School of Environment and Civil Engineering, Dongguan University of Technology, Dongguan, China; Guangdong Engineering and Technology Research Center for Advanced Nanomaterials, Dongguan University of Technology, Dongguan, China.
Division of Biomedical Engineering, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, China; Institute of Biomedicine and Biotechnology, Shenzhen Institutes of Advanced Technology, Chinese Academy of Sciences, Shenzhen, China.
Anal Chim Acta. 2018 Oct 5;1026:147-154. doi: 10.1016/j.aca.2018.04.017. Epub 2018 Apr 18.
Halobenzoquinones (HBQs) were reported as disinfection byproducts (DBPs) which had potential risk of bladder cancer. In this paper, a highly selective analytical method for HBQs was developed by HBQs-mediated assembly of amino acid modified Mn-doped ZnS/Quantum Dots (Mn: ZnS QDs). In the presence HBQs, a charge-transfer complex (CTC) was formed between aromatic rings of HBQs and the primary amino groups on the surface of the QDs. The formation of CTC led to the aggregation of QDs, as a result fluorescence decreasing occurred. The decrease was correlated with the concentration of HBQs. Then a fluorescence sensor array for discrimination of three kinds of HBQs including 2,6-Dichloro-1,4-benzoquinone (DCBQ), 2,6-Dibromo-1,4-benzoquinone (DBBQ) and 2,3,6-trichloro-1,4-benzoquinone (TCBQ) was developed. Four kinds of amino acids including cysteine, threonine, tyrosine and tryptophan were embellished on the Mn: ZnS QDs. The different extents of aggregation led to different fluorescence decreasing effect, thus distinct fluorescence patterns were created. It showed that three kinds of HBQs could be discriminated successfully by fluorescence sensor array at a range of concentrations through principal component analysis (PCA). The unknown samples were predicted by with a stepwise linear discriminant analysis (SLDA) using Mahalanobis distance as a selection criterion with accuracy of 100%. Remarkably, the practicability of the proposed sensor array was further validated by identification of three kinds of HBQs at different concentrations in real drinking water samples. Compared to LC/MS/MS, this fluorescent sensor array-based method was proved to be more convenient since the nanoparticles can be prepared flexibly according to the property of the target.
卤代苯醌（HBQs）被报道为具有膀胱癌潜在风险的消毒副产物（DBPs）。在本文中，通过 HBQs 介导的氨基酸修饰的 Mn 掺杂 ZnS/量子点（Mn: ZnS QDs）的组装，开发了一种对 HBQs 具有高选择性的分析方法。在 HBQs 的存在下，HBQs 的芳环与 QDs 表面的伯氨基之间形成了电荷转移复合物（CTC）。CTC 的形成导致 QDs 聚集，从而导致荧光强度降低。荧光强度的降低与 HBQs 的浓度相关。然后，开发了一种用于区分三种 HBQs（包括 2,6-二氯-1,4-苯醌（DCBQ）、2,6-二溴-1,4-苯醌（DBBQ）和 2,3,6-三氯-1,4-苯醌（TCBQ））的荧光传感器阵列。四种氨基酸，包括半胱氨酸、苏氨酸、酪氨酸和色氨酸，被修饰在 Mn: ZnS QDs 上。不同程度的聚集导致不同的荧光减弱效应，从而产生不同的荧光图案。结果表明，通过主成分分析（PCA），可以成功地通过荧光传感器阵列在一定浓度范围内区分三种 HBQs。使用马氏距离作为选择标准的逐步线性判别分析（SLDA）对未知样品进行预测，准确率为 100%。值得注意的是，通过在不同浓度的实际饮用水样品中识别三种 HBQs，进一步验证了所提出的传感器阵列的实用性。与 LC/MS/MS 相比，该荧光传感器阵列法具有更高的实用性，因为可以根据目标的性质灵活制备纳米粒子。
