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| 1.
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Nagatani, Hirohisa ; Fujisawa, Masataka ; Imura, Hisanori ; 永谷, 広久 ; 井村, 久則
概要:
金沢大学理工研究域物質化学系<br />Molecular association between biocompatible dendritic polymers, dendrigraft poly-l-lysines (DGLs), a
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nd an anionic fluorescent probe, 8-anilino-1-naphthalenesulfonate (ANS-), was studied at the polarized water|1,2-dichloroethane (DCE) interface. The fluorescence intensity of ANS measured in aqueous solution was enhanced by the coexistence of DGLs over a wide pH range (2 < pH < 10), where ANS and DGL exist as a monoanionic form and a polycation, respectively. The voltammetric responses indicated that the positively charged DGLs were adsorbed at the water|DCE interface, whereas ANS- was transferred across the interface accompanied by the adsorption process. The interfacial behavior of the DGL-ANS associates was analyzed by potential-modulated fluorescence (PMF) spectroscopy. The PMF results demonstrated that the ion association between DGLs and ANS at the water|DCE interface is strongly affected by the applied potential and the dendritic generation of DGL. By applying appropriate potentials, the ANS anion was dissociated from its ion associate with DGLs at the interface and transferred into the organic phase, whereas DGLs remained in the aqueous phase. The Gibbs free energy of ion association (ΔGD···ANS) was estimated for the second-fourth generation DGLs (DGL-G2-G4) and the G4 polyamidoamine (PAMAM) dendrimer as a control. The highest stability of the DGL-G4-ANS associate manifested itself through ΔGD···ANS: DGL-G4-ANS (>G4 PAMAM dendrimer-ANS) > DGL-G3-ANS > DGL-G2-ANS. The results elucidated the efficient anion-binding ability of higher generation DGLs and its potential dependence at the liquid|liquid interface. © 2018 American Chemical Society.<br />Embargo Periods 12 Months
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| 2.
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論文
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Yamamoto, Sho ; Nagatani, Hirohisa ; Imura, Hisanori ; 永谷, 広久 ; 井村, 久則
概要:
金沢大学理工研究域物質化学系<br />The adsorption and self-aggregation of anionic porphyrins were studied at the polarized water|1,2-di
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chloroethane (DCE) interface by polarization-modulation total internal reflection fluorescence (PM-TIRF) spectroscopy. 5,10,15,20-Tetrakis(4-sulfonatophenyl)porphyrin diacid (H4TPPS2-) and protoporphyrin IX (H2PP2-) exhibited high surface activities at the interface. The selective excitation of interfacial species in PM-TIRF measurements elucidated the potential-induced aggregation mechanism of the porphyrins. The J-aggregates of H4TPPS2- were reversibly formed only at the water|DCE interface by applying appropriate potentials even when the porphyrins exist as monomers in the aqueous and organic solutions. In the H2PP2- system, the slow aggregation process was found in the negative potential region. The spectral characteristics and the signal phase of PM-TIRF indicated that the H2PP2- monomers were adsorbed with relatively standing orientation and that the long axis of the J-aggregates was nearly in plane of the interface. H2PP2- was also investigated at the biomimetic phospholipid-adsorbed water|DCE interface. The competitive adsorption of neutral glycerophospholipids effectively inhibited the potential-dependent adsorption and interfacial aggregation processes of H2PP2-. The results demonstrated that the aggregation state of the charged species can reversibly be controlled at liquid|liquid interfaces as a function of externally applied potential. © 2017 American Chemical Society.<br />Embargo Period 12 months
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| 3.
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論文
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森口, 弥香 ; 永谷, 広久 ; 枝, 和男 ; 大堺, 利行
概要:
モノカチオン型の膜電位感受性色素3,3'-ジエチルオキサカルボシアニン｛diOC2(3)｝を添加した1,2-ジクロロエタン（DCE）｜水（W）界面において，水相中の支持電解質カチオン（Li＋, Na＋, K＋, Mg2＋, Ca2＋）の促進
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移動と思われる異常に大きなボルタンメトリー波が観察された．このメカニズムを解明するため，交流ボルタンメトリーによる界面の電気二重層容量の測定，及び電位変調蛍光分光測定を行った．その結果，diOC2(3)と油相中の支持電解質アニオン｛テトラキス（4-クロロフェニル）ホウ酸｝がDCE｜W界面に共吸着し，その吸着層にイオンサイズの小さいカチオンがインターカレーションされ，移動が容易になると推察された．この促進効果はアルカリ金属よりもアルカリ土類金属の方が顕著であった．<br />At the 1,2-dichloroethane (DCE) | water (W) interface upon the addition of a monocationic membrane-potential-sensitive dye, 3,3'-diethyloxacarbocyanine {diOC2(3)}, an extraordinarily large voltammetric wave, was observed. This was probably due to a facilitated transfer of the supporting-electrolyte cation in W (i.e., Li+, Na+, K+, Mg2+, Ca2+). In order to explain the mechanism, we also carried out a determination of the double-layer capacity of the interface by ac voltammetry and potential-modulated fluorescence (PMF) spectroscopy measurements. The results have suggested that monocationic diOC2(3) and the supporting-electrolyte anion in DCE {tetrakis(4-chlorophenyl)borate} are co-adsorbed (probably in multilayers) at the DCE | W interface and, into the adsorption layer, the above cations of small sizes are intercalated, and thus transferred more easily. This facilitation effect is more significant for alkali-earth metal ions than for the alkali metal ions. A possible application has been suggested concerning the voltammetric or fluorescence determination of Mg2+ and/or Ca2+ (e.g., water hardness analysis).
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| 4.
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論文
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森口, 弥香 ; 永谷, 広久 ; 枝, 和男 ; 大堺, 利行
概要:
At the 1,2-dichloroethane (DCE) | water (W) interface upon the addition of a monocationic membrane-potential-sensitive d
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ye, 3,3'-diethyloxacarbocyanine {diOC2(3)}, an extraordinarily large voltammetric wave, was observed. This was probably due to a facilitated transfer of the supporting-electrolyte cation in W (i.e., Li+, Na+, K+, Mg2+, Ca2+). In order to explain the mechanism, we also carried out a determination of the double-layer capacity of the interface by ac voltammetry and potential-modulated fluorescence (PMF) spectroscopy measurements. The results have suggested that monocationic diOC2(3) and the supporting-electrolyte anion in DCE {tetrakis(4-chlorophenyl)borate} are co-adsorbed (probably in multilayers) at the DCE | W interface and, into the adsorption layer, the above cations of small sizes are intercalated, and thus transferred more easily. This facilitation effect is more significant for alkali-earth metal ions than for the alkali metal ions. A possible application has been suggested concerning the voltammetric or fluorescence determination of Mg2+ and/or Ca2+ (e.g., water hardness analysis). モノカチオン型の膜電位感受性色素3,3'-ジエチルオキサカルボシアニン｛diOC2(3)｝を添加した1,2-ジクロロエタン（DCE）｜水（W）界面において，水相中の支持電解質カチオン（Li＋, Na＋, K＋, Mg2＋, Ca2＋）の促進移動と思われる異常に大きなボルタンメトリー波が観察された．このメカニズムを解明するため，交流ボルタンメトリーによる界面の電気二重層容量の測定，及び電位変調蛍光分光測定を行った．その結果，diOC2(3)と油相中の支持電解質アニオン｛テトラキス（4-クロロフェニル）ホウ酸｝がDCE｜W界面に共吸着し，その吸着層にイオンサイズの小さいカチオンがインターカレーションされ，移動が容易になると推察された．この促進効果はアルカリ金属よりもアルカリ土類金属の方が顕著であった．
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| 5.
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論文
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永谷, 広久 ; Nagatani, Hirohisa
概要:
金沢大学理工研究域物質化学系<br />イオン性分子とデンドリマーとの相互作用を利用した液液分配反応の電気化学的制御と光機能化デンドリマーの分光検出試薬としての応用について分光電気化学的に研究した。界面電荷移動反応の解析により、イオン性分子
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のデンドリマーへの包接は、デンドリマーのサイズと荷電状態の変化に依存することが明らかとなった。さらに、対称性や電荷数が同じ条件でも、被包接分子の中心金属への配位などが包接安定性に強く影響することを見いだした。また、金ナノドットとの複合化や化学処理を通じてデンドリマーを光機能化し、液液分配系における金属イオンの分離・検出試薬としての適応性を確認した。<br />Electrochemical control of liquid/liquid distribution of ionic species through specific interactions with the dendrimer and application of photofunctionalized dendrimers as a spectrophotometric reagent were studied by means of spectroelectrochemical techniques. The mechanistic analysis of charge transfer reactions across the liquid/liquid interface demonstrated that the encapsulation behavior of ions into the dendrimer significantly depends on the molecular size and charged state of the dendrimer. It was also indicated that the axial-coordinations of the dendrimer to the metal center of encapsulated species could enhance the ion association stability. In addition, the photofunctionalized dendrimers obtained from the hybridization with luminescent gold nanodots and chemical modifications were examined as separation and spectrophotometric reagents for metal ions in liquid/liquid systems.<br />研究課題/領域番号:24550097, 研究期間(年度):2012-04-01 - 2015-03-31
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| 6.
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論文
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永谷, 広久 ; Nagatani, Hirohisa
概要:
液液界面におけるデンドリマーのアニオン性蛍光色素に対する分子包接挙動について研究した。アニオン種は静電相互作用によってプロトン化したデンドリマーに効率的に包接された。分光電気化学的測定から、アニオンを包接したデンドリマーは吸着過程を伴ってイ
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オン移動していることが明らかになった。さらに、液液界面で隔てられた亜鉛ポルフィリンと消光剤の間で生じる光誘起電子移動反応では、デンドリマーを添加することで光電流値が増加することを見いだした。\n<br />Molecular encapsulation of anionic fluorescent dye molecules in the dendrimer was investigated at the polarized liquid/liquid interface. The anionic species was electrostatically incorporated in the dendrimer depending on the pH conditions. The spectroelectrochemical analysis demonstrated that the interfacial mechanism of the dendrimer associated with anions involves transfer and adsorption processes. In addition, a heterogeneous photoinduced electron transfer between anionic zinc porphyrin and hydrophobic quenchers at the interface was examined in the presence of the dendrimer. The photocurrent response was significantly increased by the addition of the dendrimer.<br />研究課題/領域番号:21750078, 研究期間(年度):2009-2010
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| 7.
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論文
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永谷, 広久 ; Nagatani, Hirohisa
概要:
有機分子やキレート配位子に対する種々の多分岐高分子（デンドリマー，デンドリグラフトポリマー，ハイパーブランチポリマー）の包接特性を分光電気化学的に検討し、分離化学、ナノ材料合成、生体膜のモデル反応場などで重要な液液界面における電荷移動反応の
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制御に応用した。溶液相ではイオン性官能基に起因する静電相互作用が包接特性に支配的に影響し、多分岐高分子が特異反応場として機能することを見いだした。一方、液液界面では、静電相互作用に加えて多分岐高分子や被包接化学種の界面吸着性が大きく寄与し、相間分配と界面反応の機構が変化することを明らかにした。<br />Molecular association of various organic molecules and chelating agents with dendritic polymers such as dendrimer, dendrigraft polymer and hyperbranched polymer, was spectroelectrochemically analyzed in detail. The dendritic polymers were applied to control charge transfer reactions at the liquid/liquid interface as an important reaction field for separation, nanomaterial formation, biomimetic reaction analysis and so on. The association between ionic species and dendritic polymers was dominantly affected by the electrostatic interaction in solution where the dendritic polymers provide a specific micro-reaction field. In addition at liquid/liquid interfaces, the interfacial activities of both the dendritic polymer and associated species significantly influenced the phase transfer and interfacial mechanisms.<br />研究課題/領域番号:16K05811, 研究期間(年度):2016-04-01 – 2019-03-31<br />出典：「多分岐高分子の分子包接特性を利用した液液界面の反応制御と分光計測への応用」研究成果報告書 課題番号16K05811（KAKEN：科学研究費助成事業データベース（国立情報学研究所）） （https://kaken.nii.ac.jp/ja/report/KAKENHI-PROJECT-16K05811/16K05811seika/）を加工して作成
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| 8.
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井村久則, 樋上照男編
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| 9.
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井村久則, 樋上照男編
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