Department of Physical and Environmental Sciences, University of Toronto Scarborough, 1265 Military Trail, Toronto, ON, M1C 1A4, Canada.
Anal Bioanal Chem. 2020 Mar;412(8):1769-1784. doi: 10.1007/s00216-020-02400-6. Epub 2020 Feb 10.
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.
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。