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用于选择性 Cu(II) 光学传感的荧光离子印迹聚合物。

Fluorescent ion-imprinted polymers for selective Cu(II) optosensing.

机构信息

Institute of Chemistry, University of Campinas, P.O. Box 6154, Campinas 13083-970, Brazil.

出版信息

Anal Bioanal Chem. 2012 Apr;402(10):3253-60. doi: 10.1007/s00216-011-5620-0. Epub 2011 Dec 16.

Abstract

This paper describes the synthesis and characterization of a fluorescent ion-imprinted polymer (IIP) for selective determination of copper ions in aqueous samples. The IIP has been prepared using a novel functional monomer, 4-[(E)-2-(4'-methyl-2,2'-bipyridin-4-yl)vinyl]phenyl methacrylate (abbreviated as BSOMe) that has been spectroscopically characterized in methanolic solution, in the absence and in the presence of several metal ions, including Cd(II), Cu(II), Hg(II), Ni(II), Pb(II), and Zn(II). The stability constant (2.04 × 10(8) mol(-2) l(2)) and stoichiometry (L(2)M) of the BSOMe complex with Cu(II) were extracted thereof. Cu(II)-IIPs were prepared by radical polymerization using stoichiometric amounts of the fluorescent monomer and the template metal ion. The resulting cross-linked network did not show any leaching of the immobilized ligand allowing determination of Cu(II) in aqueous samples by fluorescence quenching measurements. Several parameters affecting optosensor performance have been optimized, including sample pH, ionic strength, or polymer regeneration for online analysis of water samples. The synthesized Cu(II)-IIP exhibits a detection limit of 0.04 μmol l(-1) for the determination of Cu(II) in water samples with a reproducibility of 3%, exhibiting an excellent selectivity towards the template ion over other metal ions with the same charge and close ionic radius. The IIP-based optosensor has been repeatedly used and regenerated for more than 50 cycles without a significant decrease in the luminescent properties and binding affinity of the sensing phase.

摘要

本文描述了一种荧光离子印迹聚合物(IIP)的合成与表征,用于选择性测定水溶液中的铜离子。该 IIP 是使用一种新型功能单体,4-[(E)-2-(4'-甲基-2,2'-联吡啶-4-基)乙烯基]苯甲基丙烯酸甲酯(简称 BSOMe),通过在甲醇溶液中,在不存在和存在几种金属离子(包括 Cd(II)、Cu(II)、Hg(II)、Ni(II)、Pb(II)和 Zn(II))的情况下进行光谱表征而制备的。从其中提取了 BSOMe 与 Cu(II)形成配合物的稳定常数(2.04×10(8)mol(-2)l(2))和化学计量(L(2)M)。通过使用荧光单体和模板金属离子的化学计量量进行自由基聚合,制备了 Cu(II)-IIP。所得交联网络没有显示出任何固定配体的浸出,允许通过荧光猝灭测量来测定水溶液中的 Cu(II)。已经优化了影响光学传感器性能的多个参数,包括样品 pH 值、离子强度或聚合物的再生,以实现水样品的在线分析。合成的 Cu(II)-IIP 对水溶液中 Cu(II)的检测限为 0.04 μmol l(-1),具有 3%的重现性,对模板离子表现出优于其他具有相同电荷和相近离子半径的金属离子的优异选择性。基于 IIP 的光学传感器已被重复使用和再生超过 50 次,而其发光性能和结合亲和力没有明显下降。

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