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

研究了非增塑聚丙烯酰胺聚合物（PAA）膜与氧代（酞菁）镓（[Ga（pc）]）的偶联电极在乙腈（AN）、二甲基乙酰胺（DMA）和N-甲基吡咯烷酮（NMP）等非水溶剂中对各种阴离子的电位响应行为。PAA-（[Ga（pc）]）电极对AN中的F_（10）D_1-F_（10）D_1和CN_（10）D_1-F_（10）D_1均表现出选择性的能斯特响应，对DMA和NMP中的F_（10）D_1-F_（10）D_1则表现出近能斯特响应。另一方面，它显示出对Cl Cl-D1-NH 2-D1、Br-D1-NH 2-D1、I-D1-NH 2-D1、NO-D3-（/）2 NH 2-D3、SCN-D1-NH 2-D1、BPh-D3-（/）4 NH 2-D3、PF-D3-（/）6 NH 2-D3、ClO-D3-（/）4 NH 2-D3和CF-D23 NH 2-D2 SO-D3-（/）3 NH 2-D3的非热力学响应。结果表明，在PAA-[M（pc）]s（M=Co，VO）电极上得到的响应基本相同，在几种非质子溶剂中，F_（10）D_1-F_（10）D_1和CN_（10）D_1-F_（10）D_1的光谱研究表明， ...更多信息 与[M（pc）]之间的相互作用产生了这种特殊的响应现象。由于离子与最初与[Ga（pc）]s配位的溶剂分子或水分子的配体交换反应，可能会发生络合。用X射线衍射法确定了[Ga（pc）]与F_xD_1-F_xD_1的摩尔比为1：1，并认为配合物发生在配合物的轴位。在GBL中还观察到[Ga（pc）]与Cl ~（2+）D_1-Cl ~（2+）D_1的络合作用，这可能是由于GBL对Cl ~（2+）D_1-Cl ~（2+）D_1的弱溶剂化作用所致。在GBL中的F取代的D1-N取代的D1和CN取代的D1-N取代的D1的UV/维斯光谱与在实验中研究的其它溶剂中获得的那些不同，并且这与溶剂的酸度密切相关，即，的接受者号码。该电极可用于获得NaF在AN中的溶度积Kap。关于该项目的下一个讲座：（1）59年D1届D1文石化学研究会论文集。P15（小樽），（2）第60卷第1卷第1卷第1节文石化学斗龙会，p110（广崎），（3）第48卷第1卷第1节第1节文石化学年会，p243（科比）。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