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基于监测未修饰银纳米颗粒(AgNPs)还原用于简单快速测定汞的选择性比色传感器。

Selective colorimetric sensors based on the monitoring of an unmodified silver nanoparticles (AgNPs) reduction for a simple and rapid determination of mercury.

作者信息

Jarujamrus Purim, Amatatongchai Maliwan, Thima Araya, Khongrangdee Thatsanee, Mongkontong Chakrit

机构信息

Department of Chemistry, Faculty of Science, Ubon Ratchathani University, Warin Chamrap, Ubon Ratchathani 34190, Thailand.

Department of Chemistry, Faculty of Science, Ubon Ratchathani University, Warin Chamrap, Ubon Ratchathani 34190, Thailand.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2015 May 5;142:86-93. doi: 10.1016/j.saa.2015.01.084. Epub 2015 Feb 11.

Abstract

In this work, selective colorimetric sensors for simple and rapid detection of Hg(II) ions based on the monitoring of an unmodified silver nanoparticles (AgNPs) reduction were developed. The average diameter of synthesized AgNPs was 8.3±1.4nm which was characterized by transmission electron microscopy (TEM). The abrupt change in absorbance of the unmodified AgNPs was observed which progressively decreased and slightly shifted to the blue wavelength as the concentration of Hg(II) increased, indicating the oxidation of Ag(0) to Ag(I) occurred. It appears that the AgNPs were oxidized by Hg(II), resulting in disintegration of the AgNPs into smaller particles as well as mediating the reduction of Hg(II) to Hg(0) adsorbed onto the surface of AgNPs. The adsorption of Hg(0) resulted in the lack of sufficient charges on AgNPs surfaces due to the decrease in the surface coverage of negatively charged citrate molecules, which then leaded to enlargement of AgNPs. The calibration curve of this technique was demonstrated from 0.5 to 7ppm (r(2)=0.995), the limit of detection (LOD) was 0.06ppm (SDblank/slope of calibration curve) with the precision (RSD, n=4) of 3.24-4.53. Interestingly, the results show a significant enhance in the Hg(II) analytical sensitivity when Cu(II) is doped onto the unmodified AgNPs, which improves the quantitative detection limit to 0.008ppm. In addition, greater selectivity toward Hg(II) compared with the other metal ions tested was observed. Furthermore, the percentage recoveries of spiked drinking water, tap water and SRM1641d (mercury in water) were in acceptable range with a good precision (RSD) which were in agreement with the values obtained from graphite furnace atomic absorption spectrometer (GFAAS). The technique proposed in this study provides a rapid, simple, sensitive and selective detection method for Hg(II) in water samples.

摘要

在本研究中,基于监测未修饰的银纳米颗粒(AgNPs)还原反应,开发了用于简单快速检测Hg(II)离子的选择性比色传感器。合成的AgNPs平均直径为8.3±1.4nm,通过透射电子显微镜(TEM)进行表征。观察到未修饰的AgNPs吸光度发生突变,随着Hg(II)浓度增加,吸光度逐渐降低并轻微向蓝色波长偏移,这表明发生了Ag(0)氧化为Ag(I)的反应。似乎AgNPs被Hg(II)氧化,导致AgNPs分解成更小的颗粒,同时介导Hg(II)还原为吸附在AgNPs表面的Hg(0)。Hg(0)的吸附导致AgNPs表面由于带负电荷的柠檬酸盐分子表面覆盖率降低而缺乏足够电荷,进而导致AgNPs增大。该技术的校准曲线在0.5至7ppm范围内得到验证(r(2)=0.995),检测限(LOD)为0.06ppm(SD空白/校准曲线斜率),精密度(RSD,n = 4)为3.24 - 4.53。有趣的是,结果表明当Cu(II)掺杂到未修饰的AgNPs上时,Hg(II)分析灵敏度显著提高,定量检测限提高到0.008ppm。此外,与测试的其他金属离子相比,对Hg(II)具有更高的选择性。此外,加标饮用水、自来水和SRM1641d(水中汞)的回收率百分比在可接受范围内,精密度良好(RSD),与石墨炉原子吸收光谱仪(GFAAS)获得的值一致。本研究中提出的技术为水样中Hg(II)提供了一种快速、简单、灵敏且选择性的检测方法。

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