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铜(II)存在下硫化镉量子点的动力学荧光猝灭:动力学数据的化学计量学辅助解析及铜(II)的定量分析

Kinetic fluorescence quenching of CdS quantum dots in the presence of Cu(II): chemometrics-assisted resolving of the kinetic data and quantitative analysis of Cu(II).

作者信息

Abdollahi Hamid, Shamsipur Mojtaba, Barati Ali

机构信息

Faculty of Chemistry, Institute for Advanced Studies in Basic Sciences, Zanjan, Iran.

Department of Chemistry, Razi University, Kermanshah, Iran.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2014 Jun 5;127:137-43. doi: 10.1016/j.saa.2014.02.020. Epub 2014 Feb 26.

DOI:10.1016/j.saa.2014.02.020
PMID:24632167
Abstract

In this work, the kinetic fluorescence behavior of CdS quantum dots (QDs) in the presence of Cu(II) was investigated. In contrast to some other transition metal ions such as Ag(I), Ni(II), and Hg(II), a gradual red-shift in the emission spectrum of CdS QDs was observed for Cu(II) during the reaction course. More investigations revealed the existence of two chemical components in the recorded kinetic data in the presence of Cu(II). Multivariate curve resolution-alternating least squares (MCR-ALS) method was applied in order to extract pure emission spectra and time-dependent profiles of these two components at different concentrations of Cu(II). The results obtained from resolving the data by MCR-ALS got some information about the mechanism of the interaction between CdS QDs and Cu(II) ions which were in good agreement with those reported in the literature. Moreover, the multivariate method of analysis, partial least-squares (PLS) method, was used to develop a multivariate calibration model for quantitative analysis of Cu(II) using the entire kinetic data sets. The calibration and validation sets were created ranging from 0.02 to 1μM of Cu(II) and were successfully calibrated and predicted by the PLS model. This method allowed a sensitive determination of Cu(II) ions with a detection limit of 13nM based on three times of the standard deviation corresponding to PLS regression.

摘要

在本工作中,研究了硫化镉量子点(QDs)在铜(II)存在下的动力学荧光行为。与一些其他过渡金属离子如银(I)、镍(II)和汞(II)不同,在反应过程中观察到硫化镉量子点的发射光谱对于铜(II)存在逐渐红移。更多研究揭示在铜(II)存在下记录的动力学数据中存在两种化学成分。应用多元曲线分辨-交替最小二乘法(MCR-ALS)来提取这两种成分在不同浓度铜(II)下的纯发射光谱和随时间变化的曲线。通过MCR-ALS解析数据得到的结果获得了一些关于硫化镉量子点与铜(II)离子之间相互作用机制的信息,这些信息与文献报道的结果高度一致。此外,使用多元分析方法偏最小二乘法(PLS),利用整个动力学数据集建立了用于定量分析铜(II)的多元校准模型。校准集和验证集的铜(II)浓度范围为0.02至1μM,并通过PLS模型成功校准和预测。该方法能够灵敏地测定铜(II)离子,基于PLS回归对应标准偏差的三倍,检测限为13nM。

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