Key Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of Chemistry, Beijing Normal University, Beijing 100875, China.
Anal Chem. 2024 Aug 13;96(32):13131-13139. doi: 10.1021/acs.analchem.4c01841. Epub 2024 Aug 3.
Redox nanozymes have exhibited various applications in recognizing environmental pollutants but not aromatic amines (a type of typical pollutant). Herein, with Cu as a node and tryptophan (Trp) as a linker, Cu-Trp as a specific ascorbic acid oxidase mimic was synthesized, which could catalyze ascorbic acid (AA) oxidation to dehydroascorbic acid (DHAA). Alternatively, with other natural amino acids as linkers to synthesize Cu-based nanozymes, such catalytic performances are also observed. The as-produced DHAA could react with -phenylenediamine (OPD) and its derivatives (2,3-naphthalene diamine (NDA), 4-nitro--phenylenediamine (4-NO-OPD), 4-fluoro--phenylenediamine (4-F-OPD), 4-chloro--phenylenediamine(4-Cl-OPD), and 4-bromo--phenylenediamine(4-Br-OPD)) to form a Schiff base and emit fluorescence. Based on the results, with Cu-Trp + AA and Cu-Arg (with arginine (Arg) as a linker) + AA as two sensing channels and extracted red, green, and blue (RGB) values from emitted fluorescence as read-out signals, a visual sensor array was constructed to efficiently distinguish OPD, NDA, 4-NO-OPD, 4-F-OPD, 4-Cl-OPD, and 4-Br-OPD as low as 10 μM. Such detecting performance was further confirmed through discriminating binary, ternary, quinary, and senary mixtures with various concentration ratios, recognizing 18 unknown samples, and even quantitatively analyzing single aromatic amine. Finally, the discriminating ability was further validated in environmental waters, providing an efficient assay for large-scale scanning levels of multiple aromatic amines.
氧化还原纳米酶在识别环境污染物方面表现出了各种应用,但不能识别芳香胺(一种典型的污染物)。在此,以 Cu 为节点,色氨酸(Trp)为连接体,合成了 Cu-Trp 作为特定的抗坏血酸氧化酶模拟物,它可以催化抗坏血酸(AA)氧化为脱氢抗坏血酸(DHAA)。或者,以其他天然氨基酸为连接体合成 Cu 基纳米酶,也观察到了这种催化性能。生成的 DHAA 可以与 -苯二胺(OPD)及其衍生物(2,3-萘二胺(NDA)、4-硝基--苯二胺(4-NO-OPD)、4-氟--苯二胺(4-F-OPD)、4-氯--苯二胺(4-Cl-OPD)和 4-溴--苯二胺(4-Br-OPD))反应形成席夫碱并发射荧光。基于这些结果,以 Cu-Trp + AA 和 Cu-Arg(以精氨酸(Arg)为连接体)+ AA 作为两个传感通道,并从发射荧光中提取红色、绿色和蓝色(RGB)值作为读出信号,构建了一个可视化传感器阵列,能够高效地区分 OPD、NDA、4-NO-OPD、4-F-OPD、4-Cl-OPD 和 4-Br-OPD,检测限低至 10 μM。通过分辨二元、三元、五元和六元混合物以及具有各种浓度比的混合物,识别 18 个未知样品,甚至对单个芳香胺进行定量分析,进一步证实了这种检测性能。最后,在环境水中验证了区分能力,为大规模扫描多种芳香胺水平提供了一种有效的方法。