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基于Elsner 反应的可逆纳米灯用于即时监测氰化物

A Reversible Nanolamp for Instantaneous Monitoring of Cyanide Based on an Elsner-Like Reaction.

机构信息

School of Chemistry and Biological Engineering, Changsha University of Science and Technology , Changsha 410114, P. R. China.

State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Molecular Science and Biomedicine Laboratory, Hunan University , Changsha 410082, P. R. China.

出版信息

Anal Chem. 2016 Oct 4;88(19):9759-9765. doi: 10.1021/acs.analchem.6b02720. Epub 2016 Sep 26.

Abstract

It is well-known that cyanide ion (CN) is a hypertoxic anion, which can cause adverse effects in both the environment and living beings; thus, it is highly desirable to develop strategies for detecting CN, especially in water and food. However, due to the short half-life of free cyanide, long analysis time and/or interference from other competitive ions are general challenges for accurate monitoring of CN. In this work, through the investigation on the sequence-dependent optical interaction of DNA-CuNPs with the fluorophore (e.g., EBMVC-B), we found, for the first time, that DNA-CuNPs were an ideal alternative as fluorescence quencher in constructing a sensor which could be illuminated by CN based on an Elsner-like reaction and that the signal switching was dependent on poly(AT/TA) dsDNA sequence. By virtue of CuNPs' small size and its high chemical reactivity with cyanide, the lighting of fluorescence was ultrarapid and similar to the hairtrigger "turn-on" of a lamp, which is significant for accurately monitoring a target of short half-life (e.g., cyanide). Attributed to the unique Elsner-like reaction between CN and the Cu atoms, high selectivity was achieved for CN monitoring by the nanolamp, with practical applications in real water and food samples. In addition, because of the highly efficient in situ formation of DNA-CuNPs and the approximative stoichiometry between CN and Cu in the fluorescence switching, the nanolamp could be reversibly turned on and off through the alternate regulation of CN and Cu, displaying potential for developing reusable nanosensors and constructing optical molecular logic circuits.

摘要

众所周知,氰根离子(CN)是一种超毒性阴离子,它会对环境和生物造成不良影响;因此,开发检测 CN 的策略是非常有必要的,尤其是在水和食品中。然而,由于游离氰化物的半衰期短、分析时间长和/或其他竞争离子的干扰,对 CN 进行准确监测一直是一个挑战。在这项工作中,通过对 DNA-CuNPs 与荧光团(如 EBMVC-B)的序列依赖性光学相互作用的研究,我们首次发现,DNA-CuNPs 是构建基于 Elsner 类似反应的传感器的理想荧光猝灭剂,其信号开关取决于多聚(AT/TA)dsDNA 序列。由于 CuNPs 尺寸小且与氰化物具有高化学反应性,荧光的点亮速度超快,类似于灯的超快速“开启”,这对于准确监测半衰期短的目标(如氰化物)非常重要。由于 CN 与 Cu 原子之间独特的 Elsner 类似反应,纳米灯对 CN 监测具有高选择性,在实际水样和食品样品中具有实际应用。此外,由于 DNA-CuNPs 的高效原位形成以及荧光开关中 CN 和 Cu 之间的近似化学计量关系,纳米灯可以通过 CN 和 Cu 的交替调节可逆地开启和关闭,显示出开发可重复使用的纳米传感器和构建光学分子逻辑电路的潜力。

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