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基于新开发的源自4,13-二氮杂-18-冠-6的席夫碱套索醚的Ag(I)选择性聚氯乙烯膜传感器的比较研究

Comparative study of Ag(I) selective poly(vinyl chloride) membrane sensors based on newly developed Schiff-base lariat ethers derived from 4,13-diaza-18-crown-6.

作者信息

Gupta Vinod K, Pal Manoj K, Singh Ashok K

机构信息

Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee 247 667, India.

出版信息

Anal Chim Acta. 2009 Jan 12;631(2):161-9. doi: 10.1016/j.aca.2008.10.033. Epub 2008 Nov 1.

Abstract

The six Schiff-base lariat ether chelates based on 4,13-diaza-18-crown ether, have been synthesized and explored as a neutral ionophores for preparing poly(vinyl chloride) based membrane sensors selective to silver(I). The addition of potassium tetrakis(4-chlorophenyl) borate and various plasticizers, viz., o-NPOE, DBP, DBBP, DOP and CN has been found to substantially improve the performance of the sensors. The best performance was obtained with the sensor no. 5 having membrane of chelate (A(6)) with composition (w/w) chelate (2.8%):PVC (45.7%):o-NPOE (48.6%):KTpClPB (2.8%). This sensor exhibits Nernstian response with slope 59.3mV/decade of activity in the concentration range 5.6 x 10(-8)-1.0 x 10(-1)M Ag(I), performs satisfactorily over wide pH range of (3.0-8.0) with a fast response time (12s). The sensor was also found to work satisfactorily in partially non-aqueous media up to 25% (v/v) content of acetonitrile, methanol or ethanol and can tolerate the concentration 1.0 x 10(-2)M of ionic (SDS, TBC) and nonionic (Triton X-100) surfactants. The proposed sensor can be used over a period of 4 months without significant drift in potentials. The response of the sensor was highly selective to Ag(+) over a large number of cations and it could therefore be used for Ag(+) estimation in blood of occupationally exposed persons.

摘要

基于4,13-二氮杂-18-冠醚的六种席夫碱套索醚螯合物已被合成,并作为中性离子载体进行研究,用于制备对银(I)具有选择性的聚氯乙烯基膜传感器。已发现添加四(4-氯苯基)硼酸钾和各种增塑剂,即邻硝基苯基辛基醚(o-NPOE)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二丁基苄酯(DBBP)、邻苯二甲酸二辛酯(DOP)和氰基(CN)可显著提高传感器的性能。传感器5表现出最佳性能,其膜由螯合物(A(6))组成,组成(重量/重量)为螯合物(2.8%):聚氯乙烯(PVC,45.7%):邻硝基苯基辛基醚(48.6%):四(4-氯苯基)硼酸钾(KTpClPB,2.8%)。该传感器在5.6×10⁻⁸ - 1.0×10⁻¹ M银(I)的浓度范围内呈现能斯特响应,斜率为59.3 mV/十倍活度,在(3.0 - 8.0)的宽pH范围内性能良好,响应时间快(12秒)。还发现该传感器在乙腈、甲醇或乙醇含量高达25%(体积/体积)的部分非水介质中能正常工作,并且能够耐受1.0×10⁻² M浓度的离子型(十二烷基硫酸钠,SDS;四丁基氯化铵,TBC)和非离子型(聚氧乙烯辛基苯基醚,Triton X - 100)表面活性剂。所提出的传感器可使用4个月,电位无明显漂移。该传感器对银离子(Ag⁺)的响应相对于大量阳离子具有高度选择性,因此可用于职业暴露人员血液中银离子(Ag⁺)的测定。

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