邻苯二胺的直接蓝光诱导的自催化氧化，用于高度灵敏的视觉检测三氨基三硝基苯。,Analytical Chemistry

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邻苯二胺的直接蓝光诱导的自催化氧化，用于高度灵敏的视觉检测三氨基三硝基苯。
Analytical Chemistry ( IF 6.7 ) Pub Date : 2019-04-16 00:00:00 , DOI: 10.1021/acs.analchem.9b00759
Jinhu Wang ₁ , Hua Li ₂ , Yanhua Cai ₃ , Dunju Wang ₁ , Liang Bian ₄ , Faqin Dong ₄ , Haili Yu ₁ , Yi He ₁

Affiliation

Ø-基于苯二胺（OPD）的显色反应是开发可视比色测定的有价值的工具。发色反应通常是由各种氧化剂触发的，这些氧化剂不易调节且与某些分析物不兼容。在本文中，我们报道了直接的蓝光照射可以诱导OPD的自催化氧化以生成2,3-二氨基吩嗪（氧化态OPD，oxOPD）。OPD的自催化光氧化反应机理主要归因于电子激发的oxOPD与溶解氧之间的共振能量转移，形成具有高氧化能力的单重态氧，从而加速了OPD的氧化。我们证明了在中性和碱性环境下，三氨基三硝基苯（TATB）炸药对OPD的光致自催化氧化作用进一步增强，因为它对oxOPD的聚集引起的猝灭现象具有抑制作用。在此基础上，开发了具有可调动态范围的TATB的直观目光比色测定法。该测定法能够检测低至2.7 nM的TATB炸药浓度。值得注意的是，添加TATB后明显的颜色变化使肉眼读出，可检测到的最低TATB浓度为60 nM。

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Direct Blue Light-Induced Autocatalytic Oxidation of o-Phenylenediamine for Highly Sensitive Visual Detection of Triaminotrinitrobenzene.

o-Phenylenediamine (OPD)-based chromogenic reactions are worthy tools for the development of visual colorimetric assays. The chromogenic reactions are usually triggered by various oxidants, which is not easily tunable and incompatible with some analytes. Herein, we report that direct blue light irradiation can induce the autocatalytic oxidation of OPD to generate 2,3-diaminophenazine (oxidized-state OPD, oxOPD). The autocatalytic photo-oxidation reaction mechanism of OPD is mainly ascribed to the resonant energy transfer between ectronically excited oxOPD and dissolved oxygen to form singlet state oxygen with a high oxidation capacity, which accelerates the oxidation of OPD. We demonstrate that under neutral and alkaline environment, the photoinduced autocatalytic oxidation of OPD is able to be further enhanced by triaminotrinitrobenzene (TATB) explosive because of its inhibition effect on the aggregation caused quenching phenomenon of oxOPD. On this basis, a straightforward visual colorimetric assay for TATB with a tunable dynamic range is developed. This assay is capable of detecting TATB explosive concentrations as low as 2.7 nM. Notably, the obvious color change after addition of TATB enables a naked-eye readout with the lowest detectable TATB concentrations of 60 nM.

更新日期：2019-04-16

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