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基于席夫碱作为螯合离子载体的铬(III)选择性膜传感器。

Chromium(III) selective membrane sensors based on Schiff bases as chelating ionophores.

作者信息

Singh A K, Gupta V K, Gupta Barkha

机构信息

Department of Chemistry, Indian Institute of Technology-Roorkee, Roorkee 247667, India.

出版信息

Anal Chim Acta. 2007 Feb 28;585(1):171-8. doi: 10.1016/j.aca.2006.11.074. Epub 2006 Dec 6.

Abstract

The two chromium chelates of Schiff bases, N-(acetoacetanilide)-1,2-diaminoethane (L(1)) and N,N'-bis(acetoacetanilide)-triethylenetetraammine (L(2)), have been synthesized and explored as neutral ionophores for preparing poly(vinylchloride) (PVC) based membrane sensors selective to Cr(III). The addition of lipophilic anion excluder (NaTPB) and various plasticizers viz. o-Nitrophenyloctyl ether (o-NPOE), dioctylpthalate (DOP), dibutylphthalate (DBP), tris(2-ethylhexyl)phosphate (TEHP), and benzyl acetate (BA) have found to improve the performance of the sensors. The best performance was obtained for the membrane sensor having a composition of L(1):PVC:DBP:NaTPB in the ratio 5:150:250:3 (w/w). The sensor exhibits Nernstian response in the concentration range 8.9 x 10(-8) to 1.0 x 10(-1) M Cr(3+) with limit of detection 5.6 x 10(-8) M. The proposed sensor manifest advantages of relatively fast response (10s) and good selectivity over some alkali, alkaline earth, transition and heavy metal ions. The selectivity behavior of the proposed electrode revealed a considerable improvement as compared to the best previously PVC-membrane electrode for chromium(III) ion. The potentiometric response of the proposed sensor was independent of pH of the test solution in the range of 2.0-7.0. The sensor has found to work satisfactorily in partially non-aqueous media up to 20% (v/v) content of methanol, ethanol and acetonitrile and could be used for a period of 3 months. The proposed electrode was used as an indicator electrode in potentiometric titration of chromium ion with EDTA and in direct determination in different water and food samples.

摘要

合成了席夫碱的两种铬螯合物,即N-(乙酰乙酰苯胺)-1,2-二氨基乙烷(L(1))和N,N'-双(乙酰乙酰苯胺)-三亚乙基四胺(L(2)),并将其作为中性离子载体进行研究,用于制备对Cr(III)具有选择性的聚氯乙烯(PVC)基膜传感器。添加亲脂性阴离子排除剂(NaTPB)和各种增塑剂,即邻硝基苯基辛基醚(o-NPOE)、邻苯二甲酸二辛酯(DOP)、邻苯二甲酸二丁酯(DBP)、磷酸三(2-乙基己基)酯(TEHP)和乙酸苄酯(BA),已发现可改善传感器的性能。对于组成为L(1):PVC:DBP:NaTPB比例为5:150:250:3(w/w)的膜传感器,获得了最佳性能。该传感器在8.9×10(-8)至1.0×10(-1)M Cr(3+)的浓度范围内表现出能斯特响应,检测限为5.6×10(-8)M。所提出的传感器具有响应相对较快(10s)以及对一些碱金属、碱土金属、过渡金属和重金属离子具有良好选择性的优点。与之前性能最佳的PVC膜铬(III)离子电极相比,所提出电极的选择性行为有了显著改善。所提出传感器的电位响应在2.0-7.0的测试溶液pH范围内与pH无关。已发现该传感器在甲醇、乙醇和乙腈含量高达20%(v/v)的部分非水介质中能令人满意地工作,并且可以使用3个月。所提出的电极用作铬离子与EDTA电位滴定的指示电极以及不同水样和食品样品中铬离子的直接测定。

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