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普鲁士蓝掺杂纳米聚苯胺电化学检测苯二酚异构体。

Prussian blue-doped nanosized polyaniline for electrochemical detection of benzenediol isomers.

机构信息

Department of Physical and Environmental Sciences, University of Toronto Scarborough, 1265 Military Trail, Toronto, ON, M1C 1A4, Canada.

出版信息

Anal Bioanal Chem. 2020 Mar;412(8):1769-1784. doi: 10.1007/s00216-020-02400-6. Epub 2020 Feb 10.

Abstract

Simultaneous speciation of benzenediol isomers (BDIs), 1,2-benzenediol (catechol, CC), 1,3-benzenediol (resorcinol, RS), and 1,4-benzenediol (hydroquinone, HQ), was investigated by differential pulse voltammetry (DPV) using a graphite paste electrode (GPE) modified with Prussian blue-polyaniline nanocomposite. The modified GPE showed good stability, sensitivity, and selectivity properties for all the three BDIs. Prussian blue-doped nanosized polyaniline (PBNS-PANI) was synthesized first by using mechanochemical reactions between aniline and ferric chloride hexahydrate as the oxidants and then followed by the addition of potassium hexacyanoferrate(II) in a solid-state and template-free technique. The material was characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS). The DPV measurements are performed in phosphate electrolyte solution with pH 4.0 at a potential range of - 0.1 to 1.0 V. The proposed modified electrode displayed a strong, stable, and continuous three well-separated oxidation peaks towards electrooxidation at potentials 0.20, 0.31, and 0.76 V for HQ, CC, and RS, respectively. The calibration curves were linear from 1 to 350.5 μM for both HQ and CC, while for RS, it was from 2 to 350.5 μM. The limit of detection was determined to be 0.18, 0.01, and 0.02 μM for HQ, CC, and RS, respectively. The analytical performance of the PBNS-PANI/GPE has been evaluated for simultaneous determination of HQ, CC, and RS in creek water, commercial hair dye, and skin whitening cream samples with satisfactory recoveries between 90 and 106%. Overall, we demonstrated that the presence of NS-PANI and PB resulted in a large redox-active surface area that enabled a promising analytical platform for simultaneous detection of BDIs. Graphical abstract.

摘要

采用石墨糊电极(GPE)修饰普鲁士蓝-聚苯胺纳米复合材料,通过差分脉冲伏安法(DPV)对苯二酚异构体(BDI),即 1,2-苯二酚(邻苯二酚,CC)、1,3-苯二酚(间苯二酚,RS)和 1,4-苯二酚(对苯二酚,HQ)进行同时形态分析。修饰后的 GPE 对所有三种 BDI 均表现出良好的稳定性、灵敏度和选择性。首先通过苯胺与六水合氯化铁之间的机械化学反应,然后在固态和无模板技术中添加六氰合铁(II)酸钾,合成了普鲁士蓝掺杂纳米聚苯胺(PBNS-PANI)。采用扫描电子显微镜、透射电子显微镜、傅里叶变换红外光谱(FT-IR)和 X 射线光电子能谱(XPS)对材料进行了表征。在 pH 4.0 的磷酸盐电解质溶液中,在 -0.1 至 1.0 V 的电位范围内进行 DPV 测量。所提出的修饰电极对 HQ、CC 和 RS 的电氧化分别在 0.20、0.31 和 0.76 V 处表现出强烈、稳定且连续的三个良好分离的氧化峰。HQ 和 CC 的校准曲线均为 1 至 350.5 μM 线性,而 RS 的校准曲线为 2 至 350.5 μM。HQ、CC 和 RS 的检测限分别确定为 0.18、0.01 和 0.02 μM。PBNS-PANI/GPE 的分析性能已在溪水中 HQ、CC 和 RS 的同时测定、商业染发剂和皮肤美白霜样品中进行了评估,回收率在 90%至 106%之间。总体而言,我们证明了 NS-PANI 和 PB 的存在导致了较大的氧化还原活性表面积,从而为 BDI 的同时检测提供了有前途的分析平台。

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