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工学教育研究部 工学科化学生命プログラム担当 |
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准教授 |
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論文 【 表示 ／ 非表示 】
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Light-driven mechanical motion of a two-dimensional network of polyfluorinated surfactants having azobenzene moiety sandwiched by niobate nanosheets: Effect of pH of intercalation solution 招待あり 査読あり 国際誌
Y. Nabetani, S. Z. Hassan, K. Koganemaru, H. Tachibana, H. Inoue, T. Shiragami
Journal of Photochemistry and Photobiology A: Chemistry 466 116402 2025年9月
担当区分：筆頭著者, 責任著者 掲載種別：研究論文（学術雑誌）
A hybrid composed of polyfluoroalkyl azobenzene derivative (C3F-Azo-C6H) and layered niobate nanosheet can undergo interlayer distance change and nanosheet sliding motion upon photo-irradiations. However, such morphology changes are not yet sufficiently controlled, exhibiting somewhat fluctuating results. It is necessary to clarify what kind of intercalation environment promotes the high-order architecture formation suitable for the more efficient photo-induced morphology change. In this study, we have focused on the pH conditions of intercalation solution and analyzed the nanostructure and morphology change of the hybrid fabricated under the basic (pH = 11.0) and the acidic (pH = 2.4) conditions. Intercalating C3F-Azo-C6Hs into the nanosheets under the basic condition afforded a larger interlayer distance as compared with that under the acidic condition. Furthermore, the more substantial interlayer distance change (expansion ratio: 21 %) and the nanosheet sliding (sliding distance: ∼ 200 nm) were successfully induced upon UV–vis photo-irradiations of the hybrid fabricated under the basic conditions, while the hybrid fabricated under the acidic conditions exhibited the smaller changes (interlayer expansion ratio: 0.8 % with unstable/negligible nanosheet sliding). Under the basic conditions, the nanostructure of the C3F-Azo-C6Hs bilayer having non-interdigitation of the terminal alkyl chain of the two-monolayers faced each other in the bilayer caused the substantial morphology changes such as interlayer distance change and nanosheet sliding, whereas the deeply interdigitated terminal alkyl chains in the hybrid fabricated under the acidic conditions caused only a little/negligible morphology change. Factors controlling the drastic changes of the nanostructure derived from the different fabrication conditions have been discussed.
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Nabetani Y., Ramakrishnan V., Nakazato R., Iwata Y., Tachibana H., Inoue H., Shiragami T.
Journal of Photochemistry and Photobiology A: Chemistry 462 116245 2025年5月
担当区分：筆頭著者, 責任著者 記述言語：英語 掲載種別：研究論文（学術雑誌） 出版者・発行元：Journal of Photochemistry and Photobiology A: Chemistry
Following our previous report on the heat trapping in organic/inorganic hybrid compound with bilayer structure formed by cationic polyfluorinated surfactant containing azobenzene moiety (C3F-Azo-C6H) in the interlayer of cation-exchangeable synthetic clay (Smecton SA: SSA) nanosheets having been probed by a temperature sensing Rhodamine B (RhB) upon excitation by a fixed wavelength of visible light, a systematic study of the effect of wavelength dependency for the excitation was carried out to get deeper insight into the heat trapping. Evident wavelength effect of excitation on the temperature elevation was observed. Among three components in the fluorescence lifetime (τ1, τ2, τ3) of RhB, the local temperatures T1, T2 deduced from τ1, τ2 exhibited a systematic temperature elevation upon excitation of RhB with a shorter wavelength of visible light (570–520 nm). Estimation of the energy stored against the energy input indicated that an excess energy initially deposited at Franck-Condon state is retained in a limited number of local modes during the fluorescence lifetime through a pretty slow intramolecular vibrational relaxation (IVR) in the interlayer. Structural analysis by TD-DFT calculation strongly suggested that all the local modes within RhB are classified into four groups (I–IV), which well coincides with the prediction by a comparison analysis in respect to the energy stored against the energy input to rationalize that the IVR of RhB for τ1 component (T1) in the interlayer is limited among the local mode groups I (#1–10)–II (#11–21) and τ2 component (T2) being restricted up to group III (# 22–36). The systematic study revealed that the hybrid compound C3F-Azo-C6H/SSA provides a unique microenvironment having gaseous/vacuum-like atmosphere to a molecule incorporated in the narrow gap space sandwiched by neighboring C3F-Azo-C6H molecules in the interlayer to allow an inherently slow IVR.
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Ishihara Y., Kajino M., Iwamoto Y., Nakane T., Nabetani Y., Okuda T., Kono M., Okochi H.
Toxicological Sciences 203 ( 2 ) 242 - 252 2025年2月
記述言語：英語 掲載種別：研究論文（学術雑誌） 出版者・発行元：Toxicological Sciences
Microplastics are ubiquitous in the atmosphere, leading to human exposure through inhalation. Airborne microplastics undergo degradation due to sunlight irradiation, yet the respiratory risks associated with degraded microplastics remain poorly understood. In this study, we investigated the respiratory effects of polyethylene terephthalate (PET) degraded by artificial sunlight and created a transport and degradation model of PET for risk assessment. PET fibers were cut and subjected to artificial sunlight irradiation. Mice exposed to aged PET showed increased airway resistance induced by methacholine (MCh) inhalation, along with lung inflammation and neutrophil infiltration. Terephthalic acid (TPA) was continuously released from PET aged by artificial sunlight. Exposure to TPA also caused lung inflammation and enhanced airway resistance induced by MCh in mice. These findings indicate that aged PET can cause respiratory impairment via TPA release. A simple transport and degradation model was developed to quantitatively relate the abundance of aged PET produced in this study (i.e. 4,000 × 96 W m-2 h) and aged fractions of PET that can be generated in the atmosphere. Our results suggested 10% to 60% of PET was degraded as that produced in this study over sunny regions in summer, whereas only lower than 1% in high-latitude cities in Europe in winter. This study demonstrates the importance of considering the abundance of aged PET and further development of a transport and degradation model of PET to assess the risk of degraded PET in the atmosphere.
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Long-term exposure to urban particulate matter exacerbates mortality after ischemic stroke in mice 査読あり
Ishihara N., Tanaka M., Namba K., Kawano S., Nishimura S., Nezu N., Nakane T., Oguro A., Okuda T., Itoh K., Nabetani Y., Ishihara Y.
Journal of Toxicological Sciences 50 ( 3 ) 147 - 159 2025年
記述言語：英語 掲載種別：研究論文（学術雑誌） 出版者・発行元：Journal of Toxicological Sciences
Exposure to fine particulate matter (PM2.5) has been epidemiologically reported to wors-en the prognosis of ischemic stroke; however, the details have not been investigated. One of the major toxic mechanisms of PM2.5 inhalation is oxidative stress, which is mediated by reactive oxygen species generated by PM2.5 components such as metals and polycyclic aromatic hydrocarbons. In this study, we examined the effects of long-term exposure to urban particulate matter, focusing on oxidative stress, on prognosis after ischemic stroke in mice. When mice were intranasally exposed for 28 days to an urban aerosol collected in Beijing, China (CRM28), microglial activation was observed in the cerebral cortex, indicating that CRM28 induced neuroinflammation. CRM28 exposure resulted in increased serum levels of brain natriuretic peptide and troponin I, suggesting that cardiac injury was elicited by CRM28. Lung inflammation was also observed following CRM28 exposure; however, systemic inflammation was not detected. Mice exposed to CRM28 showed an exacerbation of mortality after ischemic stroke induction compared with vehicle mice. A vitamin E-rich diet suppressed CRM28-induced lipid peroxidation in the heart and lungs but not in the brain. A vitamin E-rich diet also attenuated cardiac injury and lung inflammation induced by CRM28 exposure, whereas neuroinflammation was not affected. Mortality after ischemic stroke improved with the administration of a vitamin E-rich diet. Considering that systemic inflammation did not occur, cardiac injury induced by oxidative stress under exposure to urban particulate matter may be involved in increased mortality after ischemic stroke. Antioxidation under air pollution is fundamental for protection against ischemic stroke.
DOI： 10.2131/jts.50.147
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Nakazato R., Ohsaki Y., Thomas A., Mathew S., Nabetani Y., Sebastian A., Kuttassery F., Remello S.N., Tachibana H., Inoue H.
Journal of Physical Chemistry C 128 ( 45 ) 19122 - 19133 2024年11月
記述言語：英語 掲載種別：研究論文（学術雑誌） 出版者・発行元：Journal of Physical Chemistry C
As one of the most promising molecular catalyst sensitized systems (MCSS) for an artificial photosynthesis, photochemical two-electron water oxidation into hydrogen peroxide catalyzed by tetra-pyridylporphyrinatetinIV (SnTPyP) adsorbed on SnO2 nanoparticles fabricated as a photoanode upon one-photon visible-light excitation was examined. Unimolecular SnTPyPaxial/SnO2 covalently bound through an axial ligand O atom (1), cationic unimolecular (SnTPyP(PrBr)4)axial/SnO2 covalently bound through an axial ligand O atom (2), cationic unimolecular (SnTPyP(PrBr)4)ionic/SnO2 bound through ionic interaction (3), cationic oligomer ((SnTPyP(PrBr)4)ionic)4/SnTPyPaxial/SnO2 with only the central SnTPyP covalently bound through axial coordination (4), cationic oligomer ((SnTPyP(PrBr)4)axial)4/SnTPyPaxial/SnO2 with all five SnTPyPs covalently bound through axial coordination (5), cationic oligomer ((SnTPyP(PrBr)4)ionic)3/SnTPyPsilyl/SnO2 covalently bound through silylation of the SnO2 surface (6), and unimolecular SnTPyPsilyl/SnO2 covalently bound through silylation of the SnO2 surface (7) were fabricated as the photoanodes, and their photoelectrochemical behavior was examined to characterize five factors: the absorbed photon to current efficiency (APCE), light harvesting efficiency (LHE), durability as the time period for 90% decay from the initial photocurrent (T90%), amount of H2O2 accumulation, and Faradaic yield of H2O2 formation. The unimolecular silylated SnTPyPsilyl/SnO2 (7) exhibited the highest APCE (45%), which could be caused by a swing motion of propylsilyloxyl bridging moieties to make one-electron oxidized SnTPyP away from the SnO2 surface just after an electron injection from the excited SnTPyP into the conduction band of SnO2 and to facilitate the charge separation by retarding the charge recombination process. On the other hand, the unimolecular SnTPyP covalently bound through coordination of an axial ligand atom (1) exhibited a modest APCE (11%), which faces rather intimately with the SnO2 surface to undergo substantial charge recombination. The modest reactivity was similarly observed for oligomeric SnTPyPs (5: APCE 12%) with all five porphyrins being covalently bound to the SnO2 surface suffering enhanced charge recombination. Other oligomeric SnTPyPs, 4 (APCE 22%) and 6 (APCE 29%), showed moderate reactivity owing to a presumed hole hopping among SnTPyPs within oligomers enabling the better charge separation. All the oligomers (4, 5, and 6) with strongly light absorptive SnTPyPs exhibited better LHE than unimolecular systems and better durability (T90%) by hanging over the SnO2 surface to protect from an attack of hydronium ion (H3O+) leading to a substantial desorption of SnTPyPs under the acidified conditions caused by a microscopic pH jumping effect in the narrow gap space between SnO2 nanoparticles, emphasizing the privileged situation for the oligomeric systems.
講演・口頭発表等 【 表示 ／ 非表示 】
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ゲルマニウム-N-混乱ポルフィリン錯体を 増感剤とする光電子移動反応に対する金属カチオンの添加効果
井上 舞香, 鍋谷 悠, 白上 努
第14回CSJ化学フェスタ2024 2024年10月22日
開催年月日： 2024年10月22日 - 2024年10月24日
記述言語：日本語 会議種別：ポスター発表
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ゲルマニウムポルフィリン‧酸化チタン複合電極を用いたメタノールのホルムアルデヒドへの光酸化反応
一宮 大起, 鍋谷 悠, 白上 努
第14回CSJ化学フェスタ2024 2024年10月22日
開催年月日： 2024年10月22日 - 2024年10月24日
記述言語：日本語 会議種別：ポスター発表
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チタン酸ナノシートを用いた光応答性層状複合体の作製と光運動誘起
鍋谷 悠, 濵砂 幸人, 白上 努
2024年光化学討論会 2024年9月3日
開催年月日： 2024年9月3日 - 2024年9月5日
記述言語：日本語 会議種別：ポスター発表
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金ナノ粒子/ニオブ酸ナノスクロール複合体のナノ構造と光学特性の制御
矢野 海竜, 宮本 大晴, 宇和田 貴之, 白上 努, 鍋谷 悠
第61回化学関連支部合同九州大会 2024年6月29日
開催年月日： 2024年6月29日
記述言語：日本語 会議種別：ポスター発表
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アゾベンゼン/ナノシート複合体による光メカニカル機能材料の開発
森井 薫, 森田 晃代, 白上 努, 鍋谷 悠
第13回CSJ化学フェスタ2023 2023年10月17日
開催年月日： 2023年10月17日 - 2023年10月19日
記述言語：日本語 会議種別：ポスター発表
受賞 【 表示 ／ 非表示 】
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8th Asian Photochemistry Conference (APC-2014), Poster prize
2014年11月 Asian Photochemistry Conference
Yu Nabetani
受賞区分：国際学会・会議・シンポジウム等の賞 受賞国：日本国
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日本化学会第88春季年会優秀講演賞（学術）
2008年4月 日本化学会 光応答性スパイラルナノチューブの形態ダイナミクス
鍋谷 悠
受賞区分：国内学会・会議・シンポジウム等の賞 受賞国：日本国
科研費（文科省・学振・厚労省）獲得実績 【 表示 ／ 非表示 】
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キラルナノ層状構造の構築と光運動機能発現のメカニズム解明
研究課題/領域番号：23K04538 2023年04月 - 2026年03月
独立行政法人日本学術振興会 科学研究費基金 基盤研究(C)
担当区分：研究代表者
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タンパク質結晶細孔をテンプレートとした三次元組織化複合ナノ構造材料の創生
研究課題/領域番号：20K05269 2020年04月 - 2023年03月
独立行政法人日本学術振興会 科学研究費補助金 基盤研究(C)
担当区分：研究分担者
タンパク質の機能や構造を知るため細心の注意を持って作られるタンパク質の結晶は、その内部に三次元状に広がる溶媒チャンネルはナノメートルサイズの細孔構造を有している。その細孔は表面のタンパク質に由来する不均一な空間であるため、タンパク質結晶は新規かつ高機能な多孔質材料であるといえる。我々はこれまでこのタンパク質結晶細孔への分子導入を明らかにし、その機能と有用性を実証してきた。本研究計画ではこれを発展させ、タンパク質結晶をテンプレートとすることで新たな光学特性を発現する三次元的複合ナノ構造材料を作り出す。同時に顕微鏡観察技術を駆使しタンパク質結晶の多孔質材料・反応容器としての機能を明らかにする。
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新規光応答性ナノスクロールの作製と光伸縮機構の解明
研究課題/領域番号：20K05267 2020年04月 - 2023年03月
独立行政法人日本学術振興会 科学研究費補助金 基盤研究(C)
担当区分：研究代表者
本研究では、チタン酸やチタンニオブ酸などのニオブ酸とは異なる表面構造をもつナノシートに注目し、多フッ素化アルキルアゾベンゼンとの複合化によって、光伸縮運動を示す新たな光応答性ナノスクロールを作製する。ナノシート表面構造によりナノスクロール内部の構造を制御して原子間力顕微鏡等により光伸縮運動を解析する。また、分子構造の視点からアルキル鎖長を変えたアゾベンゼンの導入により複合体の物性を制御し、ナノスクロールが示す光運動機能の発現機構を解明する。
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水の酸化光触媒機能を有する人工光合成システム
研究課題/領域番号：24107003 2016年10月 - 2017年03月
科学研究費補助金 新学術領域研究
担当区分：研究分担者
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光応答性ナノシート積層膜が示すフォトメカニカル機能の機構解明
研究課題/領域番号：24710108 2012年04月 - 2014年03月
科学研究費補助金 若手研究(B)
担当区分：研究代表者
その他競争的資金獲得実績 【 表示 ／ 非表示 】
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PM2.5の脳循環および脳梗塞予後に及ぼす影響の解析
2020年04月 - 2023年03月
環境省 環境再生保全機構環境研究総合推進費
担当区分：研究分担者 資金種別：競争的資金