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用于区分2,4,6-三硝基甲苯和2,4,6-三硝基苯酚的碳化聚合物点

Carbonized polymer dots for discrimination of 2,4,6-trinitrotoluene and 2,4,6-trinitrophenol.

作者信息

Qiao Ruiqi, Li Yingxing, Zhu Rongchao, Bai Huazangnaowu, Zhao Chuanfang, Zu Baiyi, Cai Zhenzhen

机构信息

School of Physics Science and Technology, Xinjiang University, Urumqi 830046, China.

Xinjiang Key Laboratory of Trace Chemical Substances Sensing, Xinjiang Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Urumqi 830011, China.

出版信息

J Hazard Mater. 2025 Jul 5;491:137944. doi: 10.1016/j.jhazmat.2025.137944. Epub 2025 Mar 15.

Abstract

It is of great significance for the discrimination of 2,4,6-trinitrotoluene (TNT) and 2,4,6-trinitrophenol (TNP) from their analogues. Here, based on the electron-deficient properties of TNT and TNP, a series of o-phenylenediamine/polyethyleneimine carbonized polymer dots (OPD/PEI CPDs) with different densities and types of amine groups (-NH) on the surface were designed by modulating the ratio of the precursors OPD and PEI. The surface -NH group of OPD/PEI CPDs could form a Meisenheimer complex with TNT, triggering the Forster resonance energy transfer, while forming hydrogen bonds with hydroxyl in TNP, triggering the charge transfer and spectral overlap to produce photoinduced electron transfer accompanied with inner filter effect. When the ratio of OPD to PEI is 1:1 and the surface -NH content is 26.06 %, the OPD/PEI CPDs demonstrated a more superior sensing performance toward targets, including a low limit of detection (TNT: 324 nM and 255 µM, TNP: 21.08 nM and 318.6 nM), a rapid response (<1 s), and a rather good selectivity in the presence of 20 interferents. Moreover, the practicality of the OPD/PEI CPDs was further verified by an OPD/PEI CPDs-based paper sensor, which is capable of discriminating TNT and TNP particles and vapors as low as pg-level and ppm-level respectively.

摘要

从类似物中鉴别2,4,6-三硝基甲苯(TNT)和2,4,6-三硝基苯酚(TNP)具有重要意义。在此,基于TNT和TNP的缺电子特性,通过调节前驱体邻苯二胺(OPD)和聚乙烯亚胺(PEI)的比例,设计了一系列表面具有不同密度和类型胺基(-NH)的邻苯二胺/聚乙烯亚胺碳化聚合物点(OPD/PEI CPDs)。OPD/PEI CPDs的表面-NH基团可与TNT形成迈森海默络合物,引发福斯特共振能量转移,同时与TNP中的羟基形成氢键,引发电荷转移和光谱重叠,产生伴随内滤效应的光致电子转移。当OPD与PEI的比例为1:1且表面-NH含量为26.06%时,OPD/PEI CPDs对目标物表现出更优异的传感性能,包括低检测限(TNT:324 nM和255 μM,TNP:21.08 nM和318.6 nM)、快速响应(<1 s)以及在存在20种干扰物时具有相当好的选择性。此外,基于OPD/PEI CPDs的纸质传感器进一步验证了其实用性,该传感器能够分别鉴别低至pg级和ppm级的TNT和TNP颗粒及蒸气。

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