Development and its application of anion sensor consist of polymer film for the use of nonaqueous solution

非水溶液用聚合物薄膜阴离子传感器的研制及其应用

• 批准号: 10640587
• 负责人: NAKAMURA Toshio
• 金额: $ 1.09万
• 依托单位: Shinshu University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10640587/
• 关键词: nonaqueous solution; anion sensor; phthalocyanine complex; hydrophilic polymer film; fluoride cyanide ions; thermodynamic parameters; potentimetric response mechanism; acceptor number; イオンセンサー; 高分子膜; フッ化物イオン; シアン化物イオン; 金属フタロシアニン; 配位子交換反応

The results obtained are as follows :The potentiometric response behavior of an electrode consisting of a non-plasticized polyacrylamide polymer (PAA) film coupled to oxo(phthalocyaninato)gallium(III) ([Ga(pc)]) was examined for various anions in such nonaqueous solvents as acetonitrile (AN), dimethylacetamide (DMA), and N-methylpyrrolidinone (NMP). The electrode, (PAA-([Ga(pc)]), shows a selective Nernstian response to FィイD1-ィエD1 and CNィイD1-ィエD1 in AN and a near-Nemstian response to those ionsin DMA and NMP. On the other hand it shows a non-thermodynamic response to ClィイD1-ィエD1, BrィイD1-ィエD1, IィイD1-ィエD1, NOィイD3-(/)2ィエD3, SCNィイD1-ィエD1, BPhィイD3-(/)4ィエD3, PFィイD3-(/)6ィエD3, ClOィイD3-(/)4ィエD3, and CFィイD23ィエD2SOィイD3-(/)3ィエD3. The result was mainly the same response as that obtained at the other electrodes, PAA-[M(pc)]s (M=Co,VO) reported by the authors and spectrometric investigations of FィイD1-ィエD1 and CNィイD1-ィエD1 in several aprotic solvents reveal that complex formation reactions of the ions … More with [M(pc)] made such special response phenomena. The complexing may occur due to ligand exchange reactions of the ions with solvent molecules or water molecule(s) coordinated originally to [Ga(pc)]s. The molar ratio of [Ga(pc)] and FィイD1-ィエD1 was confirmed by spectrophotometrically to be 1 : 1 and the complexing was considered to be occurred at the axial site of the complex. The complexing of [Ga(pc)] with ClィイD1-ィエD1 in GBL was also observed and it may occur due to the week solvation of GBL to ClィイD1-ィエD1. UV/VIS spectra for the FィイD1-ィエD1 and CNィイD1-ィエD1 in GBL was different from those obtained in other solvents investigated in the experiment and that was related firmly to the solvent acidity, I.e., their acceptor number. The electrode could be applicable to obtain solubility product, Kap, of NaF in AN.Next lectures are presented concerning the project :(1) Proceeding of 59ィイD1thィエD1 Bunsekikagaku Touronkai. P15 (at Otaru), (2) Proceeding of 60ィイD1thィエD1 Bunsekikagaku Touronkai, p110 (at Hirosaki), (3) Proceeding of 48ィイD1thィエD1 Bunsekikagaku Nennkai, p243 (at Kobe). Less

获得的结果如下：研究了由与氧代（酞菁）镓（III）（[Ga（pc）]）耦合的非增塑聚丙烯酰胺聚合物（PAA）膜组成的电极在乙腈（AN）、二甲基乙酰胺（DMA）和二甲基乙酰胺（DMA）等非水溶剂中对各种阴离子的电位响应行为。 N-甲基吡咯烷酮（NMP）。电极 (PAA-([Ga(pc)]) 显示出对 AN 中的 FィイD1-ィエD1 和 CNィイD1-ィエD1 的选择性能斯特响应，以及对 DMA 和 NMP 中的离子的近能斯特响应。另一方面，它显示出对 ClィイD1-ィエD1 的非热力学响应， BrィイD1-ィエD1, IィイD1-ィエD1、NOィイD3-(/)2ィエD3、SCNィイD1-ィエD1、BPhィイD3-(/)4ィエD3、PFィイD3-(/)6ィエD3、 ClOィイD3-(/)4ィエD3和CFィイD23ィエD2SOィイD3-(/)3ィエD3。结果主要是 作者报告的 PAA-[M(pc)]s (M=Co,VO) 与其他电极获得的响应相同，并对 FィイD1-ィエD1 和 CNィイD1-ィエD1 在几种非质子溶剂中进行的光谱研究表明，离子与 [M(pc)] 的复杂形成反应产生了这种特殊的响应现象。络合可能是由于离子的配体交换反应而发生的 溶剂分子或水分子最初与[Ga(pc)]s配位。通过分光光度法证实[Ga(pc)]和FィイD1-ィエD1的摩尔比为1:1，并且认为络合发生在络合物的轴向位点。还观察到 [Ga(pc)] 与 GBL 中的 CliiD1-ィエD1 形成络合，并且 可能是由于GBL溶解为ClィイD1-ィエD1的时间较短而发生。 GBL 中 FiiD1-iiD1 和 CNiiD1-iiD1 的 UV/VIS 光谱与实验中研究的其他溶剂中获得的紫外/可见光谱不同，并且与溶剂酸度（即它们的受体数）密切相关。该电极可用于获得 NaF 在水中的溶度积 Kap AN. 接下来的讲座将介绍有关该项目的内容：(1) 59ィイD1thィエD1 Bunsekikagaku Touronkai 论文集。 P15（小樽）、（2）60ィイD1thィエD1文石化学巡回会论文集、p110（弘前）、（3）48ィイD1thィエD1论文集 Bunsekikagaku Nennkai，第 243 页（神户）。少

项目成果

T.Nakamura, T.Ueda, T.Yanagisawa, H.Watanabe: "The Response Properties of a Platinum Electrode Coated with an Oxo(phthalocyaninato) vanadium(IV) Conjugate Polymer to Various Anions in Nonaqueous Solutions" Bull.Chem.Soc.Jpn.72・2. 235-238 (1999)

T.Nakamura、T.Ueda、T.Yanagisawa、H.Watanabe：“涂有氧代（酞菁）钒 (IV) 共轭聚合物的铂电极对非水溶液中各种阴离子的响应特性”Bull.Chem.Soc。日本.72・2。235-238 (1999)

T.Nakamura, T.Ueda, T.Yanagisawa, H.Watanabe: "Response properties of a platinum electrode coated with an oxo(phthalocyaninato) Vanadium(IV)conjugate polymer to various anins in nonaqueous solutions"Bull. Chem. Soc. Jpn. 72・2. 235-238 (1999)

T.Nakamura、T.Ueda、T.Yanagisawa、H.Watanabe：“涂有氧代（酞菁）钒（IV）共轭聚合物的铂电极对非水溶液中各种阴离子的响应特性”Soc Jpn。 72·2。235-238（1999）

T. Nakamura, T. Ueda, T. Yanagisawa, H. Watanabe: "Response properties of a platinum electrode coated with an oxo(phthalocyaninato) Vanadium(IV) conjugate polymer to various anins in nonaqueous solutions"Bull.Chem.Soc.Jpn. 72・2. 235-238 (1999)

T. Nakamura、T. Ueda、T. Yanagisawa、H. Watanabe：“涂有氧代（酞菁）钒（IV）共轭聚合物的铂电极对非水溶液中各种阴离子的响应特性”Bull.Chem.Soc.Jpn 72·2。235-238（1999）

T. Nakamura, T. Ueda, T. Yanagisawa, H. Watanabe: "Response properties of a platinum electrode coated with an oxo(phthalocyaninato) vanadium(IV) conjugate polymer to polymer to various anins in nonaqueous solutions."Bull. Chem. Soc. Jpn.. 72・2. 235-238 (1

T. Nakamura、T. Ueda、T. Yanagisawa、H. Watanabe：“涂有氧代（酞菁）钒 (IV) 共轭聚合物的铂电极对非水溶液中各种阴离子的响应特性。”日本社会.. 72・238 (1