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Lighting-up of the dye malachite green with mercury(II)-DNA and its application for fluorescence turn-off detection of cysteine and glutathione

机译:汞(II)-DNA点亮孔雀石绿染料及其在半胱氨酸和谷胱甘肽荧光关闭检测中的应用

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摘要

This work describes a novel strategy for the highly sensitive and selective detection of cysteine (Cys) and glutathione (GSH) based on the Hg ~(2+)-AGRO100-malachite green (MG) complex system. The dye MG, which has a very low quantum yield in aqueous solution by itself, can bind with the thymine-rich DNA AGRO100 in the presence of Hg ~(2+) ions to generate a striking fluorescence intensity enhancement of 1000-fold. As sulfur-containing amino acids, Cys and GSH effectively sequester Hg ~(2+) ions from the Hg ~(2+)-AGRO100-MG complex structure to switch the 'lit-up' chemosensor to the 'off' state (about a 50-fold fluorescence intensity decrease), thus providing a facile, but effective, method to probe for Cys/GSH. The fluorescence titration, UV absorption, CD, and Raman spectra provide some insight into the structural and chemical basis for the enhancement effect. The formation of the Hg ~(2+)-AGRO100-MG complex significantly affects the electronic structure and conformation of the MG molecule by leading to an extended π system, which is the likely origin of the observed striking fluorescence intensity enhancement. Notably, the proposed sensing platform exhibits exquisite selectivity and sensitivity toward Cys/GSH with limits of detection of 5 nM for Cys and 10 nM for GSH, respectively. Furthermore, the straightforward assay design avoids labeling of the probe, uses only commercially available materials, and still displays comparable sensitivity and excellent selectivity.
机译:这项工作描述了基于Hg〜(2 +)-AGRO100-孔雀绿(MG)复杂系统的半胱氨酸(Cys)和谷胱甘肽(GSH)的高灵敏度和选择性检测的新策略。 MG本身在水溶液中的量子产率非常低,它可以在Hg〜(2+)离子存在的情况下与富含胸腺嘧啶的DNA AGRO100结合,从而产生惊人的1000倍荧光强度增强。作为含硫氨基酸,Cys和GSH可有效地从Hg〜(2 +)-AGRO100-MG复合结构中螯合Hg〜(2+)离子,从而将“点亮”化学传感器切换为“关闭”状态(约(荧光强度降低50倍),因此提供了一种简便但有效的方法来探测Cys / GSH。荧光滴定,UV吸收,CD和拉曼光谱为增强效应的结构和化学基础提供了一些见识。 Hg〜(2 +)-AGRO100-MG复合物的形成通过导致扩展的π系统而显着影响MG分子的电子结构和构象,这可能是观察到的惊人荧光强度增强的起源。值得注意的是,拟议的传感平台对Cys / GSH表现出出色的选择性和敏感性,对Cys和GSH的检测限分别为5 nM和10 nM。此外,简单的测定设计避免了探针的标记,仅使用市售材料,并且仍显示出相当的灵敏度和出色的选择性。

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