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用于检测生物重要阴离子的“检测试剂盒”:基于水杨醛缩肼的希夫碱。

"Test kit" for detection of biologically important anions: a salicylidene-hydrazine based Schiff base.

机构信息

Department of Chemistry, University of Calcutta, 92, A.P.C. Road, Kolkata 700 009, India.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2013 Feb;102:314-8. doi: 10.1016/j.saa.2012.10.038. Epub 2012 Nov 1.

Abstract

Test paper coated with Schiff base [(N,N(/)-bis(5-nitro-salicylidene)hydrazine] receptor 1 (host) can selectively detect fluoride and acetate ions (guest) by developing yellow color which can be detected by naked-eye both in aqueous-acetonitrile solution and in solid supported test kit. UV-vis spectral analysis shows that the absorption peaks at 288 and 345 nm of receptor 1 gradually decrease its initial intensity and new red shifted absorption bands at 397 nm and 455 nm gradually appear upon addition of increasing amount of F(-) and AcO(-) ions over several tested anions such as H(2)PO(4)(-), Cl(-), Br(-), I(-), NO(3)(-), NO(2)(-), HSO(4)(-), HSO(3)(-), and ClO(4)(-) in aqueous-acetonitrile solvent. The colorimetric test results and UV-vis spectral analysis are in well agreement with (1)H NMR titration results in d(6)-DMSO solvent. The receptor 1 forms 1:2 stable complexes with F(-) and AcO(-) ions. However, similar kind of observation obtained from UV-vis titrations in presence of AcOH corresponds to 1:1 complexation ratio indicating the formation of H-bonding interaction between the receptor and anions (F(-) and AcO(-) ions). So, the observed 1:2 complexation ratio can only be explained on the basis of deprotonation (∼1 eqv.) and H-bonding (∼1 eqv.) interactions [1]. The ratiometric analysis of host-guest complexes corroborates well with the proposed theoretical model optimization at Density Functional Theory (DFT) level.

摘要

用席夫碱 [(N,N(/)-双(5-硝基水杨醛)腙)]受体 1 涂覆的试纸可以通过显色选择性地检测氟离子和乙酸根离子 (客体),肉眼在水-乙腈溶液中和在固体支持的测试试剂盒中都可以检测到。紫外-可见光谱分析表明,受体 1 的 288nm 和 345nm 吸收峰逐渐降低其初始强度,并且随着 F(-)和 AcO(-)离子浓度的增加,在几种测试的阴离子 (如 H(2)PO(4)(-), Cl(-), Br(-), I(-), NO(3)(-), NO(2)(-), HSO(4)(-), HSO(3)(-), 和 ClO(4)(-) 存在下,在水-乙腈溶剂中逐渐出现新的红移吸收带,其在 397nm 和 455nm 处出现。比色测试结果和紫外-可见光谱分析与 d(6)-DMSO 溶剂中的 (1)H NMR 滴定结果非常吻合。受体 1 与 F(-)和 AcO(-)离子形成 1:2 稳定配合物。然而,在存在 AcOH 的情况下从紫外-可见滴定中获得的类似观察结果对应于 1:1 络合比,表明受体与阴离子 (F(-)和 AcO(-)离子) 之间形成氢键相互作用。因此,仅基于去质子化 (∼1 eqv.) 和氢键 (∼1 eqv.) 相互作用,才能解释观察到的 1:2 络合比 [1]。主体-客体配合物的比率分析与在密度泛函理论 (DFT) 水平上提出的理论模型优化非常吻合。

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