.2010.01.040

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• 査読あり, 日本語, KOBUNSHI RONBUNSHU, Precise Structural Analysis of Polypeptides by Quantum Chemical Calculation, Hiroyuki Souma; Hiromichi Kurosu; Akira Shoji, We computed the optimized structure of alpha(R)-helical polypeptides, H-(Ala)(18)-OH and H-(Ala-Gly)(9)-OH, based on the molecular orbital calculation with density functional theory (DFT/6-31G(d)), and then the H-1, C-13, N-15 and O-17 nuclear shieldings of those optimized structures based on the GIAO-CHF method with B3LYP/6-311G(d, p). In conclusion, we demonstrated that the precise quantum chemical calculation is extremely useful for the secondary and tertiary structural analysis of some proteins and polypeptides. We demonstrated concretely that the precise secondary structural parameters (phi = -62 degrees, psi = -43 degrees), hydrogen bond parameters and the calculated isotropic C-13 and N-15 chemical shifts of the main-chain for the optimized structures were greatly in good agreement with the data by X-ray (or neutron) diffraction analysis and the chemical shifts by high-resolution solid-state NMR. Furthermore, we successfully demonstrated that the L-proline residue is certainly included in the alpha(R)-helix conformation by the quantum chemical calculation and by the C-13 and N-15 NMR chemical shifts., 2010年01月, 67, 1, 10, 27, 研究論文（学術雑誌）
• 査読あり, 英語, POLYMER JOURNAL, Molecular dynamics and orientation of stretched rubber by solid-state C-13 NMR, Hideaki Kimura; Hidehiko Dohi; Marina Kotani; Takanobu Matsunaga; Kazuo Yamauchi; Hironori Kaji; Hiromichi Kurosu; Tetsuo Asakura, The molecular dynamics and orientation of vulcanized natural rubber (NR) stretched at a low extension ratio (alpha=stretched length/original length) were studied by carbon-13 direct polarization-magic angle spinning nuclear magnetic resonance (C-13 DP-MAS NMR), C-13 cross-polarization (CP)-MAS NMR, C-13 DIP NMR without MAS, C-13 CP NMR without MAS and density functional theory (DFT) calculations. Gradual peak broadening was observed in the C-13 DP-MAS NMR spectra of stretched NR with an increasing extension ratio, indicating that the molecular mobility of NR chains is restricted by stretching. The static C-13 NMR spectra of uniaxially stretched NR (alpha=2) changed slightly depending on the angle, theta, between the stretching direction and the applied magnetic field, although the spectra of unstretched NR did not change even if theta was changed. Thus, it is noted that NR chains oriented slightly as a time average by stretching even at a low extension ratio, alpha=2, although there still exists rapid rotation around the oriented NR chain. Motionally narrowed anisotropies in the C-13 spectra of stretched NR and the directions of chemical shift anisotropy principal axes determined by DFT calculations suggest that isoprene units of oriented rubber chains in stretched NR rotate rapidly around the axis that almost aligned with the C=C bond direction of polyisoprene. Polymer Journal (2010) 42, 25-30; doi:10.1038/pj.2009.307, 2010年01月, 42, 1, 25, 30, 研究論文（学術雑誌）, 10.1038/pj.2009.307

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• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, Structure and dynamics of poly(ethylene-co-1,5-hexadiene) as studied by solid state C-13 NMR and quantum chemical calculations, Kurosu, Hiromichi; Yamamoto, Yuuri; Fujikawa, Aki; Kawabata, Emika; Sone, Masato; Naga, Naofumi, Poly(ethylene-co-1,5-hexadiene) with 1,5-hexadiene (HD) contents of 1.8, 8.1, 9.7 and 20.3% was prepared by copolymerization of ethylene and HD involving intermolecular cyclization. Higher-order structures and dynamics of these samples were Studied by solid state NMR and quantum chemistry. The C-13 solid state NMR spectra and C-13 spin-lattice relaxation time (T-1) of the samples were measured. The observed C-13 CP/MAS and PST/MAS NMR spectra for all samples were decomposed into six peaks. The cyclopentane units incorporated in the main chain of polyethylene affected not only the crystalline structure but also the noncrystalline structure. This causes a trans-rich conformation in the noncrystalline region. Even in the melt-quenched samples, incorporation of the cyclopentane structure into the polyethylene chain suppresses the increase in the gauche structure in the noncrystalline region. Based on the C-13 chemical shift of the methylene carbon. the low cyclopentane content sample assumes an orthorhombic crystal structure, and the high cyclopentane content samples assume a hexagonal-type chain packing. C-13 spin-lattice relaxation times show that the crystalline region of the low cyclopentane content sample has two regions with different mobility, although the high cyclopentane content samples have only one region with a high mobility for each peak. Furthermore, quantum chemical calculations for the C-13 NMR shieldings were carried out for precise assignment of the peaks. (C) 2008 Elsevier B.V. All rights reserved., 2009年03月, 921, 1-3, 208, 214, 研究論文（学術雑誌）, 10.1016/j.molstruc.2008.12.046

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• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, Theoretical investigations of C-13 chemical shifts in glucose, cellobiose, and native cellulose by quantum chemistry calculations, Shinji Suzuki; Fumitaka Horii; Hiromichi Kurosu, The effects of the conformation and hydrogen bonding on C-13 isotropic chemical shifts have theoretically been investigated for beta-D-glucose, D-cellobiose, and the cellobiose units of native cellulose by quantum chemistry calculations based on the DFT method. The linear relationship between the chemical shift of the C6 carbon and the torsion angle around the C6-O6 bond in the CH2OH side group, which was previously obtained in experiments, is Successfully reproduced for beta-D-glucose by the theoretical calculations. A similar linear relationship is also found to hold for the C4 carbon, supporting the previous finding in experiments. Moreover, the C5 chemical shift also depends on the conformation of the side group, but the conformation of the O6H hydrogen atom at the gamma position may mainly contribute to the dependence for the C5 carbon through the possible formation of intramolecular hydrogen bonding. The gamma(H)-gauche effect produced by the OH hydrogen atom (gamma-H) at the gamma position is found, for the first time, to induce 3-5 ppm downfield shift for the carbon in question, and this effect reduces by 2-3 ppm when the intramolecular hydrogen bonding associated with gamma-H is formed. Similar calculations for D-cellobiose and the cellobiose units in native cellulose reveal appreciable dependences of the C1 and C4 chemical shifts on the torsion angles phi and psi around the (1 -> 4)-beta-glycosidic linkage. In contrast, no significant effects of different intramolecular and intermolecular hydrogen bondings forming between neighboring glucose residues are recognized on the chemical shifts of the respective carbons associated with these hydrogen bondings. (C) 2009 Elsevier B.V. All rights reserved., 2009年03月, 921, 1-3, 219, 226, 研究論文（学術雑誌）, 10.1016/j.molstruc.2009.01.002

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• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, Theoretical investigations of the γ-gauche effect on the 13C chemical shifts produced by oxygen atoms at the γ position by quantum chemistry calculations, 黒子弘道, The gamma-gauche effect on C-13 chemical shifts that is produced by the O atoms located at the gamma positions has been evaluated by quantum chemistry calculations based on the GAIO-CHF procedure. The gamma-gauche effects produced by the O and Cl atoms in n-propanol and n-propyl chloride are found to be, respectively, +1.4 and -0.7 ppm, whereas that due to the C atom in n-butane is -3.0 ppm in good agreement of the values previously calculated. The apparent cause of such a difference in the gamma-gauche effect is mainly relatively higher shielding of the CH3 carbon in the trans conformation for the n-propanol and n-propyl chloride. Extending the n-propanol chain at both ends causes no significant change in the gamma-gauche effect produced by the O atom. In 2-butanol and 2-methyl-2-butanol as examples of secondarily and tertiarily Substituted compounds, the gamma-gauche effects produced by the gamma-OH groups are estimated to be -7 to -9 ppm. In addition, the gamma-gauche effect due to the C atom is found to increase in n-butane, secondary, and tertiary butanols in this order. The gamma-gauche effect produced by the O atom in hydroxyethylcyclohexane is as negligibly small as -0.7 ppm, whereas that produced by the C atom in ethylcyclohexane is about -5 ppm. These results suggest that the gamma-gauche effect, including downfield shift, produced by the O atom in a compound greatly depends on its chemical structure, whereas upfield shifts of -3 to -7 ppm are induced in all examined Compounds as the gamma-gauche effect due to the C atom. (C) 2008 Elsevier B.V. All rights reserved., 2009年02月, 919, 1-3, 290, 294, 研究論文（学術雑誌）, 10.1016/j.molstruc.2008.09.019

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• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, Precise structural analysis of α-helical copolypeptide H-(Ala-Gly)9-OH by quantum chemical calculation and high-resolution solid-state NMR measurement., 黒子弘道, We computed the optimized structure of sequential 18-mer copolypeptide H-(Ala-Gly)(9)-OH (C45H74N18O19) adopting an right-handed alpha-helix (alpha(R)-helix) conformation with the basis set of DFT/6-31G(d), and then calculated the nuclear shieldings of the optimized structure with the basis set of DFT/6-311G(d,p). As a result, we confirmed highly accurate conformational parameters characteristic to the alpha(R)-helical H-(Ala-Gly)(9)-OH, which were identical with those of the individual Ala and Gly residues. Most of these parameters were fundamentally the same as those obtained for the optimized CER-helical H(Ala)(18)-OH. Furthermore, it was found that the calculated isotropic C-13 and N-15 chemical shifts were dependent on the nature of individual amino acid residues, which were greatly in good agreement with those of alpha(R)-helical model copolypeptides consisting of L-alanine and glycine residues measured by high-resolution solid-state NMR., 2008年11月, 891, 1-3, 58, 63, 研究論文（学術雑誌）, 10.1016/j.molstruc.2008.03.004

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• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, Precise structural analysis of α-helical poly(L-alanine) by quantum chemical calculation, 黒子弘道, It is extremely important to elucidate the formation mechanism of the secondary structure in polypeptides and proteins. This enables the stability of the three-dimensional structure of proteins to be predicted theoretically. For this purpose, the development of a precise structural calculation is indispensable. We computed the optimized structure of a poly(L-alanine) (PLA) molecule, H-Ala(18)-OH (C54H92N18O19), adopting a right-handed alpha-heliX (OCR-helix) conformation based on the molecular orbital calculation with density functional theory (DFT/6-31G(d)). As a result, we confirmed highly accurate conformational parameters characteristic to the "most acceptable alpha(R)-helix PLA" as follows; intrinsic dihedral angles (phi,psi,omega) = (-62 degrees, -43 degrees, 178 degrees); hydrogen-bond distances R-O center dot center dot center dot H = 0.205 nm and R-O center dot center dot center dot N = 0.303 nm; hydrogen-bond angles angle C=O center dot center dot center dot H = 149 degrees and angle N-H center dot center dot center dot O = 160 degrees. Furthermore, we calculated the H-1, C-13, N-15 and O-17 nuclear shieldings of the optimized OCR-helical H-Ala(18)-OH with the base set of DFT/6-311G(d,p), and demonstrated that the calculated isotropic C-13 and H-1 chemical shifts were identical with those measured by high-resolution solid-state NMR. (C) 2008 Elsevier B.V. All rights reserved., 2008年10月, 889, 1-3, 104, 111, 研究論文（学術雑誌）, 10.1016/j.molstruc.2008.01.031

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• 査読あり, 英語, DALTON TRANSACTIONS, Formation of molecular glasses and the aggregation in solutions for lanthanum(III), calcium(II), and yttrium(III) complexes of octanoyl-DL-alaninate, Gerile Naren; Rie Masuda; Masayasu Iida; Masafumi Harada; Hiromichi Kurosu; Toshiharu Suzuki; Takayoshi Kimura, Octanoylalaninato-metal (metal = calcium(II), yttrium(III), lanthanum(III), and zinc(II)) complexes were prepared and the first three metal complexes were found to readily form transparent and stable molecular glasses from methanol and chloroform solutions. The process of glass formation from solution was studied in detail. The effect of the central metal ions on the formation of glassy states was remarkable: the lanthanum and calcium complexes assumed glassy or crystalline states depending on the isolation method and the yttrium complex had a large tendency to assume an amorphous state, whereas the zinc complex did not assume a pure and stable glassy-state. The glass transition temperatures were 50 degrees C for the yttrium complex and 70-75 degrees C for the lanthanum and calcium complexes when these complexes are monohydrates prepared by a solvent-cast method, whereas they increase by 10-30 degrees for the hemihydrates which were obtained by an annealing treatment at 110 degrees C. The coordinated water was eliminated from the solid above the glass transition temperature. The glassy state was regarded as a result of the self-aggregation of the metal complex in solution by an entanglement of the methylene chains with one another. SAXS showed the presence of two disordered bilayer structures with 2.2 nm and 4.5 nm periods in the glassy states. The structures of the molecular assemblies in the solid states and solutions were compared by SAXS and NMR studies. EXAFS studies confirmed the coordination numbers of oxygen atoms around the yttrium and lanthanum atoms in the glassy states for the yttrium and lanthanum complexes to be about 7., 2008年04月, 13, 1698, 1709, 研究論文（学術雑誌）, 10.1039/b713768k

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• 査読あり, 英語, JOURNAL OF MAGNETIC RESONANCE, High field O-17 solid-state NMR study of alanine tripeptides, Kazuo Yamauchi; Michi Okonogi; Hiromichi Kurosu; Masataka Tansho; Tadashi Shimizu; Terry Gullion; Tetsuo Asakura, O-17-chemical shifts of Ala-Ala-Ala, with parallel and anti-parallel beta-sheet structures, are observed using a 930-MHz high-resolution solid-state NMR spectrometer. Ala-Ala-Ala serves as a model sheet-forming peptide because it can be easily prepared as either a parallel or an anti-parallel beta-sheet structure. Spectral differences between the two samples are observed which arise from molecular packing differences between the two sheet structures. DFT chemical shift calculations are performed for the two samples, and the calculated spectra are in good agreement with the experimental spectra. The DFT calculations provide insight into the nature of the chemical shift differences observed between the two sheet structures. (c) 2007 Elsevier Inc. All rights reserved., 2008年02月, 190, 2, 327, 332, 研究論文（学術雑誌）, 10.1016/j.jmr.2007.11.006

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• 査読あり, 英語, Journal of Physical Chemistry B, High-field 1H MAS and15N CP-MAS NMR studies of alanine tripeptides and oligomers: Distinction of antiparallel and parallel β-sheet structures and two crystallographically independent molecules, Yu Suzuki; Michi Okonogi; Kazuo Yamauchi; Hiromichi Kurosu; Masataka Tansho; Tadashi Shimizu; Hazime Saitô; Tetsuo Asakura, β-Strand peptides are known to assemble into either antiparallel (AP) or parallel (P) β-sheet forms which are very important motifs for protein folding and fibril formations occurring in silk fibroin or amyloid proteins. Well-resolved 1H NMR signals including NH protons were observed for alanine tripeptides (Ala)3 with the AP and P structures as well as (Ala)n (n = 4-6) by high-field/fast magic-angle spinning NMR. Amide NH and amino NH3+ 1H signals of (Ala) 3 with the P structure were well resonated at 7.5 and 8.9 ppm, respectively, whereas they were not resolved for the AP structure. Notably, NH 1H signals of (Ala)3 and (Ala)4 taking the P structure are resonated at higher field than those of the AP structure by 1.0 and 1.1 ppm, respectively. Further, NH 15N signals of (Ala) 3 with the AP structure were resonated at lower field by 2 to 5 ppm than those of (Ala)3 with the P structure. These relative 1H and 15N hydrogen bond shifts of the P structure with respect to those of the AP structure are consistent with the relative hydrogen bond lengths of the interstrand N-H⋯O=C bonds. Distinction between the two crystallographically independent chains present in the AP and P structures was feasible by 15N chemical shifts but not by 1H chemical shifts because of insufficient spectral resolution in the latter. Calculated 1H and 15N shielding constants by density functional theory are generally consistent with the experimental data, although some discrepancies remain depending upon the models used. © 2007 American Chemical Society., 2007年08月02日, 111, 30, 9172, 9178, 研究論文（学術雑誌）, 10.1021/jp072755z

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• 査読あり, 英語, MACROMOLECULAR SYMPOSIA, Structure and mechanical properties of chitosan/poly(vinyl alcohol) blend films, Yumiko Nakano; Yuezhen Bin; Mami Bando; Teruo Nakashima; Tsumuko Okuno; Hiromichi Kurosu; Masaru Matsuo, The origins of the thermal and mechanical properties of chitosan and poly(vinyl alcohol) (PVA) with inter- and intra-hydrogen bonds were investigated systematically by using X-ray, DSC, positron annihilation and viscoelastic measurements. Based on their individual properties, the characteristics of the blend films were estimated in relation to their morphology and mechanical properties as a function of chitosan content. The characteristics of the blend films were also analyzed in terms of the deviation from a simple additive rule of chitosan and PVA content. These results suggested that the miscibility of chitosan and PVA could be ensured by entanglement of the amorphous chain segments of chitosan and PVA. Further detailed analysis revealed that the chitosan content on the film surface is higher than that of the admixture content of chitosan after elongation, although the chitosan and PVA chains were crystallized independently. The elongation could be achieved for the blend films whose PVA content was higher than 50% and the drawn blend films were transparent. Thus, it may be expected that sufficiently entangled meshes formed between chitosan and PVA amorphous chains within the film, the PVA content being higher than 50%, were maintained under the elongation process., 2007年, 258, 63, 81, 研究論文（国際会議プロシーディングス）
• 査読あり, その他, Polymer Preprints, Japan, Higher-order structure of poly(ethylene-co-1,5-hexadien) as studied by solid state NMR, Yuuri Yamamoto; Aki Fujikawa; Masato Sone; Shigemitsu Murase; Naofumi Naga; Hiromichi Kurosu, Poly(ethylene-co-1,5-hexadien) were prepared by copolymerization of ethylene and 1,5-hexadien(HD) and higher-order structure was studied by solid state NMR. The amorphous structure of the polymer is drastically changed as compared with that of polyethylene even for the sample of the smallest content of HD., 2006年, 55, 1, 733, 研究論文（国際会議プロシーディングス）

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• 査読あり, 英語, MAGNETIC RESONANCE IN CHEMISTRY, Structural characterization of poly(diethylsiloxane) in the crystalline, liquid crystalline and isotropic phases by solid-state O-17 NMR spectroscopy and ab initio MO calculation, H Kimura; S Kanesaka; S Kuroki; Ando, I; A Asano; H Kurosu, The structure of poly(diethylsiloxane) (PDES) has been characterized using solid-state NMR of O-17. The sample studied had a weight-average molecular weight of 2.45 x 10(5). The sample was prepared by utilizing the cationic ring-opening polymerization of O-17-enriched hexacyclotrisiloxane. Solid-state NMR of O-17-enriched PDES was measured on the low-temperature beta(1) phase, the high-temperature beta(2) phase, the two-phase system consisting of the liquid crystal and isotropic liquid phase and the isotropic phase. From these data, the molecular structure and dynamics of PDES in the various phases were characterized via the chemical shifts of O-17, and electric field gradient parameters were determined from NMR and ab initio molecular orbital (MO) calculations. In addition to the solid-state NMR of H-1, C-13 and Si-29 previously reported on these samples, knowledge of the dynamic behavior of PDES as inferred from the NMR of O-17 in the present study was enhanced significantly. Further, the potential of combining the experimental NMR of O-17 with ab initio MO calculations to characterize the dynamics of polymers containing oxygen is demonstrated. Copyright (C) 2004 John Wiley Sons, Ltd., 2005年03月, 43, 3, 209, 216, 研究論文（学術雑誌）, 10.1002/mrc.1527

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• 査読あり, 英語, JOURNAL OF PHYSICAL CHEMISTRY A, Solid-state C-13 NMR study of chiral twisted conformation attributable to chirality in smectic phases of achiral banana-shaped molecules, H Kurosu; M Kawasaki; M Hirose; M Yamada; SM Kang; M Sone; H Takezoe; J Watanabe, Solid-state C-13 NMR measurements were made for the B2 and B4 phases of the achiral banana-shaped molecule, P-14-O-PIMB, which exhibits a direct transformation from the 132 phase to the B4 phase. In both phases, an NMR resonance signal assigned to carbonyl carbons of the ester linkages appears as doublet peaks, showing that the two carbonyl carbons are circumstanced in different electronic environments on the NMR time scale. The chemical shifts of the two peaks are 165.6 and 163.9 ppm in the B2 phase, and these values are not changed in the transformation to the low-temperature B4 phase. To explain this distinct splitting of the carbonyl carbon signal, we take three assumptions into account: (1) the molecules are accommodated in the unique phase, but the conformational exchange between two states takes place slowly; (2) the two side wings of each molecule experience fast interconformational jumps, but their "average conformer" is different, thus giving two different peaks in the spectra; and (3) the individual molecule claims the twisted conformation, where the two carbonyl carbons of the ester moieties are twisted away from each other by rotating out of the molecular core plane with different dihedral angles. From the present 13 C NMR results, the first and second possibilities are ruled out, and it is concluded that the banana-shaped molecules assume the twisted conformation, which is attributable to the origin of the chirality of the 132 and B4 phases in the achiral banana-shaped molecular system., 2004年05月, 108, 21, 4674, 4678, 研究論文（学術雑誌）, 10.1021/jp031277z

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• 査読あり, 英語, POLYMER, Ultradrawing of blend films of ethylene-dimethyl-aminoethyl methacrylate copolymer and ultra-high molecular weight polyethylene prepared by gelation/crystallization from solutions, M Azuma; L Ma; CQ He; T Suzuki; Y Bin; H Kurosu; M Matsuo, Copolymer ethylene-dimethyl-aminoethyl methacrylate (EDAM) with 3.9% DAM side groups and ultra-high molecular weight polyethylene (UHMWPE) were blended in decalin solvent. The hot homogenized solution was poured into an aluminum tray to form gels and the decalin was allowed to evaporate from the resultant gels under ambient condition. Surprisingly, the resultant dry blend films could be elongated to more than 200-fold (lambda = 200) even for the blend film with 90% EDAM content (9/1 composition), although the maximum draw ratio of EDAM homopolymer films was 1.6-fold (lambda = 1.6). The mechanism of the great drawability was dependent upon the content of EDAM. The drawability for the 9/1 composite films was attributed to large crystal lamellae of UHMWPE ensuring crystal transition from a folded to a fibrous type. Accordingly, EDAM chains were independent of ultradrawing of UHMWPE and kept a random orientation under ultra-drawing process. The storage (Young's) modulus was 10 GPa at 20degreesC. In contrast, EDAM chains within the 1/1 composite films were oriented drastically together with UHMWPE crystallites. The modulus of the 1/1 composition at 20degreesC reached 68 GPa, which was higher than the value (40 GPa) of polypropylene films with lambda = 100. Such considerable difference of modulus due to EDAM content was analyzed in relation to the gelation/crystallization from solutions. (C) 2003 Elsevier Ltd. All rights reserved., 2004年01月, 45, 2, 409, 421, 研究論文（学術雑誌）, 10.1016/j.polymer.2003.09.031

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• 査読あり, 英語, MACROMOLECULES, Molecular mobility of amorphous chain segments of ethylene-methyl methacrylate copolymer films as a function of temperature estimated by positron annihilation, X-ray diffraction, and C-13 NMR, L Ma; CQ He; T Suzuki; M Azuma; YZ Bin; H Kurosu; M Matsuo, The relationship between the morphology and the mechanical properties of copolymer ethylene-methyl methacrylate (EMMA) films with different MMA contents was investigated as a function Of temperature by using positron annihilation, X-ray diffraction, and C-13 solid-state NMR. To make clear the effect of MMA. side groups on the morphology and molecular mobility of EMMA as a function of temperature, the characteristics of EMMA were discussed together with those of copolymer (dimethylamino)ethyl methacrylate (EDAM) and branched polyethylene. Three kinds of transitions were confirmed by positron annihilation: the first at temperatures around -130 degreesC, the second around -40 degreesC, and the third around 50 degreesC. The first and the second transitions were due to the commencement of molecular motions, which can remove trapped electrons from their shallow potentials, while the third transition around 50 degreesC was attributed to the partial melting of unstable small crystallites. These transitions were in good agreement with the results obtained from differential scanning calorimetry (DSC) and X-ray measurements. Namely, the DSC curves of EMMA provided a peak around -25 to -30 degreesC corresponding to the second transition and a small peak around 43-48 degreesC corresponding to the third transition. Lifetime (tau3) showed no obvious change between branched polyethylene and EMMA-I melt films. This result can be explained within the framework of the spur model of Ps formation in terms of the trapping of positrons (and may be electrons) by the polar groups, -C=O, in EMMA., 2003年10月, 36, 21, 8056, 8065, 研究論文（学術雑誌）, 10.1021/ma021543r

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• 査読あり, 英語, COLLOID AND POLYMER SCIENCE, Oriented and thermal crystallization of poly(ethylene terephthalate), T Xu; YZ Bin; H Kurosu; M Matsuo, The oriented and thermal crystallization of amorphous poly(ethylene terephthalate) (PET) films was investigated in terms of the morphological aspects. When the amorphous PET films were stretched up to the desired draw ratios in a hot water bath at 62, 72, and 80 degreesC, the birefringence of the specimens increased with increasing draw ratio (lambda). This tendency becomes most significant when the specimen was drawn in the bath at 62 degreesC. The storage modulus of the specimen drawn at 62 degreesC was higher than those of the specimens drawn at 72 and 80 degreesC. The exothermic peak in the DSC curves was observed clearly for the specimen drawn up to lambda=4 in the hot water bath at 80 degreesC, while the peak did not appear for the specimen drawn up to lambda=4 at 62 degreesC. Under an H-v polarization condition, light scattering patterns from the specimens drawn in the hot water bath showed four lobes at small azimuthal angles and four sharp streaks at large azimuthal angles. Such a profile was independent of the drawing temperatures from 62 to 80 degreesC. Based on the observed H-v patterns, a model was proposed by assuming the existence of a row-nucleated sheaf-like structure whose rows were preferentially oriented at a particular angle with respect to the stretching direction. The patterns calculated by using the above model were rather close to the patterns observed. This agreement implies that row-nucleated sheaf-like texture arises with lamellar overgrowth., 2003年07月, 281, 7, 624, 636, 研究論文（学術雑誌）, 10.1007/s00396-002-0813-x

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• 査読あり, 英語, JOURNAL OF APPLIED POLYMER SCIENCE, A study of solvent exchange process in (ethylene-vinyl alcohol) copolymer gels by a proton nuclear magnetic resonance spectroscopy imaging method, M Kanekiyo; M Kobayashi; Ando, I; H Kurosu; S Amiya, The proton nuclear magnetic resonance (H-1 NMR) image patterns of (ethylene-vinyl alcohol) copolymer (EVOH)/dimethylsulfoxide (DMSO) gels with various ethylene contents were measured to elucidate the process of solvent exchange between DMSO and water in the gels soaked in water. The results of these experiments indicate that the rate of solvent exchange between DMSO and water in the gels increased with an increase in the ethylene content of EVOH copolymers. (C) 2002 Wiley Periodicals, Inc., 2002年10月, 86, 2, 504, 508, 研究論文（学術雑誌）, 10.1002/app.11010

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• 査読あり, 英語, POLYMER, Elongation-induced phase separation of poly(vinyl alcohol)/poly(acrylic-acid) blends as studied by C-13 CP/MAS NMR and wide-angle X-ray diffraction, Q Chen; H Kurosu; L Ma; M Matsuo, The membrane samples of poly(vinyl alcohol)/poly(acrylic-acid) (PVA/PAA) blend with different draw ratios were studied by both C-13 CP/MAS NMR and wide-angle X-ray diffraction (WARD) measurements. Phase separation induced by elongation of the sample was observed and the change of the phase structure with draw ratio was found to be dependent on the composition of the blend samples. (C) 2001 Elsevier Science Ltd. All rights reserved., 2002年02月, 43, 4, 1203, 1206, 研究論文（学術雑誌）
• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, C-13 NMR chemical shift and electronic structure of a three-dimensional polyacetylene crystal by ab initio tight binding MO theory, K Fujii; S Kuroki; M Uchida; H Kurosu; Ando, I, The NMR chemical shift of a three-dimensional polyacetylene crystal in the orthorhombic, form was calculated by a combination of ab initio tight-binding MO theory and the sum-over-states method of the chemical shift theory within the STO-3G minimal basis set, in order to elucidate the inter-molecular interaction effect of the C-13 NMR chemical shift and electronic structure, as associated with the crystallographic form. The effects of inter- and intra-chain on the C-13 NMR chemical shift and the electronic structure were reasonably evaluated. (C) 2002 Elsevier Science B.V. All rights reserved., 2002年01月, 602, 3, 8, 研究論文（学術雑誌）
• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, Structural characterization of drawn (ethylene-vinyl alcohol) copolymer by high-resolution solid-state C-13 NMR, H Kurosu; K Fukushima; M Matsuo; Ando, I; S Amiya, High-resolution solid-state C-13 NMR spectra of drawn (ethylene-vinyl alcohol) copolymer (EVOH) and their C-13 spin-lattice relaxation times (T-1) were measured in order to elucidate the structure and dynamics of EVOH in the drawn state. It is found that the C-13 chemical shift of the CH carbon for drawn EVOH moved upfield as compared with that of undrawn EVOH. Further, the mobility for the CH carbons of low molecular motion components are increased by drawing the EVOH sample. From these experimental results, the changes in the structure and dynamics of the drawn EVOH sample can be elucidated. (C) 2002 Elsevier Science B.V. All rights reserved., 2002年01月, 602, 233, 237, 研究論文（学術雑誌）
• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM, Polar packing structure in copolyester comprising 4-hydroxy benzoic acid and 6-hydroxy-2-naphthoic acid as studied by high resolution solid state C-13 NMR spectroscopy and quantum chemistry, M Kurosu; T Ookubo; H Tuchiya; Ando, I; J Watanabe, The copolyester comprising 73 mol% of 4-hydroxy benzoic acid and 27 mol% of 6-hydroxy-2-naphthoic acid, so called Vectra, was known to show the strong second harmonic generation (SHG) when it has a high molecular weight. Using high-resolution solid state C-13 NMR, we investigated the intermolecular interaction in this series of copolyesters with different inherent viscosities. The observed C-13 NMR chemical shifts of carbonyl carbon moved downfield as the inherent viscosity is increased. The trend is similar to that observed in the inherent viscosity dependence of the SHG activity, showing that the downfield movement of the chemical shift is related to the polar structure. Ab initio GIAO-CHF calculations of NMR chemical shifts (NMR shieldings) were carried out for seven-molecules models with and without the polarity. The result confirms the assignment of the downfield movement of the chemical shifts to the transformation from the nonpolar structure to the polar structure. (C) 2001 Elsevier Science B.V. All rights reserved., 2001年11月, 574, 153, 162, 研究論文（学術雑誌）
• 査読あり, 英語, POLYMER, Ultra-drawing of low molecular weight polyethylene - ultra-high molecular weight polyethylene blend films prepared by gelation/crystallization from semi-dilute solutions, YZ Bin; L Ma; R Adachi; H Kurosu; M Matsuo, Greatest drawability was studied for blend films with branched low molecular weight polyethylene (B-LMWPE) and ultra-high molecular weight polyethylene (UHMWPE) prepared by gelation/crystallization from solutions. The morphology of B-LMWPE-UHMWPE dry gel film and its deformation mechanism were mainly estimated by using differential scanning calorimeter, small-angle X-ray scattering, wide-angle X-ray diffraction and solid-state C-13 NMR. The detailed analysis was carried out for the blend films including large amounts of B-LMWPE. As a result, it was found that the UHMWPE and B-LMWPE were crystallized separately from the mixed solution. The greatest drawability was attributed to a suitable number of entanglements between UHMWPE crystal lamellae that are highly oriented with their large flat faces parallel to the film surface. These entanglements play an important role to transmit the drawing force as intermolecular cross-links and ensured smooth crystal transition of UHMWPE from a folded to a fibrous. In this process, large amount of B-LMWPE is thought to be almost independent of the ultra-drawing behavior of UHMWPE, since the domains of UHMWPE and B-LMWPE within the blend have no interaction and B-LMWPE crystallites take almost a random orientation. (C) 2001 Published by Elsevier Science Ltd., 2001年09月, 42, 19, 8125, 8135, 研究論文（学術雑誌）
• 査読あり, 英語, Macromolecules, Morphology and mechanical properties of copolymer ethylene-methyl methacrylate films as a function of temperature estimated by polarized light scattering, X-ray, and 13C NMR, Lin Ma; Yuezhen Bin; Yuko Sakai; Qun Chen; Hiromichi Kurosu; Masaru Matsuo, The relationship between the morphology and the mechanical properties of copolymer ethylene-methyl methacrylate (EMMA) was estimated as a function of temperature by using polarized light scattering, X-ray diffraction and 13C Solid-state NMR. All of these measurements revealed unstable crystallites within the EMMA films having a MMA content > 14 mol %, crystallinity less than 10%, and crystal size of about 3 nm. On the other hand, the ethylene sequences in the amorphous phase had an ordered arrangement rather than a random orientation. It is evident that these characteristics are due to the strong repulsion between MMA and ethylene. Namely, MMA side groups suppress the crystallization as an essential property of ethylene sequences consequently, the difficulty of accelerating the self-arrangement of ethylene sequences as crystallites leads to a local ordered arrangement of long ethylene sequences in the amorphous phase. The maximum draw ratio of the EMMA film reached 10 times at room temperature. A specimen with a draw ratio < 2 showed a reversible change of stress-strain curves up to 40 repetitions at room temperature. This behavior appears to be within the framework of ideal rubber elasticity. However, the stress at a fixed strain decreased with passing time as well as with increasing temperature. This behavior is completely out of the framework. Such inconsistency is due to the fact that small crystallites playing a cross-linking role became disrupted by chain slippage at a constant strain and at elevated temperature., 2001年07月03日, 34, 14, 4802, 4814, 研究論文（学術雑誌）, 10.1021/ma002110w

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• 査読あり, 英語, POLYMER, Morphology and mechanical properties of swollen gels and dry gel films of poly(vinyl alcohol) prepared by crystallization from solutions under simultaneous biaxially stretching, Y Bin; Y Tanabe; C Nakabayashi; H Kurosu; M Matsuo, Simultaneous biaxial stretching was carried out by using poly(vinyl alcohol) (PVA) gel films which were prepared by crystallization from solutions in dimethyl sulfoxide (Me2SO) and water (H2O) mixtures. The Me2SO/H2O composition was set to be 70:30. The maximum biaxially draw ratio, 3 x 3, is much lower than 8.7 x 8.7 of ultra-high-molecular-weight polyethylene (UHMWPE) dry gel films. Even so, Young's modulus of the PVA film was almost equal to that of the UHMWPE. To address this problem, theoretical analysis was carried out using a three-dimensional model, in which the oriented crystalline layers are surrounded by an anisotropic amorphous phase and the strains of the two phases at the boundary are identical. Young's modulus was calculated by using the generalized orientation factors of crystallites and amorphous chain segments estimated from the orientation functions of crystallites and amorphous chain segments. The experimental values were lower than the calculated one. Such a disagreement between the experimental and calculated values was discussed in relation to the morphology estimated by high-resolution solid state C-13 NMR spectroscopy. Furthermore, the ultimate value of Young's modulus was estimated theoretically by assuming an ideal simultaneous biaxially stretched film with 100% crystallinity and the perfect orientation of the c-axes parallel to the film surface. The predicted value at absolute temperature was less than 13.5 GPa, suggesting the impossibility to produce high-modulus and high-strength PVA sheets. Incidentally, the stress-strain curves repeated up to 40 times of swollen gels with large amount of solvents >80% passed through the same hysteresis route indicating rubber elasticity. Such an interesting phenomenon was investigated in relation to crystallization by small angle light scattering under Hv polarization condition and X-ray diffraction. (C) 2000 Elsevier Science Ltd. All rights reserved., 2001年02月, 42, 3, 1183, 1200, 研究論文（学術雑誌）
• 査読あり, 英語, MACROMOLECULES, Structural and dynamic study of ethylene-vinyl alcohol copolymer gels by H-1 pulse NMR and solid-state C-13 NMR, M Kanekiyo; M Kobayashi; Ando, I; H Kurosu; S Amiya, H-1 pulse NMR and solid-state C-13 NMR spectra of ethylene-vinyl alcohol copolymer (EVOH) gels were measured as a function of ethylene content, and furthermore, the C-13 spin-lattice relaxation times (T-1) and the H-1 spin-spin relaxation times (T-2) have been measured, to elucidate the structure and dynamics of the mobile and immobile regions in the gels. From the H-1 pulse NMR experimental results, it is found that the H-1 T-2 signal is mainly composed of two or three binds of components with different molecular motions. The long T-2 component is assigned to correspond to the mobile region, which comes from the un-cross-linked region, the short T-2 component corresponds to the immobile region, which comes from the cross-linked region, and the intermediate T-2 component corresponds to the intermediate region between the mobile and immobile regions, which comes from the vicinity of the cross-linked region in the EVOH gel. Furthermore, from the solid state C-13 NMR experimental results, it is found that the formation of hydrogen bonds between the hydroxyl groups in vinyl alcohol parts of EVOH copolymers with high vinyl alcohol fraction and the formation of hydrophobic interactions between the methylene groups in ethylene parts of EVOH copolymers with high ethylene fraction contributes to its gel formation., 2000年10月, 33, 21, 7971, 7976, 研究論文（学術雑誌）, 10.1021/ma000668y

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• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, Spatial distribution of paramagnetic Mn2+ ions in a composite PMAA gel with the application of an electric field as studied by H-1 NMR imaging method, A Yamazaki; Y Hotta; H Kurosu; Ando, I, The H-1 T-2 NMR images were observed for a transverse slice of a composite poly(methacrylic acid) hydrogel consisting of two parts with a different degree of crosslinking under the application of a 3 V DC electric field as a function of elapsed time by means of 270 MHz H-1 NMR imaging method. The H-1 T-2 (spin-spin relaxation time) NMR image was converted to the Mn2+ ion concentration image by using the relationship between the Mn2+ ion concentration and the H-1 T-2 value. From these experiments, the spatial distribution of Mn2+ ions in the gel under the application of a 3 V DC electric field were determined as a function of the elapsed time. From the results of the migration process of Mn2+ ions the crosslinking structure of the interfacial region between the two parts with a different degree of crosslinking was discussed. In addition, the formation process of a composite PMAA gel was observed with polymerization time by means of H-1 NMR imaging. (C) 2000 Elsevier Science B.V. All rights reserved., 2000年10月, 554, 1, 47, 53, 研究論文（学術雑誌）
• 査読あり, 英語, BIOPOLYMERS, A study of conformational stability of polyglycine and poly(L-alanine), and polyglycine/poly(L-alanine) blends in the solid state by C-13 cross-polarization/magic angle spinning NMR, J Nakano; S Kuroki; Ando, I; T Kameda; H Kurosu; T Ozaki; A Shoji, C-13 Cross-Polarizarion/Magic Angle Spinning nmr and T-1pH experiments of polyglycine (PG), poly(L-alanine) (PLA), and PG/PLA blends prepared from dichloroacetic acid solution have been carried out, in order to elucidate the conformational stability of these polypeptides in the solid state. From these experimental results, it was clarified that the conformations of PG and PLA in their blends are strongly influenced by intermolecular hydrogen-bonding interactions that cause their miscibility at the molecular level. (C) 2000 John Wiley & Sons, Inc., 2000年08月, 54, 2, 81, 88, 研究論文（学術雑誌）
• 査読あり, 英語, MAGNETIC RESONANCE IN CHEMISTRY, C-13 NMR chemical shift as a probe for estimating the conformation of aromatic groups in the solid state. 1. Biphenyls, S Ando; T Hironaka; H Kurosu; Ando, I, The relationships between C-13 NMR chemical shifts of aromatic carbons and the inter-ring torsion angles (theta) of two phenyl rings in biphenyl and its substituted derivatives were systematically examined. The chemical shifts of C1, C2 and C6 carbons (delta(C1), delta(C2) and delta(C6)) of she biphenyl group in the solid state show systematic correlations with theta when the substituent shielding effects are removed from the solid chemical shifts by subtracting the solution chemical shifts or subtracting the substituent shielding parameters. The substituent parameters deduced from substituted benzenes are utilized for the calculation. An increase in delta(C1), delta(C2) or delta(C6) (high-frequency displacement of the signals) corresponds to an increase in theta. In particular, delta(C6) can be a good measure of theta when no substituents are attached to C6. The isotropic nuclear shielding calculated using ab initio molecular orbital theory with the GIAO-CHF method for the biphenyl agree well with the experimental results. The relationships between the C-13 chemical shifts and the inter-ring torsion angle can be used to estimate the conformation of biphenyl groups incorporated into aromatic and/or liquid crystalline compounds and polymers. Copyright (C) 2000 John Wiley & Sons, Ltd., 2000年04月, 38, 4, 241, 250, 研究論文（学術雑誌）
• 査読あり, 英語, POLYMER, A structural study of (ethylene-vinyl alcohol) copolymers by high-resolution solid-state C-13 NMR, M Kanekiyo; M Kobayashi; Ando, I; H Kurosu; S Amiya, High-resolution solid-state C-13 NMR spectra of (ethylene-vinyl alcohol) copolymers (EVOH) with various ethylene contents in the solid-state and their C-13 spin-lattice relaxation times, T-1, were measured, in order to elucidate the structure and dynamics of the copolymers. From these experimental results, the structural change of the EVOHs with changes of the ethylene content was successfully elucidated. Further, it is found that the C-13 T-1 for the CH carbon of the vinyl alcohol unit is mainly composed of two components. The fractions of short and long T-1 components increase and decrease with an increase in the ethylene fraction, respectively. From these experimental results, it can be said that changes of the ethylene content in the copolymers lead to large changes in their structure and dynamics. (C) 1999 Elsevier Science Ltd. All rights reserved., 2000年03月, 41, 7, 2391, 2404, 研究論文（学術雑誌）
• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, Structural characterization of C-13-labeled n-tetracosane adsorbed on the surface of silica gel by high-resolution solid-state C-13 NMR spectroscopy, H Kurosu; K Takahashi; D Inoue; Ando, I, C-13 CP/MAS and PST/MAS spectra of 10% C-13-labeled n-tetracosane adsorbed on the surface of silica gel were measured by means of high-resolution solid-state C-13 NMR. From these experimental results, it is found that adsorbed n-tetracosane is in three regions with different molecular motion. in the immobile region, n-tetracosane takes a layer structure with triclinic-like form, in the mobile region, n-tetracosane is undergoing fast transition between trans and gauche conformations and fast rotation along the chain axis. (C) 2000 Elsevier Science B.V. All rights reserved., 2000年01月, 516, 2-3, 177, 184, 研究論文（学術雑誌）
• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, Structural characterization of stearic acid in the crystalline state by the cross polarization in solid state C-13 NMR, S Arata; H Kurosu; S Kuroki; Ando, I, C-13 cross polarization/magic angle spinning (CP/MAS) NMR spectra of stearic acid with the crystallographic form C, deuterated the methyl and methylene groups besides a proton in the carboxylic group, were measured as a function of the contact time, in order to obtain the cross relaxation rate (1/T-CH) between the methylene carbons and protons in the compound. From these experimental results, it was found that the 1/T-CH values for the methylene carbons are proportional to r(av)(-6), which is the averaged atomic distance between any specified carbon and protons. This means that the CP experiment provides a geometrical information using the partially deuterated molecules. (C) 1999 Elsevier Science B.V. All rights reserved., 1999年12月, 513, 1-3, 133, 138, 研究論文（学術雑誌）
• 査読あり, 英語, JOURNAL OF CHEMICAL PHYSICS, Diffusional behavior of n alkanes in the rotator phase as studied by pulse field-gradient spin-echo H-1 NMR method, H Yamakawa; S Matsukawa; H Kurosu; S Kuroki; Ando, I, Self-diffusion coefficients, D, of n-C21H44, n-C23H48, n-C24H50, n-C28H58, n-C32H66, and n-C34H70 were measured in the rotator phase and the liquid phase over a wide range of temperatures by using pulse field-gradient spin-echo H-1 NMR method, in order to clarify diffusional behavior of the n-alkanes in the rotator phase. From these experimental results it was found that the self-diffusion coefficients of these n-alkanes in the rotator phase and the liquid phase are decreased with a decrease in temperature with different slopes, and at the transition temperature in going from the liquid phase to the rotator phase do not change with a transitionally large decrease. From the Arrhenius plot of diffusion coefficient against temperature, the activation energies for diffusion of n-C24H50, n-C32H66, and n-C34H70 in the rotator phase were obtained to be 19.9, 33.9, and 35.9 kcal/mol, respectively, and on the other hand those in the liquid phase to be 4.8, 4.8, and 5.1 kcal/mol, respectively. Further, the corresponding values of n-C21H44, n-C23H48, and n-C28H58 in the liquid phase were obtained to be 4.7, 4.6, and 4.9 kcal/mol, respectively. It was found that the activation energy for diffusion of n-alkanes in the rotator phase is increased with an increase in the carbon number and is much larger than that in the liquid phase. Further, it was found that in the rotator phase of a n-C24H50 single crystal, the diffusion coefficients in direction perpendicular and parallel to the long chain axis were determined to be 2.70x10(-6) and 1.64x10(-6) cm(2)/s, respectively. (C) 1999 American Institute of Physics. [S0021-9606(99)51239-7]., 1999年10月, 111, 15, 7110, 7115, 研究論文（学術雑誌）
• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, An MO study on C-13 NMR chemical shift and the electronic structure of a three-dimensional polymer crystal by ab initio tight-binding MO theory I. Polyethylene crystal, M Uchida; Y Toida; H Kurosu; Ando, I, Formulae for calculating the NMR chemical shift of a three-dimensional (3D) polymer crystal were derived by a combination of ab initio tight-binding MO theory and the sum-over-states method of the chemical shift theory. This formalism was applied to the calculation of the C-13 NMR chemical shift of 3D polyethylene chains in the orthorhombic and the monoclinic crystallographic forms by using the STO-3G minimal basis set. The effects of inter- and intra-chain interactions on the C-13 NMR chemical shift and the band structure were evaluated with a change by means of the a and c axes and the b axis in the lattice constants. The calculated results explain reasonably the experimental data. (C) 1999 Elsevier Science B.V. All rights reserved., 1999年09月, 508, 1-3, 181, 191, 研究論文（学術雑誌）
• 査読あり, 英語, PROGRESS IN POLYMER SCIENCE, Diffusion processes in polymer gels as studied by pulsed field-gradient spin-echo NMR spectroscopy, S Matsukawa; H Yasunaga; C Zhao; S Kuroki; H Kurosu; Ando, I, In order to study the diffusional behavior of molecules or polymers in a polymer network with a wide range of the diffusion coefficients, we have developed two kinds of PGSE NMR probes with a maximum strength of the field gradient ranging from 700 to 2000 G cm(-1). By using these probes it is possible to measure the diffusion coefficient D with the order of about 10(-9) cm(2) s(-1). These NMR probes lead to sophisticated knowledge concerning the diffusional behavior of molecules in polymer gels. This review article is concerned with a series of studies on the diffusional behavior of polymer gel systems by means of novel PGSE NMR probes. (C) 1999 Elsevier Science Ltd. All rights reserved., 1999年09月, 24, 7, 995, 1044
• 査読あり, 英語, MAGNETIC RESONANCE IN CHEMISTRY, Conformational analysis of the biphenyl moiety of dimer liquid crystals in the solid state by high-resolution solid-state C-13 NMR and ab initio GIAO-CHF calculations, RN Shimizu; H Kurosu; Ando, I; A Abe; H Furuya, High-resolution C-13 NMR spectra of alpha,omega-bis[(4,4'-cyanobiphenylyl)oxy]alkanes (CBA-n, n = 7, 9 and 10) were measured in chloroform solution and in the polycrystalline state. The spectra of the samples in solution are essentially the same; in the polycrystalline state, on the other hand, the spectrum of CBA-9 presents some differences in the aromatic carbon region in relation to those of CBA-7 and CBA-10' which are similar. Therefore, ab initio GIAO-CHF calculations were carried out and an analysis of the conformation of the biphenyl moiety was attempted by comparing the results of the calculations with the measured high-resolution solid-state C-13 NMR spectra. From these results it was concluded that the torsion angle for the biphenyl moiety of CBA-7 and CBA-10 stays at about 40 degrees. For CBA-9 it is suggested that conformers with torsion angles of about 30 degrees and 60 degrees are also present. Copyright (C) 1999 John Wiley & Sons, Ltd., 1999年07月, 37, 7, 479, 483, 研究論文（学術雑誌）
• 査読あり, 英語, BIOPOLYMERS, C-13-NMR chemical shift tensor and hydrogen-bonded structure of glycine-containing peptides in a single crystal, N Takeda; S Kuroki; H Kurosu; Ando, I, C-13-nmr chemical shift tensor components are reported for a C-13-labeled Gly(1) amide carbonyl carbon of a glycylglycine (Gly(1)Gly(2)) single crystal, a GlyGly . HNO3 single crystal and a GlyGly . HCl . H2O single crystal, for which the three-dimensional crystal structures have already been determined by x-ray diffraction. The tensor components were measured by changing the angle between the crystal plane and the applied magnetic field by using a goniometer designed in this work for use in conventional C-13 cross-polarization/magic angle spinning nmr probe. From these experimental data, the principal values of the C-13 chemical shift tensor and its directions for the Gly(1) amide carbonyl carbon were determined It was found that the C-13 chemical shift tensor components (delta(11), delta(22), and delta(33)) for the Gly(1) amide carbonyl carbon in GlyGly and GlyGly . HNO3 with a >NH ... O=C< type of hydrogen bond depend on the hydrogen-bond length and the directions of the delta(22) components of these peptides are along the hydrogen-bonded >C=O bond axis. In addition, the magnitude of the deviation from the bond axis depends on the hydrogen-bond angle. Further the experimental result for GlyGly . HCl . H2O with a-O-H ... O=C< type of hydrogen bond was discussed. (C) 1999 John Wiley & Sons, Inc., 1999年07月, 50, 1, 61, 69, 研究論文（学術雑誌）
• 査読あり, 英語, Macromolecular Symposia, Morphology and mechanical properties of low-molecular-weight polyethylene and ultrahigh-molecular-weight polyethylene films drawn up to 200-fold, Yuezhen Bin; Miwako Fukuda; Hiromichi Kurosu; Masaru Matsuo, Ultrahigh-molecular-weight polyethylene (UHMWPE) and low-molecular-weight polyethylene (LMWPE) blend films were prepared by gelation/crystallization from solutions. UHMWPE with the viscosity-average molecular weight (M̄v) of 6×106 and three kinds of LMWPE with M̄v < 5×104 were used. The LMWPE/ UHMWPE compositions chosen were 1/1, 2/1, 4/1 and 9/1. The resulting blend gels with the 9/1 composition (10% UHMWPE content) became films by evaporating the solvents, although LMWPE homopolymer gels have no ability to form films. The films with the above compositions could be readily elongated up to 200-fold in a hot oven. Such high elongation is assumed to be due to the existence of a suitable level of entanglements between UHMWPE and LMWPE chains. The orientational degree of LMWPE crystallites became poorer as the LMWPE content in the blend film increased, indicating a decrease in the number of entanglements. The storage modulus of the blend films at the same draw ratio decreased as the LMWPE content increased. The storage modulus of the 1/1 blend film with λ = 200 reached about 50 GPa at 20°C but the storage modulus decreased drastically with further increase in the LMWPE content: the value of the 9/1 blend film with λ = 200 was less than 10 GPa. This means that a suitable level of entanglements between LMWPE and UHMWPE chains plays an important role in transmitting the drawing force effectively and promoting the orientational degree of the c-axis, owing to the crystal transformation from a folded to a fibrous type., 1999年, 147, 1, 14, 研究論文（学術雑誌）, 10.1002/masy.19991470103

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• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, Hydrogen bonding interactions in polyureas as studied by variable-temperature high-resolution H-1 NMR spectroscopy, Q Chen; G Yang; Y Wang; Wu, X; H Kurosu; Ando, I, Variable-temperature high-resolution H-1 NMR experiments on four polyurea samples with different kinds of hard segments and soft segments were carried out in dimethylformamide solution. From these experimental results, it was found that the NH groups of the hard segments of the polymers form different styles of hydrogen-bonds between the amide group of dimethylformamide and the oxygen atom of the soft segment, and that the formation of hydrogen-bonds between the NH groups and oxygen atoms greatly depends on the molecular weight of the soft segment of the polymers. (C) 1998 Elsevier Science B.V. All rights reserved., 1998年11月, 471, 1-3, 183, 188, 研究論文（学術雑誌）
• 査読あり, 英語, POLYMER, A study on dynamics of water in crosslinked poly(N-isopropylacrylamide) gel by nmr spectroscopy, N Tanaka; S Matsukawa; H Kurosu; Ando, I, dynamics of crosslinked poly (N-isopropylacrylamide) gel have been studied by means of pulsed-gradient spin-echo (PGSE) H-1 nuclear magnetic resonance (n.m.r.), pulse H-1 n.m.r. and H-1 n.m.r. imaging. The selfdiffusion coefficients of HDO (D-HDO) in D2O (containing a small amount of HDO) in the gels with various degree of swellings were determined by the PGSE H-1 n.m.r. method. From these experimental results, it was found that the D-HDO is decreased as the degree of swelling is decreased, and D-HDO in the gels with a constant degree of swelling in going from 20 to 45 degrees C is transitionally decreased at about 32 degrees C, which corresponds to the phase transition temperature. From the detailed analysis of proton spin-spin relaxation time T-2 determined by the pulse H-1 n.m.r. method, the process of the volume phase transition of the gel has been elucidated. Furthermore, spatial information about the molecular motion of water in the gel sample was obtained by T-2 enhanced H-1 n.m.r. imaging. (C) 1998 Elsevier Science Ltd. All rights reserved., 1998年09月, 39, 20, 4703, 4706, 研究論文（学術雑誌）
• 査読あり, 英語, POLYMER, A study on dynamics of water in crosslinked poly(N-isopropylacrylamide) gel by nmr spectroscopy, N Tanaka; S Matsukawa; H Kurosu; Ando, I, dynamics of crosslinked poly (N-isopropylacrylamide) gel have been studied by means of pulsed-gradient spin-echo (PGSE) H-1 nuclear magnetic resonance (n.m.r.), pulse H-1 n.m.r. and H-1 n.m.r. imaging. The selfdiffusion coefficients of HDO (D-HDO) in D2O (containing a small amount of HDO) in the gels with various degree of swellings were determined by the PGSE H-1 n.m.r. method. From these experimental results, it was found that the D-HDO is decreased as the degree of swelling is decreased, and D-HDO in the gels with a constant degree of swelling in going from 20 to 45 degrees C is transitionally decreased at about 32 degrees C, which corresponds to the phase transition temperature. From the detailed analysis of proton spin-spin relaxation time T-2 determined by the pulse H-1 n.m.r. method, the process of the volume phase transition of the gel has been elucidated. Furthermore, spatial information about the molecular motion of water in the gel sample was obtained by T-2 enhanced H-1 n.m.r. imaging. (C) 1998 Elsevier Science Ltd. All rights reserved., 1998年09月, 39, 20, 4703, 4706, 研究論文（学術雑誌）
• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, A structural and dynamic study of poly(vinyl alcohol) in the gel state by solid-state C-13 NMR and H-1 pulse NMR, M Kanekiyo; M Kobayashi; Ando, I; H Kurosu; T Ishii; S Amiya, H-1 pulse NMR and high-resolution solid-state C-13 NMR spectra of poly(vinyl alcohol) (PVA) gel were measured to clarify the structure and dynamics of the immobile component of the gel. From H-1 pulse NMR experiments, it was found that the T-2 Signal is mainly composed of three components. The long T-2 component was assigned to the mobile component which comes from the non-crosslinked region, the intermediate T-2 component corresponds to the intermediate immobile component which comes from the vicinity of the crosslinked region, and the short T-2 component corresponds to the immobile component which comes from the crosslinked region in the PVA gel. From high-resolution solid-state C-13 NMR experiments, the mechanism of gel formation was satisfactorily elucidated. Further, dynamic viscoelastic modulus measurements were carried out. These experimental results were satisfactorily explained on the basis of the NMR results. (C) 1998 Elsevier Science B.V. All rights reserved., 1998年06月, 447, 1-2, 49, 59, 研究論文（学術雑誌）
• 査読あり, 英語, MACROMOLECULES, Self-diffusion behavior of solvents in polypeptide gel as studied by pulsed-gradient spin-echo H-1 NMR spectroscopy, CH Zhao; S Matsukawa; H Kurosu; Ando, I, 1998年05月, 31, 9, 3139, 3141, 研究論文（学術雑誌）
• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, High resolution C-13 NMR studies for crystalline and liquid crystalline phases of PB-18 polyester composed of 4,4 '-dihydroxybiphenyl and octadecanedioic acid, M Tokita; M Sone; H Kurosu; Ando, I; J Watanabe, Main-chain liquid crystalline PB-18 polyester composed of 4,4'-dihydroxybiphenyl and octadecanedioic acid forms two distinct crystalline phases, K-1 and K-2, and smectic H (S-H) phase in the order of increasing temperature. The detailed structures of the three phases were studied by C-13 solid-state NMR spectroscopy with variable temperature accessories. With a comparison of the observed C-13 chemical shifts to the calculated C-13 NMR shieldings by FPT-INDO method, the conformations of the mesogenic moiety and alkylene spacer are discussed among these three phases. (C) 1998 Elsevier Science B.V., 1998年05月, 446, 3, 215, 221, 研究論文（学術雑誌）
• 査読あり, 英語, CHEMICAL PHYSICS LETTERS, A study of the dynamics of n-alkane in the rotator phase by using the pulse-field-gradient spin-echo H-1 NMR method, H Yamakawa; S Matsukawa; H Kurosu; S Kuroki; Ando, I, The self-diffusion coefficient (D) and H-1 spin-spin relaxation time (T-2) of n-alkane, n-C24H50, were measured in the rotator and liquid phases over a wide range of temperatures by means of pulse-field-gradient spin-echo H-1 NMR, in order to clarify the molecular motion of the alkane in the rotator and liquid phases. With a decrease in temperature from the liquid phase (65 to 51 degrees C) to the rotator phase (50 to 45 degrees C), the temperature dependence of D is abruptly changed at the transition temperature and the slope for the rotator phase is much larger than that for the liquid phase. This means that the mechanism of their diffusional processes is different. Further, it is found that the temperature dependence of the H-1 T-2 shows similar behavior. (C) 1998 Elsevier Science B.V., 1998年02月, 283, 5-6, 333, 336, 研究論文（学術雑誌）
• 査読あり, 英語, Studies in Physical and Theoretical Chemistry, Chapter 9 Polyethylene and paraffins, Takeshi Yamanobe; Hiromichi Kurosu, 1998年, 84, C, 327, 349, 研究論文（学術雑誌）, 10.1016/S0167-6881(98)80017-7

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• 査読あり, 英語, Studies in Physical and Theoretical Chemistry, Chapter 16 Electrically-Conducting Polymers, Hiromichi Kurosu, 1998年, 84, C, 589, 611, 研究論文（学術雑誌）, 10.1016/S0167-6881(98)80024-4

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• 査読あり, 英語, Polymer, Image analysis of the spatial distribution of paramagnetic Mn2+ ions in a PMAA gel with the application of an electric field by an 1H n.m.r. imaging method, Aki Yamazaki; Yoshio Hotta; Hiromichi Kurosu; Isao Ando, The 1H T2 images for a transverse slice of a PMAA hydrogel with paramagnetic Mn2+ ions under the application of a 3 V DC electric field were observed as a function of elapsed time by means of 270 MHz 1H n.m.r. imaging. By using the relationship between the concentration of Mn2+ ions and the 1H T2 value of water in the gel obtained by 1H pulse n.m.r., the 1H T2 image was converted to the Mn2+ ion concentration image. From these experiments, the spatial distribution of paramagnetic Mn2+ ions in the gel under the application of a 3 V DC electric field was obtained as a function of the elapsed time. © 1997 Elsevier Science Ltd. All rights reserved., 1998年, 39, 8-9, 1511, 1514, 研究論文（学術雑誌）, 10.1016/S0032-3861(97)00265-6

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• 査読あり, 英語, WILEY POLYMER NETWORKS GROUP REVIEW SERIES, VOL 1 - CHEMICAL AND PHYSICAL NETWORKS, Structures and dynamics of polymer gels observed by H-1 NMR imaging and H-1 PGSE NMR methods, Ando, I; H Kurosu; S Matsukawa; A Yamazaki; Y Hotta; N Tanaka, Structure and dynamics of hydropolymer gel systems have been elucidated microscopically and macroscopically by means of H-1 NMR imaging method and pulse-field gradient spin echo (PGSE) H-1 NMR method. Further, it was demonstrated that H-1 NMR imaging and H-1 PGSE NMR methods are very powerful means for elucidating structure and dynamics of polymer gels., 1998年, 331, 346, 研究論文（国際会議プロシーディングス）
• 査読あり, 英語, Annual Reports on NMR Spectroscopy, Structural Studies of Hydrogen-bonded Peptides and Polypeptides by Solid-state NMR, N. Asakawa; T. Kameda; S. Kuroki; H. Kurosu; S. Ando; I. Ando; A. Shoji, 1998年, 35, C, 55, 137, 研究論文（学術雑誌）, 10.1016/S0066-4103(08)60112-X

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• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, Structure of peptides and polypeptides in the solid state as elucidated by NMR chemical shift, Ando, I; T Kameda; N Asakawa; S Kuroki; H Kurosu, It is reviewed that through the observation of solid-state C-13 NMR chemical shift, the main-chain conformation and hydrogen-bonded structure of peptides, polypeptides and proteins in the solid state have been successfully elucidated, and the combination of solid stale C-13 NMR and chemical shift calculation by quantum chemistry is a powerful means for the structural characterization. Furthermore, it is briefly introduced that solid state NMR of N-15 and O-17 nuclei is very useful for obtaining information about hydrogen-bonded structure. This review article is communicated on the basis of our recent works on structural characterization of peptides and polypeptides including proteins in the solid state by high-resolution solid-state NMR spectroscopy and its combination with quantum chemical calculation. (C) 1998 Elsevier Science B.V., 1998年01月, 441, 2-3, 213, 230, 研究論文（学術雑誌）
• 査読あり, 英語, POLYMER GELS AND NETWORKS, Spatial information on a polymer gel as studied by H-1-NMR imaging: 4. Shrinkage by the application of an alternating electric field to a polymer gel, Y Hotta; T Shibuya; H Yasunaga; H Kurosu; Ando, I, We have measured the spatial distribution of H-1 spin density and H-1 spin-spin relaxation timer T-2, of water molecules in a crosslinked poly(methacrylic acid) (PMAA) gel under an alternating current (AC) electric field by means of proton nuclear magnetic resonance imaging. The experimental results show that a cylindrical gel shrinks to a cylindrical shape at long elapsed time after the application of an AC electric field, and that the H-1 spin densities on both electrode sides of the gel are high and the mobilities are low. The translational behavior of water molecules in the gel during shrinkage processes under an AC electric field is discussed at the molecular level. (C) 1998 Elsevier Science Ltd. All rights reserved., 1998年, 6, 1, 1, 11, 研究論文（学術雑誌）
• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, Conformational behaviour of poly(aspartic acid) and its sodium salt in the solid state as studied by high-resolution solid-state C-13-NMR spectroscopy, PX Wang; S Matsukawa; T Kameda; H Kurosu; Ando, I, High-resolution C-13 CP/MAS NMR spectra of poly(aspartic acid) (PAA) and its sodium salt (PAANa) obtained with various neutralization numbers, n ( = [COONa]/[COOH + COONa], where [x] is the molar concentration of x), have been measured over a wide range of temperatures, in order to elucidate the conformation and its stability in the solid state. From these experimental results it was found that, at room temperature (25 degrees C), the main chain of PAA takes a mixture of right-handed alpha (alpha(R))-helix, omega-helix and beta-sheet forms and, with an increase in temperature from 25 degrees C to 180 degrees C, changes from alpha(R)-helix form and omega-helix form to beta-sheet forms. On the other hand, the main chain of PAANa takes the right-handed omega(R)-helix form in the temperature range from 25 degrees C to 210 degrees C. With a decrease in the neutralization number, PAANa changes to PAA and the NMR spectra are correspondingly changed. (C) 1997 Elsevier Science B.V., 1997年12月, 435, 3, 229, 234, 研究論文（学術雑誌）
• 査読あり, 英語, SOLID STATE NUCLEAR MAGNETIC RESONANCE, Solid-state variable-temperature H-1 MAS NMR studies on deuterated polyethylene, Q Chen; H Hurosu; Ando, I; Wu, X, Solid-state varible-temperature/magic angle spinning(VT/MAS) H-1 NMR measurements were carried out on deuterated polyethylene. From these experimental results it was found that the H-1 chemical shift induced by conformational and morphological changes of the polyethylene sample is within the linewidth of approximate to 0.5 ppm. Furthermore, from MAS/dipolar decoupling experiments it was found that the resonance frequency of the proton varies linearly with the inverse square of the deuterium decoupling power. This experimental finding is discussed theoretically. (C) 1997 Elsevier Science B.V., 1997年02月, 7, 4, 319, 325, 研究論文（学術雑誌）
• 査読あり, 英語, POLYMER JOURNAL, Orientational ordering of a dimer liquid crystal by high-resolution solid-state C-13 NMR spectroscopy, RN Shimizu; H Kurosu; Ando, I; A Abe; H Furuya; S Kuroki, The ordering of a dimer liquid crystal, alpha,omega-bis[(4,4'-cyanobiphenylyl)oxy]decane (CBA-IO), was studied by variable-temperature high-resolution solid-state C-13 NMR. A large transitional change of the C-13 chemical shift was observed on going from the isotropic to the nematic phase due to uniaxial alignment of the molecule. The principal values of the C-13 chemical shift tensor have been determined by the Herzfeld-Berger method for CBA-IO itself. The molecular axis is assumed to lie parallel to the line connecting the centers of both mesogenic cores, and the evaluation of the order parameters along the molecular axis, (S-zz), mesogene axis (S-zz(ring)) and C-gamma-C-epsilon, axis (S-zz(C nu-C epsilon)) was attempted here, using the obtained isotropic C-13 chemical shift and principal values of the C-13 chemical shift tensor, and taking into account the conformational behavior of the flexible spacer in the frame of rotational isomeric state (RIS) approach. The order parameter of the molecule S-zz increased from 0.79 to 0.89 with decrease of 17.5 degrees C in temperature from nearby the nematic-isotropic transition point. S-zz(ring) increased from 0.74 to 0.80 with decrease of temperature whereas S-zz(C gamma-C epsilon) and the conformation of the spacer was essentially unaltered in the same temperature range., 1997年, 29, 7, 598, 602, 研究論文（学術雑誌）
• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, Hydrogen-bonded structure and C-13 NMR chemical shift tensor of amino acid residue carbonyl carbons of peptides and polypeptides in the crystalline state .1., T Kameda; N Takeda; S Kuroki; H Kurosu; S Ando; Ando, I; A Shoji; T Ozaki, C-13 chemical shift tensor components (delta(11) delta(22) and delta(33)) Of glycine (Gly), L-valine (Val), L-leucine (Leu), and L-asparagine (Asp) residue carbonyl carbons (C = O) of peptides and polypeptides covering a wide range of hydrogen-bond lengths (R(N-O)) in the crystalline state have been measured by slow magic-angle-spinning solid-state C-13 NMR. From these experiments, it is found that delta(22), which lies approximately along the amide C = O bond, moves linearly downfield with a decrease in R(N-O) and the slope and intercept of the variation of delta(22) against R(N-O) depend on the amino acid residue. Using this relationship, the R(N-O) values for polypeptides were determined by observation of the 822 Of the guest Gly residue incorporated into host polypeptides. delta(11), and delta(33) are found to be insensitive to the change in R(N-O) and amino acid residues. Moreover, it is found that the sum of delta(11) and delta(33) is almost constant (337.5 +/- 3.5 ppm) and is independent of the amino acid residue. The quantum-chemical calculation on the C-13 shielding constant for a peptide model compound was carried out by the finite perturbation theory within the INDO framework. This calculation acceptably explains the experimental results., 1996年10月, 384, 1, 17, 23, 研究論文（学術雑誌）
• 査読あり, 英語, MACROMOLECULES, Solid-state C-13 MAS NMR studies of hyper-cross-linked polystyrene resins, RV Law; DC Sherrington; CE Snape; Ando, I; H Kurosu, C-13 CP/MAS NMR techniques have been used to evaluate the structure of four hyper-cross-linked polystyrene resins. Single-pulse excitation (SPE) C-13 spectra have allowed the various types of carbon atoms present in the resins to be quantified, and similarly H-1 CRAMPS spectra have facilitated quantification of the various hydrogen atom types. Two hyper-cross-linked resins prepared by exhaustive methylene bridging of conventional lightly cross-linked styrene-divinylbenzene resins have very high quaternary aromatic carbon contents. These can be explained adequately only if vert high levels of double methylene bridging of aromatic groups occurs. Approximately 10% of aromatic groups also retain a chloromethyl group from incomplete methylene bridging. Two further hyper-cross-linked resins reportedly prepared from conventional heavily cross-linked divinylbenzene (55% technical grade) resins appear in one instance to exploit residual unreacted double bonds (and possibly additional divinylbenzene) to generate the secondary cross-links, and in another to use SOCl2/Lewis acid to introduce very high levels of sulfoxide secondary cross-links. Dynamic NMR experiments suggest that the latter two hyper-cross-linked species retain more flexibility and mobility than those prepared via more conventional methylene bridging techniques., 1996年09月, 29, 19, 6284, 6293, 研究論文（学術雑誌）
• 査読あり, 日本語, JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN, Structural and dynamical analyses of small and large molecules in the solid state by high resolution solid state NMR, H Kurosu; Ando, I, The application of high-resolution solid-state NMR spectroscopy to structural and dynamical analyses of solid peptides, polypeptides, calixalene, conductive polymers, polyesters and poly (ethylene oxide) in the solid state have been introduced. It has been demonstrated that the high-resolution solid-state NMR spectroscopy is a very powerful means for elucidating the structure and dynamics of molecules in the solid state., 1996年05月, 54, 5, 367, 374, 研究論文（学術雑誌）
• 査読あり, 英語, JOURNAL OF MATERIALS CHEMISTRY, Chemical modification of monolithic poly(styrene-divinylbenzene) PolyHIPE(R) materials, NR Cameron; DC Sherrington; Ando, I; H Kurosu, Monolithic samples of highly porous poly(styrene/DVB) PolyHIPE(R) have undergone a number of electrophilic aromatic substitution reactions, namely sulfonation, nitration and bromination. Mild, hydrophobic reagents and homogeneous reaction conditions were sought in an effort to achieve uniform chemical modification, to a reasonable degree of substitution, throughout the large polymeric structures. Thus, sulfonation was Carried out with lauroyl sulfate in cyclohexane, nitration with tetrabutylammonium nitrate-trifluoroacetic anhydride (TBAN-TFAA) in dichloromethane and bromination with bromine-stannic chloride in dichloromethane. An average degree of sulfonation of 2.4 mmol g(-1) was achieved, with a drop in sulfonic acid content of approximately 1 mmol g(-1) from surface to centre. Nitration occurred to a lesser extent, with similar differences in substitution between surface and centre being observed. PolyHIPE(R) monolithic samples were brominated to an extent of 3.6 mmol g(-1) furthermore, this was uniform across the entire substrate. The differences in extent of each reaction are explained by consideration of such factors as the nature of the solvent, polarity of the reagents and compatibility between the reagents and the polymer matrix throughout the reactions., 1996年05月, 6, 5, 719, 726, 研究論文（学術雑誌）
• 査読あり, 英語, POLYMER JOURNAL, Spatial information on a polymer gel as studied by H-1 NMR imaging .3. Shrinkage by the application of an electric field to a composite polymer gel, H Kurosu; T Shibuya; H Yasunaga; Ando, I, H-1 NMR imaging patterns of a composite poly(methacrylic acid) (PMAA) gel being a double cylindrical rod, for which the swelling degrees of the inside and outside gels are different from each other, were measured under the application of an electric field. On the basis of these experimental results the shrinkage process was studied. It was found that the shrinkage process of the composite PMAA gel is different from the case of a homogenous cylindrical PMAA gel as reported previously [Macromolecules, 28, 4377 (1995)]. Details of the shrinkage process were discussed at the molecular level., 1996年, 28, 1, 80, 85, 研究論文（学術雑誌）
• 査読あり, 英語, ACTA POLYMERICA, Structural and dynamical studies of C-13-labeled polyethylene adsorbed on the surface of silica gel by high-resolution solid-state C-13 NMR spectroscopy, D Inoue; H Kurosu; Q Chen; Ando, I, C-13 CP/MAS NMR spectra of 10% C-13-labeled polyethylene adsorbed on the surface of silica gel were measured by means of high-resolution solid-state C-13 NMR. From these experimental results, it was found that adsorbed polyethylene has immobile and mobile parts. In the immobile part, the polyethylene takes the trans conformation as the major conformation and gauche as the minor conformation, and in the mobile part fast transition between trans and gauche conformations occurs. Furthermore, in order to elucidate the dynamics of the polyethylene, C-13 spin-lattice relaxation times T-1 were measured. It was found that the molecular motion of the polyethylene in the mobile part is strongly restricted, compared with the noncrystalline component of polyethylene in bulk., 1995年12月, 46, 6, 420, 423, 研究論文（学術雑誌）
• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, STRUCTURAL CHARACTERIZATION OF POLYACENIC POLYMERS IN THE SOLID-STATE BY HIGH-RESOLUTION C-13 NMR-SPECTROSCOPY, H KUROSU; Y NAKAJIMA; ANDO, I, The solid-state C-13 CP/MAS NMR spectra of undoped and iodine-doped polyacenic polymers with different electrical conductivity which were prepared by heating at high temperatures of 590 to 670 degrees C have been measured by means of solid-state high-resolution C-13 NMR. The C-13 Signal of the polyacenic polymer consists of four peaks. The four peaks obtained have been assigned to the structures of polyacenic polymer and a small amount of unreacted phenolformaldehyde resin. Further, the structure of polyacenic polymer in the solid state was discussed as related to the electrical conductivity., 1995年08月, 355, 1, 27, 32, 研究論文（学術雑誌）
• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, C-13 CPMAS NMR-STUDY OF THE STRUCTURE OF P-T-BUTYLCALIX[4]ARENE-ALKYLBENZENE CLATHRATES IN THE SOLID-STATE, T YAMANOBE; NAKAMURA, I; K HIBINO; T KOMOTO; H KURUSU; ANDO, I; Y NAKAMOTO; S ISHIDA, The NMR chemical shifts measured by the C-13 CPMAS method for clathrates of p-t-butylcalix[4]arenes including mobile alkylbenzenes in the solid state revealed that the alkyl groups of the guest molecules are located in the cavity of p-t-butylcalix[4]arene, depending on the size of the alkyl group. It was found that n-alkylbenzenes are easily incorporated into p-t-butylcalix[4]arene in the order of toluene > ethylbenzene greater than or equal to n-propylbenzene. For isopropylbenzene, the bulky isopropyl group prevents incorporation into the cavity of the host molecule., 1995年08月, 355, 1, 15, 20, 研究論文（学術雑誌）
• 査読あり, 英語, MACROMOLECULES, SPATIAL INFORMATION ON A POLYMER GEL AS STUDIED BY H-1-NMR IMAGING .2. SHRINKAGE BY THE APPLICATION OF AN ELECTRIC-FIELD TO A POLYMER GEL, T SHIBUYA; H YASUNAGA; H KUROSU; ANDO, I, H-1 NMR imaging patterns with information about the spatial distribution of H-1 spin density and H-1 spin-spin relaxation time T-2 of water molecules in a cross-linked poly(methacrylic acid) (PMAA) gel were measured, in order to clarify the translational behavior of water molecules in the gel under shrinkage processes by the application of an electric field. From the experimental result it was found that a cylindrical gel shrank to a wine-stopper-like shape at long elapsed time after the application of an electric field. On the positive electrode side, the H-1 spin densities were high and the mobilities were low, and on the negative electrode side, the H-1 spin densities were low and the mobilities high. Further, details of the shrinkage process were discussed at the molecular level., 1995年06月, 28, 13, 4377, 4382, 研究論文（学術雑誌）
• 査読あり, 英語, JOURNAL OF POLYMER SCIENCE PART B-POLYMER PHYSICS, STRUCTURAL CHARACTERIZATION OF POLYPYRROLE IN THE SOLID-STATE BY HIGH-RESOLUTION N-15 NMR-SPECTROSCOPY .2., H KUROSU; M KIKUCHI; ANDO, I, The solid-state N-15 CP/MAS NMR spectra and N-15 spin-lattice relaxation times (T-1) of doped and dedoped N-15-labeled polypyrroles prepared by electrochemical polymerization, have been measured by means of high-resolution solid-state N-15 NMR. The N-15 Signal of polypyrrole consists of four peaks decomposed by line shape analysis. The four peaks obtained have been assigned to the various structures of polypyrrole. Further, the half-width of the N-15 NMR spectra of polypyrroles is discussed as related to the electrical conductivity. (C) 1995 John Wiley and Sons, Inc., 1995年04月, 33, 5, 769, 775, 研究論文（学術雑誌）
• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, CONFORMATION AND MOLECULAR-MOTION OF A POLY(L-GLUTAMATE) WITH LONG N-ALYL SIDE-CHAINS IN THE SOLID-STATE AND THE LIQUID-CRYSTALLINE STATE AS STUDIED BY HIGH-RESOLUTION C-13 NMR-SPECTROSCOPY .2., E KATOH; H KUROSU; S KUROKI; ANDO, I, C-13 CP/MAS and PST/MAS NMR experiments are carried out on poly(gamma-n-octadecyl L-glutamate) (POLG) over a wide range of temperatures from -40 to 230-degrees-C to elucidate dynamical and conformational features in the solid state and the liquid-crystalline state, in addition to the experimental findings reported previously. From these experimental results it was found that as the temperature is increased and the methylene carbons of the n-alkyl side-chains are away from the main-chain, the gauche fraction is increased but the magnitude of its temperature change is decreased. Furthermore, from the experimental results on the temperature dependence of the C-13 chemical shift of the main-chain carbonyl carbon, it was found that the main-chain takes the right-handed alpha-helix form in the temperature range from -40 to 230-degrees-C, and that as the temperature is increased, the amide hydrogen-bond length in the main-chain is increased slightly., 1994年09月, 326, 145, 150, 研究論文（学術雑誌）
• 査読あり, 英語, MAGNETIC RESONANCE IN CHEMISTRY, NITROGEN NMR OF SOME SULFUR DIIMIDE ANIONS AND CALCULATED (GIAO) NITROGEN SHIELDING CONSTANTS, B WRACKMEYER; S GERSTMANN; M HERBERHOLD; GA WEBB; H KUROSU, Sulphur diimide anions of the type [NSN](2-) (1), [RNSN](-) (1), [R = (1)Bu (3), SiMe(3) (4), (1)Bu(2)P (5)] were prepared with the counter ions [(1)Bu(4)N](+) or [(Me(2)N)(3)S](+) (for 1, 3, 4) and K+ (for 5) and studied in solution by N-14 NMR, and for assignment purposes by N-15 NMR (4). The experimentally determined N-14 chemical shifts (delta N) were compared with nitrogen shielding constants calculated by the gauge included atomic orbitals (GIAO) technique, and a linear relationship between sigma(N(calc)) and delta N was obtained. This correlation serves to support the Z configuration of the anions [RNSN](-), analogous to the isoelectronic N-sulphinylamines. On this basis, two N-14 resonance signals reported in the literature with uncertain assignment can be attributed to [HNSN](-) (2), and the previously assigned delta N values suggest that the anion [HNSNS](-) (6) adopts the Z/E configuration., 1994年08月, 32, 8, 492, 495, 研究論文（学術雑誌）
• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, STRUCTURAL STUDY OF PEPTIDES CONTAINING L-ALANINE RESIDUES BY AB-INITIO CHEMICAL SHIELDING CALCULATION, N ASAKAWA; H KUROSU; ANDO, I, The correlation between the chemical shifts and the main-chain dihedral angles of peptides containing L-alanine residues are estimated by carrying out chemical shielding calculations using the coupled Hartree-Fock method with the gauge invariant atomic orbitals (GIAO-CHF). This aids understanding of the C-13 chemical shift behavior of the peptides and polypeptides., 1994年07月, 323, 279, 285, 研究論文（学術雑誌）
• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, AN NMR-STUDY OF STRUCTURE AND DYNAMICS OF POLY(FUMARATE)S IN THE SOLID-STATE (II), H KUROSU; K SUZUKI; ANDO, I; T OTSU, C-13 spin-lattice relaxation times (T1c) and C-13 CP-MAS NMR spectra of poly(methyl tert-butyl fumarate) (PMETBF) and poly(isopropyl tert-butyl fumarate) (PIPTBF) were measured over a wide range of temperatures (-30 to 100-degrees-C). From these results, the molecular motion of the main chain and side chains of these polymers was elucidated, and the reorientation frequency of the main chain of PMETBF and PIPTBF was found to be below 67.8 MHz in this temperature range. Further, it was found that the mobilities for the meso-meso (mm) and meso-racemic (mr) triads of PIPTBF were almost the same below 85-degrees-C, but above 85-degrees-C the mobility for the mm triad was lower than that for the mr triad. However, there was no difference in the mobility between the mm and mr triads of PMETBF within the measured temperature range., 1994年05月, 321, 3, 229, 237, 研究論文（学術雑誌）
• 査読あり, その他, Macromolecules, Rigid-Rod Polyesters with Flexible Side Chains Based on 1,4-Dialkyl Esters of Pyromellitic Acid and 4,4′-Biphenol. 5. High-Resolution ¹³C NMR Studies for Crystalline and Liquid Crystalline Layered Phases, Masato Sone; Brian R. Harkness; Hiromichi Kurosu; Isao Ando; Junji Watanabe, Rigid-rod aromatic B-Cn polyesters with long alkyl side chains, composed of 1,4-dialkyl esters of pyromellitic acid and 4,4′-biphenol, form two distinct types of crystalline phases, K1 and K2, depending on the length of alkyl side chain. These crystalline phases are characterized by a layered structure, in which the aromatic main chains are packed into a layer with the side chains crystallized in the space between the layers. The detailed structures for these two crystalline phases were studied by 13C solid-state NMR spectroscopy from which it was found that there are remarkable differences in the main-chain conformation and in the packing structure of the side chains. In the K1 crystal formed by the B-Cn polymers with shorter side chains, the aromatic main chain assumes a twisted conformation with the side chains packed into an orthorhombic lattice. In contrast, in the K2 crystal of the longer side-chain B-Cn polymers, the main chains assume a coplanar conformation with the side chains packed into a triclinic lattice. The NMR studies have also been extended to the two types of layered mesophases, LC-1 and LC-2, formed by these polymers. In these phases, the side chains are molten, with the main chains in the LC-1 and LC-2 phases assuming conformations similar to those in the K1 and K2 crystals, respectively. FPT-INDO calculations for the conformational energy have shown that the coplanar conformation in the K2 and LC-2 phases is strongly disfavored whereas the twisted conformation is stable. It is believed that the disfavored coplanar conformation observed in the K2 and LC-2 phases is forced by the layered segregation of the aromatic main chains and the long aliphatic side chains. © 1994, American Chemical Society. All rights reserved., 1994年05月01日, 27, 10, 2769, 2777, 研究論文（学術雑誌）, 10.1021/ma00088a018

  DOI URLScopus URLScopus Citedby URL
• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, CONFORMATION AND MOLECULAR-MOTION OF POLY(L-GLUTAMATE) WITH LONG N-ALKYL SIDE-CHAINS IN THE SOLID-STATE AND THE LIQUID-CRYSTALLINE STATE AS STUDIED BY HIGH-RESOLUTION C-13 NMR-SPECTROSCOPY, E KATOH; H KUROSU; ANDO, I, C-13 CP-MAS NMR experiments are carried out for poly(gamma-n-octadecyl-L-glutamate) over a wide range of temperatures, in order to elucidate exact dynamic and conformational features in the solid state and the liquid crystalline state, as well as from the experimental findings reported previously by C-13 CP-MAS NMR and H-1 pulsed NMR methods. From these experimental results, it was found that at low temperatures n-alkyl side chains take an all-trans zigzag conformation, above 40-degrees-C they behave like liquid alkanes in a mobile state, and in the temperature range 0-20-degrees-C they are in a phase similar to the rotator phase of n-alkanes. The main chain takes on a right-handed alpha-helix conformation within the temperature range -40-230-degrees-C. Further, it was found that at temperatures above 40-degrees-C the polymer forms several liquid crystalline phases, in which the molecular motions of the polymer are different from each other., 1994年03月, 318, 123, 131, 研究論文（学術雑誌）
• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, A STRUCTURAL STUDY OF PEPTIDES AND PROTEINS CONTAINING L-ALANINE RESIDUES BY C-13 NMR-SPECTROSCOPY COMBINED WITH AB-INITIO CHEMICAL-SHIFT CALCULATIONS, N ASAKAWA; H KUROSU; ANDO, I; A SHOJI; T OZAKI, From the observation of solid-state C-13 NMR chemical shifts of L-alanine residues which are contained in some peptides, and the C-13 chemical shift calculations employing the coupled-Hartree Fock method with gauge-invariant-atomic-orbital, it was found that the C-13 chemical shift of the C(beta)-carbon in the L-alanine residue is related to the main-chain dihedral angles, phi, psi, but that of the C(alpha)-carbon is affected not only by dihedral angles but also by hydrogen-bonding structure. These results were successfully applied to the structural study of proteins in solution, ribonuclease H from Escherichia coli and basic pancreatic trypsin inhibitor., 1994年01月, 317, 1-2, 119, 129, 研究論文（学術雑誌）
• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, SIDE-CHAIN CONFORMATION OF POLY(L-PROLINE) FORM-II IN THE CRYSTALLINE STATE AS STUDIED BY HIGH-RESOLUTION SOLID-STATE C-13 NMR-SPECTROSCOPY, M SONE; H YOSHIMIZU; H KUROSU; ANDO, I, High-resolution C-13 NMR spectra of poly(L-proline) form II in the solid state were measured using the CP MAS and PST/MAS techniques over a wide range of temperatures. From these results. it was found that the pyrrolidine ring in the form II takes two types of conformations, and the mobilities of the pyrrolidine rings in the two types of conformations are different from each other. The behaviour of the main-chain and side-chain conformations of poly(L-proline) was elucidated through the observed C-13 NMR chemical shifts and the calculations of the C-13 NMR shielding constant and total energy of these polypeptides within the tight-binding INDO/S sum-over-states framework., 1994年01月, 317, 1-2, 111, 118, 研究論文（学術雑誌）
• 査読あり, その他, Journal of Molecular Structure, Ring puckering of the pyrrolidine ring of poly (l-proline) form I as studied by variable-temperature high-resolution ¹³C NMR spectroscopy, Masato Sone; Hiroaki Yoshimizu; Hiromichi Kurosu; Isao Ando, 1993年12月10日, 301, C, 227, 230, 研究論文（学術雑誌）, 10.1016/0022-2860(93)80247-S

  DOI URLScopus URLScopus Citedby URL
• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, AN NMR-STUDY OF STRUCTURE AND DYNAMICS OF POLY(FUMARATE)S IN THE SOLID-STATE, H KUROSU; T YAMADA; ANDO, I; K SATO; T OTSU, C-13 cross polarization/magic angle spinning (CP/MAS) NMR spectra and partially-relaxed C-13 NMR spectra of poly(diisopropyl fumarate) (PDiPF) and poly(dicyclohexyl fumarate) (PDCHF) in the solid state were measured over a wide range of temperatures. On the basis of these experiments, C-13 spin-lattice relaxation times (T1C) for the polymers were determined as a function of temperature. From these results, the molecular motion of the main chain and side chains of the polymers was clearly elucidated. In addition, H-1 spin-lattice relaxation times (T1H) and H-1 spin-lattice relaxation times in the rotating frame (T1rho(H)) of the polymers were measured by H-1 pulse NMR over a wide range of temperatures. From these results, dynamics of the main chain and side chains of these polymers was elucidated. The reorientation frequency of the main chain of PDiPF is about 43 kHz at 120-degrees-C, while that of PDCHF at 120-degrees-C is less than this. These pulse NMR results do not conflict with the CP/MAS NMR results., 1993年12月, 300, 303, 311, 研究論文（学術雑誌）
• 査読あり, 英語, MAGNETIC RESONANCE IN CHEMISTRY, THEORETICAL-STUDY OF THE GAMMA-GAUCHE EFFECT FOR AN N-PARAFFIN BY USING AN ABINITIO GIAO-CHF PROCEDURE, H KUROSU; ANDO, I; GA WEBB, Ab initio C-13 nuclear shielding calculations of the gamma-gauche effect for an n-paraffin using the GIAO-CHF procedure are reported. The geometrical parameters used are optimized for each dihedral angle. The dihedral angle dependences of shielding constant calculations are carried out and the gamma-gauche effect on n-octane is discussed., 1993年04月, 31, 4, 399, 402, 研究論文（学術雑誌）
• 査読あり, 英語, COMPUTER AIDED INNOVATION OF NEW MATERIALS II, PTS 1 AND 2, STRUCTURE AND MOLECULAR-MOTION OF POLY(ETHYLENE OXIDE) IN THE SOLID-STATE AS STUDIED BY QUANTUM-CHEMISTRY AND SOLID-STATE NMR, H KUROSU; ANDO, I, 1993年, 1401, 1404, 研究論文（国際会議プロシーディングス）
• 査読あり, 英語, COMPUTER AIDED INNOVATION OF NEW MATERIALS II, PTS 1 AND 2, A QUANTUM-CHEMICAL STUDY OF PVA CRYSTAL-STRUCTURE, T ISHII; S AMIYA; H KUROSU; ANDO, I, 1993年, 1405, 1408, 研究論文（国際会議プロシーディングス）
• 査読あり, 英語, MACROMOLECULES, SPATIAL INFORMATION ON A POLYMER GEL AS STUDIED BY H-1-NMR IMAGING .1. IMAGE-ANALYSIS OF STRESS-STRAIN, H YASUNAGA; H KUROSU; ANDO, I, H-1 NMR imaging experiments were carried out to obtain spatial information on the propagation of the strain induced by stress in a cross-linked poly(methacrylic acid) (PMAA)/water gel. The H-1 spin density and spin-spin relaxation time enhanced NMR imaging patterns for water contained in a PMAA gel under stress were successfully observed. From these results it was found that the spatial distributions of the H-1 spin density and the molecular motion of water molecules in the gel are changed by altering the strength of stress and that the H-1 spin density and the molecular motion of water in the compressed region become lower and slower, respectively, compared with those in the surrounding uncompressed region., 1992年11月, 25, 24, 6505, 6509, 研究論文（学術雑誌）
• 査読あり, 英語, MAGNETIC RESONANCE IN CHEMISTRY, ABINITIO C-13 NUCLEAR SHIELDING CALCULATIONS FOR SOME HYDROCARBONS USING THE GIAO PROCEDURE, H KUROSU; GA WEBB; ANDO, I, The results of some ab initio GIAO-CHF C-13 shielding calculations for some hydrocarbons, performed with several basis sets, are reported and compared with experimental data. Optimized and experimental molecular geometries have been used in these calculations. The effect of the choice of basis set and geometric parameters on the calculated shieldings are discussed., 1992年11月, 30, 11, 1122, 1124, 研究論文（学術雑誌）
• 査読あり, 英語, MACROMOLECULES, CONFORMATIONAL BEHAVIOR OF POLY(BETA-BENZYL L-ASPARTATE) IN THE SOLID-STATE AS STUDIED BY VARIABLE-TEMPERATURE C-13 CROSS-POLARIZATION MAGIC ANGLE SPINNING NUCLEAR-MAGNETIC-RESONANCE SPECTROSCOPY, T AKIEDA; H MIMURA; S KUROKI; H KUROSU; ANDO, I, Carbon-13 cross-polarization/magic angle spinning nuclear magnetic resonance experiments are carried out for poly(beta-benzyl L-aspartate)(PBLA) over a wide range of temperatures, in order to elucidate the stability of the conformation in the solid state. From these experimental results, we obtained the following results on the thermal stability of the main chain. The main chain of PBLA takes on a right-handed a-helical conformation (alpha(R)-helix) within the temperature range from room temperature (23-degrees-C) to 117-degrees-C, and the main-chain conformation predominantly changes at about 128-degrees-C from an alpha(R)-helix form to a left-handed omega-helical form (omega(L)-helix), although minor transition to the beta-sheet form occurs. In the temperature range from 128 to 139-degrees-C a mixture of three types of conformations, the alpha(R)-helix, omega(L)-helix, and beta-sheet forms, coexist. At 150-degrees-C the alpha(R)-helix form completely transforms to the omega(L)-helix or beta-sheet form, and in the temperature range from 150 to 161-degrees-C a mixture of both the forms exists. At 173-degrees-C the maim-chain conformation completely becomes the beta-sheet conformation., 1992年10月, 25, 21, 5794, 5797, 研究論文（学術雑誌）
• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, STRUCTURE AND C-13 NMR CHEMICAL-SHIFT BEHAVIOR OF N-ALKANE CHAINS IN THE ROTATOR PHASE AS STUDIED BY THE TIGHT-BINDING MO THEORY WITHIN THE INDO/S FRAMEWORK, S ISHIKAWA; H KUROSU; ANDO, I, Tight-binding MO calculations on the C-13 NMR chemical shifts for n-alkane chains in the rotator phase have been carried out within the INDO/S sum-over-states framework, taking into account the interchain interactions. The calculations show that the interchain interactions play an important role in determining chemical shift behaviour in the rotator phase. The relationship between the structure and C-13 NMR chemical shift was further clarified through the understanding of the electronic state of the n-alkane chains in the rotator phase., 1992年10月, 273, 233, 241, 研究論文（学術雑誌）
• 査読あり, 英語, Molecular Crystals and Liquid Crystals Science and Technology. Section A. Molecular Crystals and Liquid Crystals, Anomalous temperature dependence of low-energy-electron transmission spectra of thin films of tetrakis(nonylth10)-tetrathiafulvalene (TTC9-TTF), N. Ueno; K. Sugita; H. Kurosu; K. Seki; G. Saito; H. Inokuchi, Temperature dependence of low-energy-electron transmission spectra was measured for thin films of a molecular fastener, tetrakis(nonylthio)tetrathiafulvalene. 10 spectral features, which can be ascribed to the structure of the conduction bands, were observed in the energy region of incident electron of 0 — 15 eV. They showed a large temperature dependence of the energy position as well as of the sharpness and the intensity. The energy positions shifted ∼0.6 eV to high-energy side by cooling from room temperature to −124°C. Such a large energy shift was not observed for other thin films consisting of Iong-alkyl molecules, and is considered as a result of the molecular fastener effects. © 1992, Taylor & Francis Group, LLC. All rights reserved., 1992年06月01日, 218, 1, 171, 176, 研究論文（学術雑誌）, 10.1080/10587259208047035

  DOI URL
• 査読あり, 英語, JOURNAL OF POLYMER SCIENCE PART B-POLYMER PHYSICS, DYNAMIC STUDY OF THE NONCRYSTALLINE PHASE OF C-13-LABELED POLYETHYLENE BY VARIABLE-TEMPERATURE C-13 CP MAS NMR-SPECTROSCOPY, Q CHEN; T YAMADA; H KUROSU; ANDO, I; T SHIONO; Y DOI, The C-13 spin-lattice relaxation times T1 of C-13-labeled polyethylene crystallized under different conditions were measured at temperatures from -120 to 44-degrees-C by variable-temperature solid-state high-resolution C-13 nuclear magnetic resonance (NMR) spectroscopy, in order to determine accurately the dynamics of the noncrystalline region of the polymer. From these results, it was found that the T1 minimum for the CH2 carbons in the noncrystalline region of solution-crystallized polyethylene with high crystallinity appears at higher temperature by about 20-degrees-C than that of melt-quenched polyethylene with low crystallinity. This means that the molecular motion of the CH2 carbons in the noncrystalline regions is more constrained at a given temperature in the material of higher crystallinity. Furthermore, dynamics of the noncrystalline region is discussed in terms of the C-13 dipolar dephasing times., 1992年05月, 30, 6, 591, 601, 研究論文（学術雑誌）
• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, STRUCTURAL CHARACTERIZATION OF POLYPYRROLE IN THE SOLID-STATE BY HIGH-RESOLUTION N-15 NMR-SPECTROSCOPY COMBINED WITH QUANTUM-CHEMISTRY, M KIKUCHI; H KUROSU; ANDO, I, The N-15 CP/MAS NMR spectra of doped and undoped N-15-labeled polypyrroles in the solid state, prepared by electrochemical polymerization, were measured by means of high-resolution solid-state NMR and related to electrical conductivity. From these results, it was found that the N-15 signal of polypyrrole consists of at least four peaks which were decomposed by computer-fitting. In order to obtain systematic information on the structure and electronic structure, a quantum chemical calculation was carried out to assist in analyzing the four N-15 peaks., 1992年05月, 269, 1-2, 183, 195, 研究論文（学術雑誌）
• 査読あり, 英語, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, HYDROGEN-BONDING EFFECT ON C-13 NMR CHEMICAL-SHIFTS OF L-ALANINE RESIDUE CARBONYL CARBONS OF PEPTIDES IN THE SOLID-STATE, N ASAKAWA; S KUROKI; H KUROSU; ANDO, I; A SHOJI; T OZAKI, In order to investigate the relationship between hydrogen-bond length and C-13 NMR chemical shifts of L-alanine carbonyl carbons in peptides in the solid state, C-13 CP-MAS NMR spectra were measured for a series of peptides containing L-alanine residues, for which the crystal structures were already determined by X-ray diffractions. From the results of the observed C-13 chemical shifts, it was found that the isotropic C-13 chemical shifts (delta(iso)) of L-alanine residues move linearly downfield with a decrease of hydrogen-bond length (R(N...O)) as expressed by delta(iso) = 237.5-21.7 R(N...0) ppm. Such a downfield shift of delta(iso) predominantly arises from the large downfield shift of delta-22, one of the chemical shift tensor components (delta-11, delta-22, and delta-33) with decreasing R(N...0). Delta-11 moves somewhat upfield with R(N...0) and delta-33 is not sensitive to a change of R(N...0). The quantum-chemical calculation of the C-13 shielding constant for the model compound was carried out by the FPT-INDO method, and the hydrogen-bonding effect on the C-13 chemical shift in the ]C = O...H-N[ type hydrogen bond and the nature of the hydrogen bond are discussed., 1992年04月, 114, 9, 3261, 3265, 研究論文（学術雑誌）
• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, PHASE-TRANSITION IN CYCLOHEXATRIACONTANE AS STUDIED BY VARIABLE-TEMPERATURE C-13 CP MAS NMR-SPECTROSCOPY, Q CHEN; H KUROSU; ANDO, I; H SATO, Variable-temperature C-13 CP/MAS spectra of cyclohexatriacontane (C36H72) in the solid state over a wide range of temperatures were measured, in order to study the phase transition and conformational change of the molecule with temperature. The signals associated with the constrained gauche conformations clearly appear in the spectra at temperatures below 0-degrees-C. A new peak at about 30.3 ppm is observed in the C-13 CP/MAS spectrum at 0-degrees-C. The relative intensity of this peak increases gradually and the other signals become broad with an increase in temperature. This indicates the existence of the "pseudorotator phase" in which C36H72 is undergoing fast conformational interconversion before the melting transition., 1992年01月, 265, 1-2, 153, 161, 研究論文（学術雑誌）
• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, PHASE-TRANSITION IN CYCLOHEXATRIACONTANE AS STUDIED BY VARIABLE-TEMPERATURE C-13 CP MAS NMR-SPECTROSCOPY, Q CHEN; H KUROSU; ANDO, I; H SATO, Variable-temperature C-13 CP/MAS spectra of cyclohexatriacontane (C36H72) in the solid state over a wide range of temperatures were measured, in order to study the phase transition and conformational change of the molecule with temperature. The signals associated with the constrained gauche conformations clearly appear in the spectra at temperatures below 0-degrees-C. A new peak at about 30.3 ppm is observed in the C-13 CP/MAS spectrum at 0-degrees-C. The relative intensity of this peak increases gradually and the other signals become broad with an increase in temperature. This indicates the existence of the "pseudorotator phase" in which C36H72 is undergoing fast conformational interconversion before the melting transition., 1992年01月, 265, 1-2, 153, 161, 研究論文（学術雑誌）
• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, STRUCTURAL CHARACTERIZATION OF SOLUTION-CRYSTALLIZED C-13-LABELED POLYETHYLENE OVER A WIDE-RANGE OF TEMPERATURES BY MEANS OF HIGH-RESOLUTION C-13-NMR SPECTROSCOPY, Q CHEN; T YAMADA; H KUROSU; ANDO, I; T SHIONO; Y DOI, C-13 CP/MAS spectra of C-13-labeled solution crystallized polyethylene at temperatures from -120 to 144-degrees-C are measured, in order to study changes of structure and molecular motion of the polymer with temperature variation. From these results, it was found that the non-crystalline C-13 signal monotonically shifts downfield with a decrease of temperature, whereas the crystalline C-13 signal does not change obviously with temperature. The maximum of the non-crystalline peak width appears at -30-degrees-C and that of the crystalline peak width appears at 110.4-degrees-C. The appearance of the maximum of the crystalline peak width is considered to correlate with the alpha-transition. Another component besides the crystalline and non-crystalline components is found between 88 and 132.8-degrees-C, and is attributed to the interface and defects created in the heating process., 1991年12月, 263, 319, 327, 研究論文（学術雑誌）
• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, STRUCTURAL STUDIES OF N-ALKANES BY VARIABLE-TEMPERATURE SOLID-STATE HIGH-RESOLUTION C-13 NMR-SPECTROSCOPY, S ISHIKAWA; H KUROSU; ANDO, I, High-resolution C-13 NMR spectra of some n-alkanes (n-C19H40, n-C24H50, n-C32H66 and n-C44H90) in the solid state have been measured by means of variable-temperature, solid-state, high-resolution C-13 NMR spectroscopy as a function of temperature, in order to clarify the structural change over a wide range of temperatures. From these results, it was found that the C-13 chemical shift value of the internal CH2 carbons in n-CH24H50 moves from 34.2 to 33.3 ppm in going from the triclinic form to the rotator phase, and the C-13 chemical shift of the internal CH2 carbons of n-C19H40 and n-C32H66 moves from 32.8(32.9) to 33.3 ppm in going from the orthorhombic form to the rotator phase. This shows that the C-13 chemical shift values of n-alkanes in the rotator phase are the same irrespective of their chain length. Further, it was found that the structure of the chain-end parts in the intermediate phase and the rotator phase of longer n-alkanes is similar to that in the noncrystalline phase in which fast transition between trans and gauche isomers occurs., 1991年08月, 248, 3-4, 361, 372, 研究論文（学術雑誌）
• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM, INTERCHAIN INTERACTION OF C-13 NMR CHEMICAL-SHIFT AND ELECTRONIC-STRUCTURE OF POLYPEPTIDE-CHAINS IN THE SOLID-STATE AS STUDIED BY TIGHT-BINDING MO THEORY - POLY(L-ALANINE) WITH THE RIGHT-HANDED AND LEFT-HANDED ALPHA-HELIX FORMS, H KUROSU; ANDO, I, Tight-binding MO-INDO/S sum-over-states theory has been employed to calculate the C-13 NMR chemical shifts and electronic structures for seven right- and left-handed alpha-poly (L-alanine) chain models taking into account interchain interactions. The calculations show that the interchain interactions play an important role in determining the chemical shift behavior. Further, the effects of interchain distance on the chemical shift and electronic structure are discussed., 1991年06月, 77, 231, 242, 研究論文（学術雑誌）
• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, SIDE-CHAIN STRUCTURE OF POLY(METHACRYLIC ACID) AND ITS ZINC SALTS IN THE SOLID-STATE AS STUDIED BY HIGH-RESOLUTION SOLID-STATE C-13 NMR-SPECTROSCOPY, M ASADA; N ASADA; A TOYODA; ANDO, I; H KUROSU, High-resolution solid-state C-13 CP/MAS NMR experiments for isotactic and syndiotactic poly(methacrylic acid)s (PMAA) have been carried out at room temperature, and further those for the zinc salts have been carried out at temperatures from room temperature to about 170-degrees-C. The carboxyl carbon resonance of PMAA was separated into four peaks, three of which move about 3, 6 and 9 ppm downfield, respectively, as compared with the corresponding chemical shift values in solution. The chemical shift value of the remaining peak agrees with that in solution. Based on these experimental results and quantum chemical calculations on the C-13 NMR chemical shift, the observed large downfield shift in the solid state is ascribed to the formation of intermolecular or intramolecular hydrogen bonds. Both the C-13 chemical shift values and the relative peak intensities of the carboxyl carbon in PMAA-zinc salt were almost independent of temperature at temperatures from room temperature to 170-degrees-C. This suggests that the interaction between carboxyl group and zinc does not change within its temperature range., 1991年04月, 244, 237, 248, 研究論文（学術雑誌）
• 査読あり, 英語, MACROMOLECULES, STRUCTURAL CHARACTERIZATION OF POLYALLENE IN THE SOLID-STATE AS STUDIED BY VARIABLE-TEMPERATURE HIGH-RESOLUTION C-13 NMR-SPECTROSCOPY, KH MIN; H KUROSU; ANDO, I; T YAMAMOTO; T KANBARA, High-resolution C-13 NMR spectra of polyallenes in the solid state were measured over the temperature range from room temperature to 100-degrees-C by means of the variable-temperature cross polarization/magic angle spinning NMR and pulse saturation transfer/magic angle spinning NMR techniques. It was shown that the C-13 resonance lines of the noncrystalline, orthorhombic, monoclinic, and paracrystalline forms are chemically shifted from one another. On the basis of these peak assignments, the structural change was studied over the course of the temperature change., 1991年04月, 24, 8, 2011, 2014, 研究論文（学術雑誌）
• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, STRUCTURE AND MOLECULAR-MOTION OF POLY(ETHYLENE OXIDE) IN THE SOLID-STATE AS STUDIED BY VARIABLE-TEMPERATURE HIGH-RESOLUTION SOLID-STATE C-13 NMR, H KUROSU; ANDO, I, 1990年10月, 239, 149, 159, 研究論文（学術雑誌）
• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, SIDE-CHAIN CONFORMATION AND C-13-NMR CHEMICAL-SHIFT OF POLY(L-PHENYLALANINE) AND OLIGOPEPTIDES CONTAINING L-PHENYLALANINE AND TYROSINE RESIDUES IN THE SOLID-STATE, H MIYAMOTO; T KOMOTO; H KUROSU; ANDO, I; T OZAKI; A SHOJI, 1990年04月, 220, 251, 260, 研究論文（学術雑誌）
• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM, C-13 NMR CHEMICAL-SHIFT AND CRYSTAL-STRUCTURE OF POLYETHYLENE CHAINS IN THE SOLID-STATE AS STUDIED BY TIGHT-BINDING THEORY WITHIN THE INDO-S FRAMEWORK, H KUROSU; ANDO, I; T YAMANOBE, 1989年11月, 60, 239, 247, 研究論文（学術雑誌）
• 査読あり, その他, J.Mol.Struct(THEOCHEM), 13C NMR chemical shift and Crystal Structure of Polyethylene chains in the solid state as studied by Tight-Binding theory within the INDD/S framework, YAMANOBE TAKESHI; Isao?Ando; Hiromichi?Kurosu, NMR?chemical?shift?of?polyethylene?is?calculated?by?tight?binding?theory., 1989年, 201
• 査読あり, 英語, JOURNAL OF CHEMICAL PHYSICS, EFFECT OF INTERCHAIN INTERACTIONS ON C-13 NUCLEAR MAGNETIC-RESONANCE CHEMICAL-SHIFTS AND ELECTRONIC-STRUCTURES OF POLYACETYLENE IN THE SOLID-STATE AS STUDIED BY TIGHT-BINDING MOLECULAR-ORBITAL THEORY, T ISHII; H KUROSU; T YAMANOBE; ANDO, I, 1988年12月, 89, 12, 7315, 7319, 研究論文（学術雑誌）
• 査読あり, 英語, JOURNAL OF MOLECULAR STRUCTURE, C-13 NMR CHEMICAL-SHIFT AND CRYSTAL-STRUCTURE OF POLYOXYMETHYLENE IN THE SOLID-STATE, H KUROSU; T KOMOTO; ANDO, I, 1988年05月, 176, 279, 283, 研究論文（学術雑誌）
• 査読あり, 英語, J. Chem. Phys., Interchain effect of ¹³C Nuclear Magnetic Reconance Chemical Shift and Electronic Structure of Poly oxymethylene chains in the Solid State, 黒子弘道, 1988年, 89, 5216-5223, 5216, 10.1063/1.455612

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• 査読あり, 英語, J. Chem. Phys., Effect of Interchain Interactions on ¹³C NMR Chemical Shifts and Electronic Structure of Polyasetylene in the solid state as Studied by Tight-Binding MO Theory, 黒子弘道, 1988年, 89, 7315-7319
• 査読あり, 英語, CHEMICAL PHYSICS, C-13 NMR CHEMICAL-SHIFT AND ELECTRONIC-STRUCTURE OF POLYOXYMETHYLENE IN THE SOLID-STATE, H KUROSU; T YAMANOBE; T KOMOTO; ANDO, I, 1987年09月, 116, 3, 391, 398, 研究論文（学術雑誌）
• 査読あり, その他, PeerJ Materials Science, The influence of thermal treatments on the secondary structure of silk fibroin scaffolds and their interaction with fibroblasts, Tomoko Hashimoto; Yuka Nakamura; Yasushi Tamada; Hiromichi Kurosu; Tsunenori Kameda, Recently, silk fibroin-based biomaterials have received attention for application in tissue engineering and drug delivery systems. The usefulness of heat sterilization methods for silk fibroin-based biomaterials was investigated in this study as all biomaterials are required to undergo a sterilization process when they are used in medical devices. The influence of wet and dry heating on the properties of fibroin molecules in silk fibroin sponges was investigated by measurements of solid-state ¹³C cross-polarization/magic angle spinning (CP/MAS) nuclear magnetic resonance (NMR) spectroscopy, thermogravimetric analyses, strength tests, and cell proliferation/migration assays. ¹³C CP/MAS NMR spectra of wet-heated sponges revealed no changes in the molecular structure below 50 °C. However, above 60 °C, the crystalline structure of the silk proteins transitioned from silk I to silk II; the silk II:silk I ratio increased with temperature. In contrast, dry heating (below 190 °C for up to 180 min) induced no structural changes in the fibroin molecules. These results indicate that, although autoclave sterilization (121 °C for 20 min) induces structural changes in silk fibroin sponges, no such changes are observed with the dry-heat sterilization (180 °C for 30 min). Sterilized sponges with a silk I structure can be obtained using dry-heat method during sterilization. Moreover, the structural differences between the wet- and dry-heated silk fibroin sponges did not influence their interaction with fibroblasts. This study indicates that both autoclaving and dry heating are acceptable sterilization methods for silk fibroin-based sponges as the scaffold. In particular, dry heating maintains the stability of the secondary structure of the sterilized silk fibroin-based biomaterials. , 2020年09月01日, 2, e8, e8, 研究論文（学術雑誌）, 10.7717/peerj-matsci.8

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• その他, American Chemical Society, Polymer Preprints, Division of Polymer Chemistry, Characterization of molecular behavior of stretched rubber by solid-state NMR, Hideaki Kimura; Hidehiko Dohi; Marina Kotani; Hiromichi Kurosu; Hironori Kaji; Kazuo Yamauchi; Tetsuo Asakura, 2008年, 49, 1, 649, 650, 研究論文（国際会議プロシーディングス）

  Scopus URLScopus Citedby URL
• その他, Polymer Preprints, Japan, ¹⁷O NMR studies of biopolymers with β-sheet structure using 930MHz solid state NMR and chemical shift calculation, Kazuo Yamauchi; Michi Okonogi; Hiromichi Kurosu; Takahiro Nemoto; Masataka Tansho; Shimizu Tadashi; Tetsuo Asakura, The solid-state 17O NMR spectra of Ala-Ala-Ala peptides with parallel and anti-parallel β-sheet structures and silk model peptides were measured by magic-angle spinning under the 930MHz NMR instrument. NMR parameters such as the chemical shift, quadrupolar coupling constant and asymmetry parameter were obtained from the spectra. Two different peaks were observed in Ala-Ala-Ala with anti-parallel β-sheet structure depending on two different coordinates of the molecules in unit cell, but for the β-sheet parallel structure, almost one peak were observed because the chemical shift is almost the same., 2006年, 55, 2, 4188, 4189, 研究論文（国際会議プロシーディングス）

  Scopus URLScopus Citedby URL
• その他, ACS Symposium Series, ¹⁷O NMR chemical shifts in peptides, S. Kuroki; K. Yamauchi; Hiromichi Kurosu; S. Ando; Isao Ando; A. Shoji; T. Ozaki, The O-17 NMR spectra of L-alanine containing polypeptides in the solid state were measured chemical shift, quadrupolar coupling constant and asymmetric parameter information obtained. The relationship between the hydrogen-bonding structure and these NMR parameters was investigated. Theoretical calculations of the electric field gradients and chemical shielding values of hydrogen-bonded carbonyl oxygens in peptides were also carried out, and it was found that there exists a relationship between hydrogen-bonding structure and the NMR parameters such as quadrupolar coupling constants and chemical shieldings., 1999年, 732, 126, 137, 研究論文（学術雑誌）, 10.1021/bk-1999-0732.ch009

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• 日本語, 繊維学会誌, The Society of Fiber Science and Technology, Japan, 固体ＮＭＲおよび量子化学計算を併用した高分子の高精度構造解析法の開発, 黒子 弘道, 2010年, 66, 12, P.420, P.424, 10.2115/fiber.66.P_420

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• 査読あり, 英語, Micro and Nano Engineering, Supercritical carbon dioxide-assisted platinum metallization of polyethylene terephthalate textile toward wearable device, Masaki Mitsumoto; Chun-Yi Chen; Wan-Ting Chiu; Tso-Fu Mark Chang; Yasushi Watanabe; Arisa Jinno; Hiromichi Kurosu; Masato Sone, Platinum metallization of polyethylene terephthalate (PET) textile is realized by a supercritical carbon dioxide catalyzation process using palladium (II) hexafluoroacetylacetonate as the source of Pd catalyst, and epsilon-caprolactam as an additive. A commercially available Pt electroless plating solution is used to deposit Pt on the catalyzed PET textile. Surface morphology of the Pt metallized PET textile changes from granular particle to plate-like morphology when the Pt deposition time increases from 1 to 40 min. The Pt layer thickness reaches 270 nm, 580 nm, and 780 nm after 20 min, 60 min and 240 min, respectively, of the Pt deposition time. The Pt metallized PET textile prepared with 240 min of the Pt deposition time shows the lowest electrical resistance at 0.4 omega, and the electrical resistance merely increases to 0.7 omega and 1.0 omega after one and two times, respectively, of a tape adhesion test., 2022年06月, 15, 100132, 100132, 研究論文（学術雑誌）, 10.1016/j.mne.2022.100132

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• 査読あり, 英語, Macromolecules, Roles of Conformational Flexibility in the Crystallization of Stereoirregular Polymers, Navin Kafle; Yuta Makita; Ying Zheng; Derek Schwarz; Hiromichi Kurosu; Pengju Pan; James M. Eagan; Yuki Nakama; Shigetaka Hayano; Toshikazu Miyoshi, 2021年06月22日, 54, 12, 5705, 5718, 研究論文（学術雑誌）, 10.1021/acs.macromol.1c00888

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• 日本語, 高分子, 公益社団法人 高分子学会, ^1H NMRイメージング法による高分子ゲルの構造とダイナミックスの三次元画像化, 黒子 弘道; 安藤 勲, 1997年03月, 46, 3, 140, 140, 10.1295/kobunshi.46.140

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• その他, Novel Metal Electrodeposition and the Recent Application, Electrodeposition of High-Functional Metal Oxide on Noble Metal for MEMS Devices, Wan-Ting Chiu; Chun-Yi Chen; Tso-Fu Mark Chang; Tomoko Hashimoto; Hiromichi Kurosu, 2019年, 研究論文（学術雑誌）, 10.5772/INTECHOPEN.82394

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• 査読あり, 英語, The Journal of Supercritical Fluids, Solid-State 13C NMR Spectroscopic Study of Supercritical CO2 Catalyzation Treated Polyethylene Terephthalate Textiles for Platinum Metallization, Arisa Jinno; Yuna Ogasawara; Tomoko Hashimoto; Masaki Mitsumoto; Tso-Fu Mark Chang; Masato Sone; Hiromichi Kurosu, 2023年03月, 197, 105896, 105896, 研究論文（学術雑誌）, 10.1016/j.supflu.2023.105896

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• その他, Materials, Platinum Metallization of Polyethylene Terephthalate by Supercritical Carbon Dioxide Catalyzation and the Tensile Fracture Strength, Po-Wei Cheng; Tomoyuki Kurioka; Chun-Yi Chen; Tso-Fu Mark Chang; Wan-Ting Chiu; Hideki Hosoda; Kei Takase; Hiroshi Ishihata; Hiromichi Kurosu; Masato Sone, Polyethylene terephthalate (PET) is known to be highly inert, and this makes it difficult to be metallized. In addition, Pt electroless plating is rarely reported in the metallization of polymers. In this study, the metallization of biocompatible Pt metal is realized by supercritical CO2 (sc-CO2)-assisted electroless plating. The catalyst precursor used in the sc-CO2 catalyzation step is an organometallic compound, palladium (II) acetylacetonate (Pd(acac)2). The electrical resistance is evaluated, and a tape adhesion test is utilized to demonstrate intactness of the Pt layer on the PET film. The electrical resistance of the Pt/PET with 60 min of the Pt deposition time remains at a low level of 1.09 Ω after the adhesion test, revealing positive effects of the sc-CO2 catalyzation step. A tensile test is conducted to evaluate the mechanical strength of the Pt/PET. In-situ electrical resistances of the specimen are monitored during the tensile test. The fracture strength is determined from the stress value when the short circuit occurred. The fracture strength is 33.9 MPa for a specimen with 30 min of the Pt deposition time. As the Pt deposition time increases to 45 min and 60 min, the fracture strengths reach 52.3 MPa and 65.9 MPa, respectively. The promoted fracture strength and the decent electrical conductivity demonstrate the advantages toward biomedical devices., 2023年03月16日, 16, 6, 2377, 2377, 研究論文（学術雑誌）, 10.3390/ma16062377

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MISC

• 英語, Novel Metal Electrodeposition and the Recent Application, IntechOpen, Electrodeposition of High-Functional Metal Oxide on Noble Metal for MEMS Devices, 2018年, 1, 22, 10.5772/intechopen.82394
• 査読無し, 英語, POLYMER DEGRADATION AND STABILITY, ELSEVIER SCI LTD, Changes in the properties and protein structure of silk fibroin molecules in autoclaved fabrics, Tomoko Hashimoto; Yuki Taniguchi; Tsunenori Kameda; Yasushi Tamada; Hiromichi Kurosu, The influence of autoclaving on the properties of silk fibroin fabrics (SF(fab)s) was evaluated. High-performance liquid chromatography revealed that the molecular weight (Mw) of the fibroin molecule in SFfabs decreased as the treatment temperature and time increased, which suggests that the fibroin molecule in the fabrics was thermal degraded. Additionally, differential scanning calorimetry experiments revealed a shift of the endothermic peak to higher temperature with increasing treatment temperature and time, which indicates an improvement in the thermal stability of the fibroin molecule in the autoclaved fabrics. Furthermore, C-13 cross-polarization/magic angle spinning (CP/MAS) nuclear magnetic resonance (NMR) analysis revealed that the intensity ratios for the beta-sheet and random-coil peaks fluctuated during autoclaving. The NMR analysis also revealed the presence of an unknown structure in the autoclaved SF(fab)s under certain conditions. The changes in the Mws and degradation temperatures for the autoclaved SF(fab)s are assumed to be induced by the structural changes observed via NMR. Consequently, autoclaving is considered to be an effective technique for modifying the secondary structure and properties of SF(fab)s with high beta-sheet contents using only water and heat without added reagents. (C) 2014 Elsevier Ltd. All rights reserved., 2015年02月, 112, 20, 26, 10.1016/j.polymdegradstab.2014.12.007

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• 査読無し, 英語, Nuclear Magnetic Resonance, Synthetic macromolecules, Hiromichi Kurosu; Takeshi Yamanobe, In this chapter, the papers devoted to NMR application to study synthetic polymers over a period from June 2011 through May 2012 have been reviewed. It includes analysis of primary structure of polymers such as tacticity, regioregularity, end group, sequence distribution (section 2), application of imaging, diffusion and solidstate NMR techniques to characterize the synthetic macromolecules (sections 3 and 4). Finally in section 5, papers devoted to dynamics and polymer blend of the synthetic macromolecules have been surveyed. © The Royal Society of Chemistry 2013., 2013年, 42, 420, 449, 書評論文,書評,文献紹介等, 10.1039/9781849737678-00420

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• 査読無し, 英語, Nuclear Magnetic Resonance, Synthetic macromolecules, Hiromichi Kurosu; Takeshi Yamanobe, 2011年, 40, 391, 431, 書評論文,書評,文献紹介等, 10.1039/9781849732796-00391

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• 査読無し, 英語, JOURNAL OF MOLECULAR STRUCTURE, ELSEVIER SCIENCE BV, Precise structural analysis of α-helical polypeptide by quantum-chemical calculation related to reciprocal side-chain combination of two L-phenylalanine residues, 黒子弘道, To clarify the positive role of side-chain conformation in the stability of protein secondary structure (main-chain conformation), we successfully calculated the optimization structure of a series of well-defined alpha-helical octadecapeptides composed of two L-phenylalanine (Phe) and 16 L-alanine (Ala) residues, based on the molecular orbital calculation with density functional theory (DFT/B3LYP/6-31G(d)). From the total energy calculation and the precise secondary structural analysis, we found that the conformational stability of the alpha-helix is closely related to the reciprocal side-chain combinations (such as positional relation and side-chain conformation) of two Phe residues in this system. Furthermore, we demonstrated that the H-1, C-13, N-15 and O-17 isotropic chemical shifts of each Phe residue depend on the respective side-chain conformations of the Phe residue. (C) 2010 Elsevier B.V. All rights reserved., 2010年04月, 970, 1-3, 96, 100, 10.1016/j.molstruc.2010.02.049

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• 査読無し, 英語, JOURNAL OF MOLECULAR STRUCTURE, ELSEVIER SCIENCE BV, Conformational analysis of α-helical polypeptide included l-proline residue by \nhigh-resolution solid-state NMR measurement and quantum chemical calculation., 黒子弘道, We challenged the problem about the stabilization mechanism of an alpha-helix formation for polypeptides containing L-proline (Pro) residue. We computed the optimized structure of alpha-helical poly(L-alanine) molecules including a Pro residue, H-(Ala)(8)-Pro-(Ala)(9)-OH, based on the molecular orbital calculation with density functional theory, B3LYP/6-31G(d) and the C-13 and N-15 chemical shift values based on the GIAO-CHF method with B3LYP/6-311G(d,p), respectively. It was found that two kinds of optimized structures, 'Bent structure' and 'Included alpha-helix structure', were preferred structures in H-(Ala)(8)-Pro-(Ala)(9)-OH. In addition, based on the precise C-13 and N-15 chemical shift data of the simple model, we successfully analyzed the secondary structure of well-defined synthetic polypeptide H-(Phe-Leu-Ala)(3)-Phe(C)-Pro-Ala(N)-(Phe-Leu-Ala)(2)-OH (FLA-11P), the secondary structure of which was proven to the 'Included alpha-helix structure'. (C) 2008 Elsevier B.V. All rights reserved., 2008年10月, 889, 1-3, 237, 243, 10.1016/j.molstruc.2008.02.012

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• 査読無し, 英語, ANNUAL REPORTS ON NMR SPECTROSCOPY, VOL 61, ELSEVIER ACADEMIC PRESS INC, Solid-state NMR studies on semicrystalline polymers, Qun Chen; Hiromichi Kurosu, In this review, we summarize recent works on semicrystalline polymers as studied by solid-state NMR, with the emphasis on demonstrating the potential of NMR techniques in characterizing the phase structures, chain conformation, intermolecular interactions as well as chain dynamics of semicrystalline polymers., 2007年, 61, 247, 281, 10.1016/S0066-4103(07)61104-1

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• 査読無し, 英語, Specialist Periodical Reports Nuclear Magnetic Resonance, Synthetic Macromolecules, 黒子弘道, 2006年, 35, 389-418
• 査読無し, 英語, Specialist Periodical Reports Nuclear Magnetic Resonance, Synthetic Macromolecules, 黒子弘道; H.Kurosu他, 2005年, 34, 415-470
• 査読無し, 英語, ADVANCES IN SOLID STATE NMR STUDIES OF MATERIALS AND POLYMERS: A SPECIAL VOLUME DEDICATED TO ISAO ANDO, ACADEMIC PRESS LTD, Structural studies of polymer blends by solid-state NMR, H Kurosu; Q Chen, In this review, we introduce recent research works on polymer blends as studied by solid state NMR and focus on the miscibility and phase separation of polymer blends that are responsible for the improvement in their physical properties., 2004年, 52, 167, 200, 書評論文,書評,文献紹介等, 10.1016/S0066-4103(04)52004-5

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• 査読無し, 英語, Specialist Periodical Reports Nuclear Magnetic Resonance, Synthetic Macromolecules, 黒子弘道, 2002年, 31, 353-387
• 査読無し, 英語, PROGRESS IN NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY, PERGAMON-ELSEVIER SCIENCE LTD, NMR chemical shift calculations and structural characterizations of polymers, Ando, I; S Kuroki; H Kurosu; T Yamanobe, 2001年08月, 39, 2, 79, 133, 書評論文,書評,文献紹介等
• 査読無し, 英語, Specialist Periodical Reports Nuclear Magnetic Resonance, Synthetic Macromolecules, 黒子弘道, 2001年, 30, 377-411
• 査読無し, その他, Report on Progress in Polymer Physics in Japan, NMR Chemical Shifts and Structures of Polymers, YAMANOBE TAKESHI; Isao Ando; Shigeki Kuroki; Hiromichi Kurosu, 2000年, Vol.43 467
• 査読無し, 英語, Exp. Methods Polym. Sci., NMR spectroscopy in polymer science, 黒子弘道, 2000年, 261-493
• 査読無し, 英語, ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, AMER CHEMICAL SOC, Oxygen-17 NMR chemical shifts in peptides and hydrogen-bonding structures, S Kuroki; H Kurosu; S Ando; Ando, I, 1998年08月, 216, U724, U724, 研究発表ペーパー・要旨（国際会議）
• 査読無し, 英語, ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, AMER CHEMICAL SOC, Conformational study of the L-alanine residue in polypeptides by ab initio C-13 NMR shielding calculation., H Kurosu; K Fukuyama; Ando, I, 1998年08月, 216, U724, U724, 研究発表ペーパー・要旨（国際会議）
• 査読無し, 英語, ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, AMER CHEMICAL SOC, Modeling chemical shifts in polymers and amorphous matter, Ando, I; H Kurosu; M Uchida; T Yamanobe, 1998年08月, 216, U701, U701, 研究発表ペーパー・要旨（国際会議）
• 査読無し, 英語, Specialist Periodical Reports Nuclear Magnetic Resonance, Synthetic Macromolecules, 黒子弘道, 1998年, 127, 337-369
• 査読無し, 英語, Specialist Periodical Reports Nuclear Magnetic Resonance, Synthetic Macromolecules, 黒子弘道, 1998年, 27, 337-369
• 査読無し, 英語, Annual Reports on NMR Spectroscopy, Structures and Dynamics of Polymer Gel Systems Viewed Using NMR Spectroscopy, Hidekazu Yasunaga; Masatoshi Kobayashi; Shingo Matsukawa; Hiromichi Kurosu; Isao Ando, Recent fundamental research on hydro-polymer gel systems by means of NMR techniques such as pulse NMR, pulsed field-gradient spin-echo NMR, solid-state high-resolution NMR and NMR imaging methods have been reviewed. Such NMR techniques have elucidated structures and dynamics of gel systems as a function of the degree of crosslinking and their response process by an application of stimulus such as change in temperature, stress and electric field. It has been demonstrated that NMR techniques are powerful means of determining micro- and macroscopic structures and dynamics of more complicated systems with mobile components such as gel systems. © 1997 Academic Press Inc., 1997年, 34, C, 39, 104, 10.1016/S0066-4103(08)60101-5

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• 査読無し, 英語, Encyclopedia of NMR,John Wiley & Sons,New York, John Wiley & Sons, Solid Polymer : Shielding & Electronic States, 黒子弘道, 1995年, 4468-4474, 4474
• 査読無し, 日本語, 新高分子実験学5「高分子の構造」、講談社サイエンティクィック, 核磁気共鳴法, 黒子弘道, 1995年
• 査読無し, 日本語, 高分子学会予稿集, 固体高分解能NMRによる長鎖n‐アルキル基を有するポリ(γ‐グルタメート)の構造と分子運動に関する研究 (2), 加藤悦子; 黒木重樹; 黒子弘道; 安藤勲, 1993年09月, 42, 10, 4219, 4221
• 査読無し, 英語, Annual Reports on NMR Spectroscopy, NMR Studies of High-order Structures of Solid Polymers, 黒子弘道, 1993年, 28, 189-275
• 査読無し, 英語, POLYMER JOURNAL, SOC POLYMER SCIENCE JAPAN, APPEARANCE OF NEW STRUCTURES OF POLYALLENE IN THE SOLID-STATE AT LOW-TEMPERATURES AS OBSERVED BY VARIABLE-TEMPERATURE HIGH-RESOLUTION C-13 NMR-SPECTROSCOPY, KH MIN; H KUROSU; ANDO, I; T YAMAMOTO; T KANBARA, 1992年, 24, 8, 829, 831, 記事・総説・解説・論説等（学術雑誌）
• 査読無し, 日本語, 高分子(40巻11月号), The Society of Polymer Science, Japan, 高分子における計算科学の進歩, 黒子弘道, 1991年, 40, 11, 740, 743, 10.1295/kobunshi.40.740

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• 査読無し, 英語, Annual Reports on NMR Spectroscopy, NMR Nuclear Shielding and Electronic Structure of Macromolecules, 黒子弘道, 1989年, 22, 205-248, 205
• その他, 高分子学会予稿集, 磁場勾配パルス¹H NMR法を用いた回転相におけるn-アルカンのダイナミックス研究, 山川秀之; 松川真吾; 黒子弘道; 黒木重樹; 安藤勲, 1999年, 48, 5
• その他, 高分子学会予稿集, 磁場勾配パルス¹H NMR法を用いた回転相におけるn-アルカンのダイナミクス研究, 山川秀之; 松川真吾; 黒子弘道; 黒木重樹; 安藤勲, 1997年, 46, 13
• その他, 高分子学会予稿集, 磁場勾配¹H NMR法を用いたポリペプチドゲルのダイナミックスに関する研究, ZHAO C; 松川真吾; 黒子弘道; 安藤勲, 1997年, 46, 10
• その他, 高分子学会予稿集, NMRを用いたポリアスパラギン酸のナトリウム塩の水和特性及び分子運動についての研究, WANG P; 松川真吾; 黒子弘道; 安藤勲, 1997年, 46, 5
• その他, 高分子学会予稿集, 固体¹³CNMRにおけるポリアスパラギン酸とそのナトリウム塩のコンホメーションの安定性についての研究, WANG P; 松川真吾; 亀田恒徳; 黒子弘道; 安藤慎治; 安藤勲, 1996年, 45, 10
• その他, 高分子学会予稿集, NMR法を用いたポリ(N-イソプロピルアクリルアミド)ゲルの構造とダイナミックスに関する研究, 田中紀行; 松川真吾; 黒子弘道; 安藤勲, 1996年, 45, 3
• その他, 高分子学会予稿集, 固体¹³C NMRによるポリアスパラギン酸とそのナトリウム塩のコンホメーションに関する研究, WANG P; 松川真吾; 亀田恒徳; 黒子弘道; 安藤慎治; 安藤勲, 1996年, 45, 5
• その他, 高分子学会予稿集, NMR法を用いたポリ(N-イソプロピルアクリルアミド)の構造とダイナミックスに関する研究 II, 田中紀行; 松川真吾; 黒子弘道; 安藤勲, 1996年, 45, 8
• その他, 高分子学会予稿集, ¹HパルスNMR法を用いたゲル内の物質拡散についての研究, 田中紀行; 松川真吾; 黒子弘道; 安藤勲, 1995年, 44, 8
• その他, 高分子学会予稿集, 磁場勾配NMR法を用いた高分子ゲル内における物質拡散に関する研究, 松川真吾; 黒子弘道; 安藤勲, 1994年, 43, 8
• 日本語, 蚕糸・昆虫バイオテック, 日本蚕糸学会, シルクの新しい修飾技術 (特集 : マテリアルとしてのシルク研究最前線), 橋本 朋子; 黒子 弘道; 亀田 恒徳; 玉田 靖, 2017年04月, 86, 1, 13, 17

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• その他, 繊維学会予稿集(CD-ROM), シルクフィブロインの表面特性と細胞との相互作用解析, 橋本朋子; 水野しおり; 山岡哲二; 亀田恒徳; 玉田靖; 黒子弘道, 2021年, 76, 1
• その他, 繊維学会予稿集(CD-ROM), 新しい機能を有するシルク縫合糸の創出, 橋本朋子; 亀田恒徳; 黒子弘道; 山岡哲二; 玉田靖, 2021年, 76, 2
• その他, 繊維学会予稿集, 異なる二次構造を有するシルクフィブロイン材料と細胞との相互作用解析, 橋本朋子; 水野しおり; 山岡哲二; 亀田恒徳; 玉田靖; 黒子弘道, 2020年, 75, 1
• その他, 繊維学会予稿集, シルクフィブロインへの機能性ペプチド固定化, 橋本朋子; 水野しおり; 佐野奈緒子; 山岡哲二; 亀田恒徳; 玉田靖; 黒子弘道, 2019年, 74, 2
• その他, 繊維学会予稿集, 創傷被覆材への応用を指向したシルクフィブロインへの機能性ペプチド固定化, 橋本朋子; 中村優佳; 佐野奈緒子; 山岡哲二; 亀田恒徳; 玉田靖; 黒子弘道, 2019年, 74, 1
• その他, 繊維学会予稿集, シルクフィブロインの二次構造制御と細胞との相互作用解析, 橋本朋子; 水野しおり; 佐野奈緒子; 山岡哲二; 亀田恒徳; 玉田靖; 黒子弘道, 2019年, 74, 1
• その他, 日本バイオマテリアル学会大会予稿集(Web), シルク縫合糸への生分解性・抗菌性付与, 橋本朋子; 橋本朋子; 太田真由; 佐野奈緒子; 佐野奈緒子; 山岡哲二; 亀田恒徳; 玉田靖; 黒子弘道; 黒子弘道, 2019年, 41st
• その他, 日本バイオマテリアル学会大会予稿集(Web), 異なる二次構造を有するシルクフィブロイン上での細胞挙動評価, 水野しおり; 橋本朋子; 佐野奈緒子; 山岡哲二; 亀田恒徳; 玉田靖; 黒子弘道, 2019年, 41st
• その他, 日本バイオマテリアル学会大会予稿集(Web), 創傷被覆材への応用を指向したシルクフィブロインの構造制御と細胞との相互作用解析, 橋本朋子; 道法志帆; 大槻直美; 佐野奈緒子; 山岡哲二; 亀田恒徳; 玉田靖; 黒子弘道, 2018年, 40th
• その他, 日本バイオマテリアル学会大会予稿集(Web), シルクフィブロインの二次構造解析と機能性ペプチド固定化, 橋本朋子; 中村優佳; 佐野奈緒子; 山岡哲二; 亀田恒徳; 玉田靖; 黒子弘道, 2017年, 39th
• 日本語, 液晶討論会講演予稿集, 日本液晶学会, 2B513 ピロメリット酸の1,4-ジアルキルエステルを含む剛直棒状ポリエステル. 1, 曽根 正人; 渡辺 順次; Harkness Brian R.; 黒子 弘道; 安藤 勲, 1992年09月11日, 18, 250, 251
• 日本語, 液晶討論会講演予稿集, 日本液晶学会, 2B514 ピロメリット酸の1,4-ジアルキルエステルを含む剛直棒状ポリエステル. 2, 曽根 正人; 渡辺 順次; Harkness Brian R.; 黒子 弘道; 安藤 勲, 1992年09月11日, 18, 252, 253
• 査読無し, 英語, Abstracts of Papers of the American Chemical Society, AMER CHEMICAL SOC, 【62】POLY 384-Characterization of molecular behavior of stretched rubber by solid-state NMR, H. Kimura; H. Dohi; M. Kotani; H. Kurosu; H. Kaji; K. Yamauchi; T. Asakura, 2008年04月, 235, 研究発表ペーパー・要旨（国際会議）
• 査読無し, 日本語, 生体医工学, 公益社団法人 日本生体医工学会, シルク縫合糸の生分解性評価, 橋本 朋子; 佐野 奈緒子; 山岡 哲二; 亀田 恒徳; 玉田 靖; 黒子 弘道,

  蚕の繭から得られるシルクは優れた生体親和性や力学特性を有し、また成形加工や加熱滅菌処理が可能であることから、再生医療用生体材料として着目され、広く研究されている。また、編糸状のシルクは、外科手術用縫合糸として長い歴史をもち、現在も非吸収性の縫合糸として利用されている。われわれは、これまで、高温かつ高圧力で飽和水蒸気状態での処理を行うオートクレーブ（AC）処理による処理がシルク繊維の二次構造を変化させることを明らかにしてきた。また、この二次構造の変化に伴いシルクの分子量等、諸物性に変化が認められた。本研究では、AC処理に加え、アルコール処理を組み合わせて縫合糸の物性改変を試みた。異なる条件で作成したシルク縫合糸のin vitro分解挙動を調べ、さらに全反射測定赤外吸収スペクトル測定により縫合糸の二次構造解析を行った。また、抗張力の指標として、分解前後の力学特性を引張試験機により調べ、分解挙動と物性の関連性について評価することにより、シルク縫合糸の吸収性材料としての可能性を検討した。

  , 2018年, 56, 0, S415, S415, 10.11239/jsmbe.Annual56.S415

  DOI URL
• 査読無し, 日本語, 蚕糸・昆虫バイオテック, 社団法人 日本蚕糸学会, シルクの新しい修飾技術, 橋本 朋子; 黒子 弘道; 亀田 恒徳; 玉田 靖, 2017年, 86, 1, 1_013, 1_017, 10.11416/konchubiotec.86.1_013

  DOI URL
• 査読無し, 日本語, 日本バイオマテリアル学会大会予稿集, 日本バイオマテリアル学会, タンパク質二次構造を利用したシルクフィブロインへの機能性ペプチド固定化, 橋本 朋子; 中村 優佳; 山岡 哲二; 亀田 恒徳; 玉田 靖; 黒子 弘道, 2015年11月, 37回, 104, 104

書籍等出版物

• Noble Metallic Pt Metallization on the Silk textile by a Supercritical Carbon Dioxide Assisted Metallization Technique towards the Wearable Device in Biocompatible Medical Applications, Jenny Stanford Publishing, 英語, 学術書, 9789814877633
• Highly Reliable Metallization on Polymer and Their Fundamental Characteristics Toward Wearable Devices Applications, International Frequency Sensor Association Publishing, 黒子 弘道, 2018年, その他, 査読無し, その他
• Specialist Periodical Reports Nuclear Magnetic, The Royal Society of Chemistry, 黒子弘道, 筆頭著者, 2015年, 431-455, 英語, 査読無し, その他
• Specialist Periodical Reports Nuclear Magnetic, The Royal Society of Chemistry, 黒子弘道, 筆頭著者, 2014年, 423-456, 英語, 査読無し, その他
• Specialist Periodical Reports Nuclear Magnetic Resonance,Synthetic Macromolecules, The Royal Society of Chemistry, 黒子弘道, 筆頭著者, 2013年, Vol. 42, pp. 420-449, 英語, 査読無し, その他
• Encyclopedia of NMR, John Wiley & Sons, 黒子弘道, 分担, 2012年, 英語, 査読無し, その他
• Specialist Periodical Reports Nuclear Magnetic Resonance,Synthetic Macromolecules, The Royal Society of Chemistry, 黒子弘道, 筆頭著者, 2012年, Vol. 41, pp.386-428, 英語, 査読無し, その他
• Specialist Periodical Reports Nuclear Magnetic Resonance,Synthetic Macromolecules, The Royal Society of Chemistry, 黒子弘道, 筆頭著者, 2011年, Vol. 40, pp.391-431, 英語, 査読無し, その他
• Specialist Periodical Reports Nuclear Magnetic Resonance,Synthetic Macromolecules, The Royal Society of Chemistry, 黒子弘道, 筆頭著者, 2010年, Vol. 39, pp. 322-362, 英語, 査読無し, その他
• Specialist Periodical Reports Nuclear Magnetic Resonance,Synthetic Macromolecules, The Royal Society of Chemistry, 黒子弘道, 筆頭著者, 2009年, Vol. 38, pp.370-410, 英語, 査読無し, その他
• Specialist Periodical Reports Nuclear Magnetic Resonance,Synthetic Macromolecules, The Royal Society of Chemistry, 黒子弘道, 筆頭著者, 2008年, Vol. 37, pp.293-326, 英語, 査読無し, その他
• Specialist Periodical Reports Nuclear Magnetic Resonance,Synthetic Macromolecules, The Royal Society of Chemistry, 黒子弘道, 筆頭著者, 2007年, Vol. 36, pp.309-343, 英語, 査読無し, その他
• Modern Magnetic Resonance, NMR Chemical Shifts Based on Band Theory, Springer, 黒子弘道, 分担, 2006年, 英語, 査読無し, その他
• Specialist Periodical Reports Nuclear Magnetic Resonance,Synthetic Macromolecules, The Royal Society of Chemistry, 黒子弘道, 筆頭著者, 2006年, Vol. 35, pp389-432, 英語, 査読無し, その他
• Specialist Periodical Reports Nuclear Magnetic Resonance,Synthetic Macromolecules, The Royal Society of Chemistry, 黒子弘道, 筆頭著者, 2005年, Vol. 34, pp.415-470, 英語, 査読無し, その他
• Specialist Periodical Reports Nuclear Magnetic Resonance,Synthetic Macromolecules, The Royal Society of Chemistry, 黒子弘道, 筆頭著者, 2004年, Vol. 33, pp.386-438, 英語, 査読無し, その他
• Specialist Periodical Reports Nuclear Magnetic Resonance,Synthetic Macromolecules, The Royal Society of Chemistry, 黒子弘道, 筆頭著者, 2003年, Vol. 32, pp.361-400, 英語, 査読無し, その他
• Specialist Periodical Reports Nuclear Magnetic Resonance,Synthetic Macromolecules, The Royal Society of Chemistry, 黒子弘道, 筆頭著者, 2002年, Vol. 31, pp.353-387, 英語, 査読無し, その他
• Specialist Periodical Reports Nuclear Magnetic Resonance,Synthetic Macromolecules, The Royal Society of Chemistry, 黒子弘道, 筆頭著者, 2001年, Vol. 30, pp.377-411, 英語, 査読無し, その他
• Specialist Periodical Reports Nuclear Magnetic Resonance,Synthetic Macromolecules, The Royal Society of Chemistry, 黒子弘道, 筆頭著者, 2000年, Vol. 29, pp.419-452, 英語, 査読無し, その他
• Specialist Periodical Reports Nuclear Magnetic Resonance,Synthetic Macromolecules, The Royal Society of Chemistry, 黒子弘道, 筆頭著者, 1999年, Vol. 28, pp.364-394, 英語, 査読無し, その他
• Solid State NMR of Polymers&0d0a;&0d0a;, 黒子弘道, 1998年, 英語, 査読無し, その他
• Specialist Periodical Reports Nuclear Magnetic Resonance,Synthetic Macromolecules, The Royal Society of Chemistry, 黒子弘道, 筆頭著者, 1998年, Vol. 27, pp.337-369, 英語, 査読無し, その他
• Solid Polymers : Shielding & Electronic States&0d0a;, Encyclopedia of NMR, John Wiley & Sons, New York, 黒子弘道, 1995年, 4468-4474頁, 英語, 査読無し, その他
• 高分子の固体NMR, 講談社サイエンティフィク, 黒子弘道, 1994年, 日本語, 査読無し, その他
• 各種分析手法におけるサンプリング・試料調製法と前処理技術, 技術情報協会, 黒子弘道, 1993年, 日本語, 査読無し, その他
• 新材料開発とコンピュータケミストリー, 化学工業日報社, 黒子弘道, 1989年, 日本語, 査読無し, その他

講演・口頭発表等

• Hikaru Kondo, 国際, 49th international conference on Micro and Nano Engineering, Metallization of UHMW-PE Fibers by Supercritical CO2 Catalyzation toward Weavable Devices, 口頭発表（一般）, 2023年09月25日, 2023年09月28日, 英語
• Hikaru Kondo, 国際, 244th ECS Meeting, Ni-P Electroless Plating of Polyethylene Terephthalate Fibers with Various Twist Number Utilizing Supercritical CO2-Assisted Catalyzation, 口頭発表（一般）, 2023年10月08日, 2023年10月12日, 英語
• 美馬由布子, 国内, 繊維学会秋季研究発表会, PETを用いた新規インテリジェント繊維の高次構造解析, ポスター発表, 2023年11月27日, 2023年11月28日, 日本語
• 田中りら, 国内, 繊維学会秋季研究発表会, 新規インテリジェント繊維(綿)の高次構造解析, ポスター発表, 2022年11月09日, 2022年11月10日, 日本語
• 神野有沙, 国内, 繊維学会年次大会, 新規インテリジェント繊維の高次構造解析, 口頭発表（一般）, 2021年06月09日, 2021年06月11日, 日本語
• 橋本朋子, 国内, 繊維学会年次大会, シルクフィブロインの表面特性と細胞との相互作用解析, 口頭発表（一般）, 2021年06月09日, 2021年06月11日, 日本語
• 橋本朋子, 国内, 繊維学会秋季研究発表会, 新しい機能を有するシルク縫合糸の創出, 口頭発表（一般）, 2021年11月18日, 2022年11月19日, 日本語
• 神野有沙, 国内, 生体医歯工学共同研究拠点　令和2年度成果報告会, 新規インテリジェント繊維の高次構造解析, ポスター発表, 2021年03月05日, 2020年03月05日, 日本語
• 水野しおり, 国内, 高分子研究発表会（神戸）, 創傷被覆材への応用を目指したシルクフィブ口インの二次構造解析, 口頭発表（一般）, 日本語
• 水野しおり, 国内, 日本バイオマテリアル学会関西ブロック第14会若手研究発表会, 創傷被覆材を指向したシルクフィブロインの二次構造含有率と細胞挙 動との関係, ポスター発表, 日本語
• 神野有沙, 国内, 繊維学会秋季研究発表会, 新規インテリジェント繊維の高次構造解析, 口頭発表（一般）, 2020年11月05日, 2020年11月06日, 日本語
• 黒子 弘道, 高分子学会・ＮＭＲ研究会, 固体NMRおよび量子化学計算を併用した構造解析, 2013年05月, 日本語, 東京, 国内会議
• 黒子 弘道, 繊維学会年次大会・繊維学会賞受賞講演, 固体ＮＭＲおよび量子化学計算を併用した高分子の高精度構造解析法の開発, 2010年06月, 日本語, 東京, 国内会議

Works（作品等）

• 固体ＮＭＲを用いた高分子材料の研究, 2013年08月, 2014年07月

受賞

• 繊維学会賞, 社団法人繊維学会, 2010年06月
• 高分子研究奨励金（現：高分子研究奨励賞）, 高分子学会, 黒子 弘道, 1997年05月

共同研究・競争的資金等の研究課題

• 基盤研究(B), 2021年, 2024年, 21H01668, 研究分担者, 超臨界ナノプレーティング反応によるナノ空間での金属成長機序の研究
• 基盤研究（B), 2021年, 2024年, 21H00807, 研究代表者, 次世代インテリジェントテキスタイルの創製とウェアラブルシステムへの応用
• 基盤研究(B), 2014年04月01日, 2017年03月31日, 26282013, 研究代表者, 次世代センシング繊維の創成とウェアラブルセンサへの応用
• 基盤研究(B), 2017年, 2020年, 17H01956, 研究代表者, 次世代生体適合性インテリジェント繊維の創成と双方向ウェアラブルシステムへの応用
• 高分子の構造と電子構造, 0, 0, 0, 競争的資金
• 高分子の構造・物性に関する研究, 0, 0, 0, 競争的資金
• Structure and electronic state of polymers, 0, 0, 0, 競争的資金
• Study on structure and physical propaty of polymers, 0, 0, 0, 競争的資金
• 基盤研究(B), 2017年04月01日, 2021年03月31日, 17H01956, 次世代生体適合性インテリジェント繊維の創成と双方向ウェアラブルシステムへの応用, 黒子 弘道; 曽根 正人; 才脇 直樹; 佐藤 克成; 橋本 朋子; チャン ツォーフーマーク, 日本学術振興会, 科学研究費助成事業, 奈良女子大学, 17680000, 13600000, 4080000, 超臨界二酸化炭素を用いることで、絹への白金被覆を欠陥無しで実現することができ、更にその上に酸化チタンなどの高機能性無機酸化物の電気化学的電析することに成功した。これらの繊維を固体NMR測定によりめっきによる高次構造変化の情報を得ることができ、さらなる機能改良へのフィードバックが可能となった。 これらのインテリジェント繊維の応用として、心拍数や呼吸、運動などを可視化できるセンシングウェアの開発に取り組み、睡眠時における健康見守りの実現可能性を示した。さらに、快適性が高まる温度刺激の条件を示した。また、視覚障碍者支援やぬいぐるみを介したコミュニケーション支援などへの応用可能性を示した。, kaken

  対象リソースIRI
• 基盤研究(B), 2005年, 2006年, 17350110, 新規主鎖型液晶ポレオレフィンの創成と液晶構造制御に関する研究, 黒子 弘道; 永 直文; 曽根 正人, 日本学術振興会, 科学研究費助成事業, 奈良女子大学, 14900000, 14900000, 本研究では、ポリオレフィンの主鎖に特異な環状構造を周期的に導入することにより剛直性を持たせ、自発的配向する液晶相を形成する高分子を合成し、更に、合成した高分子を液晶紡糸することにより、折畳みを形成しない高強度配向繊維を作製する技術を開発することを目的としている。このため、平成17年度はポリエチレンにシクロペンタン構造をランダムに導入した(エチレン-ヘキサジエン)共重合体および、シクロペンタン構造とメチレンが交互に有するポリ(メチレン-1,3-シクロペンタン)の結晶および液晶の固体高分解能^<13>C NMRスペクトルを固体NMR装置を用いて化学シフトおよび緩和時間測定を行った。 用いた試料は架橋ジルコノセン触媒によるエチレンと1,5-ヘキサジエン(HD)の環化反応を伴う共重合により得たシクロペンタン構造の含有率1.8, 9.7, 20.3mol%のランダム共重合体である。 固体高分解能NMRでは、結晶領域のみならず、非晶の構造についてもコンホメーション、分子運動性を議論することが可能である。上記試料のCP/MAS測定を行ったところ、シクロペンタン構造の含有率が9.7mol%以上では(エチレン-HD)共重合体の非晶部が明らかに通常のポリエチレン非晶と異なるトランスリッチな構造をとっていることが明らかとなった。シクロペンタン構造の取り込みによって、通常のポリエチレン非晶とは異なる、トランスリッチな構造を形成させるという興味深い結果が得られた。 また、分子運動性の情報を得るために^<13>Cスピン-格子緩和時間(T_1^c)の測定を行った。これにより、シクロペンタン構造の含有率の低い試料では結晶部、非晶部共に分子運動性の異なる2つの領域が存在することが明らかとなり、シクロペンタン構造の含有率が20.3mol%の試料では、結晶相、非晶相ともに分子運動性の高い1成分のみが存在するという興味深い結果を得た。, kaken

  対象リソースIRI
• 基盤研究(A), 2004年, 2006年, 16200044, ナノテク繊維の開発とアパレル素材への応用, 松生 勝; 黒子 弘道, 日本学術振興会, 科学研究費助成事業, 奈良女子大学, 49140000, 37800000, 11340000, 近年産業界におけるナノテクの発展は目覚しく、その分野は多岐にわたっている。素材分野においてもナノ材料と呼ばれる研究とその進展は、21世紀における材料の革命的変革を期待しえる。本研究は、ナノテク繊維の開発とアパレル素材への応用を目指して、その基礎研究に視点をおいて研究を展開している。 本科学研究費により、走査型電子顕微鏡を購入し、1nm以上の繊維の観察を詳細に行うと共に、繊維や微粒子の化学構造を、入射電子線ビームから跳ね返って来るX線の波長から判別しえるEDS(energy dispersion X-ray spectrometry)を附属装置として購入した。これによる成果の概略は以下の通りである。 本研究の意義の概略は、ゲルー結晶化法で作成した多層カーボンナノチューブ(MWNT)-超高分子量ポリエチレン(UHMWPE)並びにカーボンファイバー(CF)-UHMWPE複合材料の導電性機構について解明し、それをアパレル素材の開発の糸口になるような問題提起を行うことである。 ゲルー結晶化の際にMWNTの表面を全面的にUHMWPEが覆うように結晶化する。PEは絶縁体であるので、この試料の電気伝導率は極めて低く10^<-11>S/cm以下である。殆どのUHMWPEがMWCNFの表面を被覆していると考えざるを得ない。しかし、この試料を150℃で熱処理してUHMWPEをいったん融解し、再び冷却するとこれを証明するために、色々な組成比を持つMWNTとPEの試料を作成し、SEM観察によって求まるPBの被覆厚とPEと電気伝導度の関係から、どの程度PEの薄さに被膜がなされ時に導電性が生じ、この効果が何に起因するかを検討した。また素材としては、ポリエチレン以外に極性基を有するポリビニルアルコール(PVA)やポリアクリロニトリル(PAN)についても同様の実験を行い、用いる高分子の電気伝導度の違いが複合材料の電気伝導率に及ぼす影響を明らかにした。 またアパレル素材への応用についても検討したが、基礎研究から応用研究への橋渡しは容易でなかった。, kaken

  対象リソースIRI
• 国際学術研究, 1997年, 1998年, 09044145, 固体フッ素化高分子の完全構造解析の方法論の開発と構造-物性・機能の関係の解明, 安藤 勲; WEBB Graham; HARRIS Robin; 黒子 弘道, 日本学術振興会, 科学研究費助成事業, 東京工業大学, 5300000, 5300000, 昨年度からの継続として、固体フッ素化高分子の完全構造解析の新しい方法論の確立と構造と物性・機能の研究を行い得られた成果の概要を報告する。 共同研究グループのうち安藤・黒子らは今年度は三次元規則構造をもつフッ素化高分子の電子状態および^<19>F NMR遮蔽定数を評価するab initio MOレベルのソフトを完成し、それをフッ素化高分子および種々の高分子に適用し、分子内および分子間相互作用が及ぼす電子状態とNMR遮蔽定数を高い精度で計算し、NMR化学シフトを通して高分子の構造解析および電子状態解析の方法論を確立した。 また、サリー大学のWebb教授はフッ素化低分子化合物の^<19>F NMR遮蔽定数を最も高い近似レベルのab initio MO法を用いた新しいNMR化学シフト理論により評価し、高い精度で分子の構造解析に応用できることがわかった。また、この方法は上記の安藤らの方法と組み合わせることにより、より高い精度の構造解析の方法論となることが明らかとなった。 ダーラム大学のHarris教授はフッ素化高分子の高分解能固体^<19>F NMRスペクトルの測定方法の確立を行い、その方法を用いて種々のフッ素化高分子の固体高分解能^<19>F NMRスペクトルを行い、高い精度で構造解析を行った。また、上記の理論的な方法論と組み合わせた新しい優れた方法の開発を確立した。 2年間の本国際共同研究によりこの分野において大きな研究成果を得たことを3つの研究グループで確認し、米国にて開催された国際会議で発表したことと、また研究論文を発表し、内外で高い評価を受けた。, kaken

  対象リソースIRI
• 基盤研究(B), 1996年, 1997年, 08455449, 高分子ゲルの電気的刺激-応答のイメージ画像と分子設計への応用, 安藤 勲; 黒木 重樹; 黒子 弘道; 安藤 慎治, 日本学術振興会, 科学研究費助成事業, 東京工業大学, 8300000, 8300000, ハイドロ高分子ゲルは電場を印加することにより収縮することにより,人工筋肉,物質の移動量の制御などの開発に期待され,広く研究されている。このためにゲルの収縮の機構についての分子レベルからの基礎的な研究の進展が必務である。このような考えのもとに,^1HNMRイメージング法が核の空間分布の情報を与えることに注目して本研究課題を発展させるとともに,その方法論を確立した。 電場印加にともないゲルの収縮過程の機構および金属イオンの空間分布を^1HNMRイメージング法を用いて,ミクロな面から解明した。また,これらの方法論が分子設計に大きく貢献することを明らかにした。, kaken

  対象リソースIRI
• 奨励研究(A), 1995年, 1995年, 07750987, 固体高分解能NMRによるシリカ表面へ吸着したポリエチレンの構造と分子運動の研究, 黒子 弘道, 日本学術振興会, 科学研究費助成事業, 東京工業大学, 1000000, 1000000, 本研究では、吸着したポリエチレンの構造及び分子運動を明らかにするために、シリカゲルに吸着させた^<13>Cラベルしたポリエチレンの固体高分解能^<13>CNMRスペクトルを観測した。その結果から、ポリエチレンはシリカゲル表面にトランス及びゴ-シュコンホメーションをとり吸着し、この割合はおよそ16:1であり、ポリエチレン鎖は所々で表面から離れループ状になっており、トランス-ゴ-シュ間で速い転移が生じていることがわかった。バルクのポリエチレンの非晶部分のメチレン鎖は、両端あるいは片端が結晶領域に入っているので、その部分で分子運動が束縛されていると考えられる。溶融急冷ポリエチレンでは非晶部分が大きく、非晶部のメチレン鎖はほとんど束縛されず、トランス-ゴ-シュ間の障壁エネルギーはn-ブタンに近い値をとる。一方、結晶化ポリエチレンでは非晶部分が小さく、結晶部分によってメチレン鎖の運動が束縛され、トランス-ゴ-シュ間の障壁エネルギーが大きくなる。シリカゲルに吸着したポリエチレンにおいて、表面から離れた運動性の良い部分も両端あるいは片端が束縛されているのでバルクのポリエチレンの非晶領域と似ているといえる。この表面から離れている部分のトランス-ゴ-シュ間の障壁エネルギーは、結晶化ポリエチレンの非晶領域と比較して大きく、よって、表面から離れた部分は結晶化ポリエチレンの非晶部よりも小さいと考えられる。すなわち、この部分のメチレン鎖は結晶化ポリエチレンの非晶部のメチレン鎖よりも短いといえる。以上より、吸着したポリエチレン鎖には分子運動が強く束縛されたオールトランスおよびゴ-シュコンホメーションをとった部分と、トランス-ゴ-シュ間で速い転移が生じている部分の存在が明らかとなった。また、緩和時間測定を行い分子運動を調べた結果、トランス-ゴ-シュ間で速い転移をしている部分は、バルクのポリエチレンの非晶領域に比べて、シリカゲル表面の影響により分子運動が大きく束縛されていることがわかった。, kaken

  対象リソースIRI
• 試験研究(B), 1995年, 1995年, 06555288, 固体NMRイメージングプローブの開発と高分子材料への応用, 安藤 勲; 樋口 啓一郎; 黒子 弘道, 日本学術振興会, 科学研究費助成事業, 東京工業大学, 11900000, 11900000, 固体NMRイメージングプローブ(検出器)を製作を行い、運動性の悪い高分子材料の^<1)>HNMRイメージング画像を観測し、高分子材料の物性・機能についての三次元立体解析を行い高分子材料研究の重要な方法論として確立することを本研究課題の目的としている。 分子運動が悪い高分子材料のNMRシグナルは大変ブロードとなりNMRイメージング画像の分解能が極端に悪くなる。このために、本研究ではシグナルがブロードの原因となる双極子相互作用を消去するためのプローブを作成した。このプローブの性能テストもかねて高分子ゲル材料の電場印加による収縮過程を、^1HNMRイメージング画像を測定し画像解析を行うことにより明らかにした。また、開発した固体NMRイメージングが高分子材料の研究に優れた方法であることが明かとなった。今後の発展が大いに期待される。, kaken

  対象リソースIRI
• 一般研究(B), 1994年, 1995年, 06453152, ^1HNMRイメージング法による高分子ゲル中の応力-歪みの伝播の画像化, 安藤 勲; 黒子 弘道, 日本学術振興会, 科学研究費助成事業, 東京工業大学, 6800000, 6800000, 高分子ゲルの物性および機能の発現機構の解明にはどうしてもミクロとマクロを結び付けられる方法のアプローチが必務である。 本研究では、^1HNMRイメージング法がゲル中の核の空間密度分布また核の運動性の空間分布の情報を高い分解能で得るのに優ぐれた方法であることに注目し、ハイドロ高分子ゲルに圧力を印加することによる応力-歪みがどのようにゲルの中を伝播するかを分子レベルで解明したことと電場を印加することによるゲルの収縮の過程を試料中の水分子の空間密度分布および分子運動性の空間分布の情報にもとずいて解明した。また、高分子ゲルの変形過程の研究に^1HNMRイメージングが優ぐれた方法論であることを明らかにした。, kaken

  対象リソースIRI
• 奨励研究(A), 1993年, 1993年, 05750799, ポリフマレートの構造と分子運動についての研究, 黒子 弘道, 日本学術振興会, 科学研究費助成事業, 東京工業大学, 700000, 700000, 本研究課題ではpoly(diisopropyl fumarate)(PDiPF),poly(dicyclohexyl fumarate)(PDCHF),poly(methyl tert-buthyl fumarate)(PMETBF)およびpoly(isopropyl tert-buthyl fumarate)(PIPTBF)の構造と分子運動についての知見を得るため、温度可変固体高分解能NMR分光計(270MHz)を用いてCP/MAS測定および^<13>C,^1Hスピン-格子緩和時間測定を行った。PDiPFについては-30℃から115℃まで温度を変化させてCP/MAS測定を行ったところ、115℃で主鎖炭素,カルボニル炭素そして側鎖CH炭素のピーク強度が著しく減少した。これは主鎖炭素,カルボニル炭素そして側鎖CH炭素の運動性がこの温度で約63kHzの運動をしていることを意味し、これ以下の温度では63kHz以下の運動をしていることがわかった。また、メチル炭素についてはこの温度範囲においてほとんど強度変化を示していないことから、C_<3V>軸まわりの速い回転運動をしていると考えられる。綬和時間測定から、主鎖炭素,カルボニル炭素そして側鎖CH炭素はBPP理論におけるslow motion regionにあり、メチル炭素はextreme narrowing regionにあることがわかった。さらに、110℃でのmmとmrのトリアッドについてそれぞれT_1^Cを求めると、それぞれ13.8秒,9.8秒となり、mrトリアッドの運動性はmmトリアッドに比ベ高いことがわかった。さらに、プロトンのT_1を広い温度範囲で測定することにより、PDiPFの主鎖の運動性は120℃で約43kHzであることが明らかとなった。同様の測定・解析を他のポリフマレ一トにも行い、よりかさ高い側鎖を持つポリフマレートの主鎖の運動性はより束縛される等、多くの知見を得ることができた。, kaken

  対象リソースIRI
• 重点領域研究, 1990年, 1990年, 02230210, 固体状態における高分子鎖・金属イオン間相互作用と導電性発現についての分子設計, 安藤 勲; 黒子 弘道, 日本学術振興会, 科学研究費助成事業, 東京工業大学, 2500000, 2500000, 高分子の構造,電子状態,物性・機態(導電性など)の間には密接な関係がある。この関係を高い精度で解明できれば分子設計・材料設計および高分子科学に大きな発展が見られることは明らかである。このような考え方を基礎いして,高分子の導電性発現の理解及び予測する方法を開発し分子設計への基盤を確立することを本研究課題の目的としている。 本研究課題を進めるいあたり,ポリピロ-ルを研究対象とした。この高分子の導電性発現の機構は,ポリアセチレンのようなソリトンの生成によるものでなくポ-ラロン,バイポ-ラロンの生成によるものと考えられている。本研究で調製したポリピロ-ルの構造を固体を固体高分解能NMRで精度高く決定し,その構造に基いた電子状態をNMRしゃへい定数及びtightーbinding MO,FPTなどを用いて評価する。 ^<15>Nをラベルしたポリピロ-ルフィルを電解重合法で調製した。この際,未ド-プ及びド-プ試料を調製し,電気伝導度を測定した。 ^<15>NNMRスペクトルの解析から,NMRしゃへい定数が大きな範囲で分布した4本のシグナルの存有が確認された。低磁場側の2本のシグナルはキノイド構造に由来することが量子化学計算の助けで帰属できることが明らかとなった。また,ド-パントの量の増加とともにこれらの2本のシグナル強度が増加することがわかった。また,電気伝導度が大きくなり,これらのピ-クの強度と密接な関係があることが明らかとなった。また,tightbindingMO計算からキノイド型ポリピロ-ルのバンドギャップが芳香族型ポリピロ-ルのものより著るしく小さいことがわかった。本研究において開発された方法論が高分子の導電性発現の解明及び分子設計に大きく寄与することが明らかとなった。, kaken

  対象リソースIRI
• 基盤研究(B), 2021年04月01日, 2025年03月31日, 21H01668, 超臨界ナノプレーティング法によるナノ空間での金属成長機序の研究, 曽根 正人; 細田 秀樹; チャン ツォーフーマーク; 黒子 弘道, 日本学術振興会, 科学研究費助成事業, 東京工業大学, 17290000, 13300000, 3990000, 研究代表者らは、超臨界二酸化炭素（Sc-CO2）と電解質溶液を混合して乳濁状態としてめっきを行う方法である超臨界ナノプレーティング（SNP）法を開発した。２０２１年度において、この超臨界ナノプレーティング（SNP）法による電気化学反応を解析するため、新規高圧回転電極セルを設計・製造に成功した。 この高圧回転電極セルを用いて、Sc-CO2を混合した硫酸銅電解めっき液における銅電析の電気化学的特性を、硫酸銅電解めっき液にSc-CO2を混合した場合と混合しない場合の分極特性から調べた。限界電流密度と回転電極の回転速度との関係、いわゆるLevichプロットから、Sc-CO2を混合することで限界電流が大幅に増加すること、およびSc-CO2を混合する前と比較して、拡散係数は2倍以上増加し、動粘性係数は1/2以下に減少することを明らかにした。このことから、Sc-CO2混合めっき液を用いることで、対流による銅イオンの移動が大きく促進され、従来のめっき法では困難であった対流の小さい狭小空間の電析に対しても、Sc-CO2を用いた銅電着では銅イオンの供給が改善されるため、高アスペクト比のTSVのビア・フィリングに有効であることを見出した。 同時に高分子繊維表面においてナノ領域に触媒を輸送して、貴金属を被覆する技術の開発に成功した。特に重要な知見は、金属被覆が難しいとしられているポリエチレンテレフタレート繊維への貴金属被覆であり、新しい触媒反応系を見出し、密着性の高い金属被覆に成功した。, kaken

  対象リソースIRI
• 基盤研究(B), 2021年04月01日, 2025年03月31日, 21H00807, 次世代インテリジェントテキスタイルの創製とウェアラブルシステムへの応用, 黒子 弘道; 曽根 正人; 才脇 直樹; 佐藤 克成; チャン ツォーフーマーク; 橋本 朋子, 日本学術振興会, 科学研究費助成事業, 奈良女子大学, 15990000, 12300000, 3690000, 次世代インテリジェントテキスタイルを実現するために、超臨界二酸化炭素を用いた触媒化技術によるフレキシブルセンサー用触媒電極としてのPETフィルムの機能化が実現した。また、白金は生体適合性のある金属だが、ポリマー材料の白金メタライゼーションは難しいことが知られている。超臨界二酸化炭素を用いた触媒化技術により、PETと白金の統合が実現された。この白金被覆したPETフィルムについて、SEM観察により表面の状態を明らかにし、さらに高次構造解析を固体ＮＭＲ法により詳細に行うことにより、触媒化とめっき処理による構造変化に関する知見を得た。また、センシング、光触媒による抗菌・抗ウイルス性、および身体情報提示の各機能を有するインテリジェントウェアラブル材料の基布となる各繊維を用いて、全反射測定法によるフーリエ変換赤外吸収スペクトル測定などにより、比較のための材料表面情報を得た。また各機能性ウェアラブル材料の安全性評価のための予備検討を進めた。 導電性に優れたスマートテキスタイルを情報処理技術と組み合わせることで、日々の暮らしを見守ったり日常生活を豊かにするインタフェースとして構築する研究に取り組んだ。特に、乳がん患者支援や水難事故防止といった、問題解決が困難な事象にもスマートテキスタイルを用いたシステムが役立つ事を示した。また、その成果を生かし、技術の国際標準化や啓蒙活動にも貢献することができた。 導電性繊維のウェアラブルヒータとしての応用にむけ、温度勾配のある面的な刺激の有効性を評価し、一様な刺激よりも効率良く温感を提示しうることが示唆された。また、筋電気刺激用ウェアラブル電極としての応用に向け、姿勢維持の補助デバイスとしての効果を確認した。さらにに、月経痛の再現デバイスとして、実際の月経痛よりも腹部の浅い位置ではあるが同等の強度を提示しうることを確認した。, kaken

  対象リソースIRI
• 基盤研究(B), 2014年04月01日, 2017年03月31日, 26282013, 次世代センシング繊維の創成とウェアラブルセンサへの応用, 黒子 弘道; 曽根 正人; 才脇 直樹; 佐藤 克成; 橋本 朋子, 日本学術振興会, 科学研究費助成事業, 奈良女子大学, 16900000, 13000000, 3900000, 超臨界二酸化炭素に有機金属錯体を用いて、ナイロン繊維内部に触媒としてのパラジウム原子あるいは白金原子を析出させ、無電解めっき法により安定性の高いニッケルおよび白金を被覆した繊維を作成することができた。さらにこの繊維の触媒化の際のナイロン繊維の構造変化を固体NMR及び量子化学計算を用いて解析を行った結果、パラジウム原子はナイロン繊維のカルボニル炭素近傍に存在することが分かった。導電性繊維を用いた応用についても検討し、導電性繊維を配線に用いることで、布や衣服とデバイスを一体化して使用できる可能性が確かめられた。さらに、人の健康を支援する2種類のウェアラブルコンピュータの試作評価を行った。, kaken

  対象リソースIRI

Ⅲ．社会連携活動実績

１．公的団体の委員等（審議会、国家試験委員、他大学評価委員，科研費審査委員等）

• 日本家政学会, 監事, 2023年05月, 2024年05月
• 日本家政学会, 理事、関西支部長, 2020年年5月, 2022年年5月
• 日本家政学会, 理事、関西支部長, 2020年
• 学協会
• 日本家政学会, 被服材料部会幹事, 学協会
• 学協会
• 繊維学会, 関西支部役員, 学協会
• 学協会
• 高分子学会, ＮＭＲ研究会 運営委員会 副運営委員長, 学協会
• 学協会
• 高分子学会, 高分子学会関西支部常任幹事, 学協会