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基于新合成的六氮杂大环配体制备包覆石墨电极对镱(III)进行纳米级监测。

Nano-level monitoring of Yb(III) by fabrication of coated graphite electrode based on newly synthesized hexaaza macrocyclic ligand.

作者信息

Singh Ashok K, Singh Prerna

机构信息

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

出版信息

Anal Chim Acta. 2009 Jun 8;643(1-2):74-82. doi: 10.1016/j.aca.2009.03.047. Epub 2009 Apr 5.

Abstract

The two macrocyclic ligands 2,12-(2-methoxyaniline)2-4,14-Me2-[20]-1,4,11,14-tetraene-1,5,8,11,15,18-N6 (L1) and 2,12-(2-methoxyaniline)(2)-4,14-Me2-8,18-dimethylacrylate-[20]-1,4,11,14-tetraene-1,5,8,11,15,18-N6 (L2) have been synthesized and explored as neutral ionophores for preparing poly(vinylchloride) (PVC) based membrane sensors selective to Yb(III) ions. Effects of various plasticizers and anion excluders were studied in detail and improved performance was observed. The best performance was obtained for the membrane sensor having a composition of L2:PVC:BA:NaTPB in the ratio of 5: 40: 52: 3 (w/w; mg). The performance of the membrane based on L2 was compared with polymeric membrane electrode (PME) as well as with coated graphite electrode (CGE). The electrodes exhibit Nernstian slope for Yb3+ ions with limits of detection of 4.3 x 10(-8) M for PME and 5.8 x 10(-9) M for CGE. The response time for PME and CGE was found to be 10 s and 8 s, respectively. The potentiometric responses are independent of the pH of the test solution in the pH range 3.0-8.0 for PME and 2.5-8.5 for CGE. The CGE has found to work satisfactorily in partially non-aqueous media upto 30% (v/v) content of methanol, ethanol and 20% (v/v) content of acetonitrile and could be used for a period of 5 months. The CGE was used as indicator electrode in the potentiometric titration of Yb3+ ions with EDTA and in determination of fluoride ions in mouthwash samples. It can be used for determination of sulfite in red and white wine samples and also in determination of Yb3+ in various binary mixtures with quantitative results.

摘要

已合成了两种大环配体2,12-(2-甲氧基苯胺)2-4,14-Me2-[20]-1,4,11,14-四烯-1,5,8,11,15,18-N6(L1)和2,12-(2-甲氧基苯胺)(2)-4,14-Me2-8,18-二甲基丙烯酸酯-[20]-1,4,11,14-四烯-1,5,8,11,15,18-N6(L2),并将其作为中性离子载体进行研究,用于制备对Yb(III)离子具有选择性的聚氯乙烯(PVC)基膜传感器。详细研究了各种增塑剂和阴离子排除剂的影响,并观察到性能有所改善。对于组成比例为L2:PVC:BA:NaTPB = 5:40:52:3(重量/重量;毫克)的膜传感器,获得了最佳性能。将基于L2的膜的性能与聚合物膜电极(PME)以及涂覆石墨电极(CGE)进行了比较。这些电极对Yb3+离子呈现能斯特斜率,PME的检测限为4.3×10(-8) M,CGE的检测限为5.8×10(-9) M。发现PME和CGE的响应时间分别为10秒和8秒。对于PME,在pH范围3.0 - 8.0内,电位响应与测试溶液的pH无关;对于CGE,在pH范围2.5 - 8.5内,电位响应与测试溶液的pH无关。已发现CGE在甲醇、乙醇含量高达30%(体积/体积)以及乙腈含量高达20%(体积/体积)的部分非水介质中能令人满意地工作,并且可以使用5个月。CGE用作Yb3+离子与EDTA电位滴定以及漱口水样品中氟离子测定的指示电极。它可用于红葡萄酒和白葡萄酒样品中亚硫酸盐的测定,也可用于各种二元混合物中Yb3+的测定,并获得定量结果。

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