Li Wenyang, Xie Qiangrong
Institute of Oceanic and Environmental Chemical Engineering, Center for Membrane and Water Science &Technology, State Key Lab Breeding Base of Green Chemical Synthesis Technology, Zhejiang University of Technology, 310014, Hangzhou, People's Republic of China.
Anal Sci. 2025 Jan;41(1):35-44. doi: 10.1007/s44211-024-00671-y. Epub 2024 Sep 19.
Recently, the misuse of organic arsenic feed additives, such as roxarsone (ROX), has increasingly jeopardized both human health and the environment. In response, a unique electron-rich pyrazine-cored fluorescent covalent organic framework (COF) nanosheet, named as COF-TMP, was synthesized using an alkali-catalyzed reaction between 2, 3, 5, 6-tetramethylpyrazine (TMP) and terephthalaldehyde (TPA). Characterization demonstrated that COF-TMP boasted high porosity, pronounced fluorescence, and an abundance of (E)-2-styrylpyrazine (SPA) groups. These attributes render it an exceptional fluorescent sensor for the ultrahigh sensitivity detection of electron-deficient ROX molecules. The limit of detection (LOD) for COF-TMP in detecting ROX was found to be 0.015 ppb through fluorescence-quenching titration experiments-surpassing all previously reported fluorescent sensors. A combination of experimental results and theoretical calculations suggests that the extraordinary detection capability of COF-TMP for ROX arises from a static quenching mechanism. This study paves the way not only for a novel pyrazine-based fluorescent COF nanosheet with high porosity, exceptional fluorescent capabilities, and abundant SPA groups suitable for highly sensitive and selective ROX detection but also hints at its potential application as a fluorescent sensor for environmental pollution management and related domains.
最近,诸如洛克沙胂(ROX)等有机砷饲料添加剂的滥用日益危及人类健康和环境。作为回应,一种独特的以富电子吡嗪为核心的荧光共价有机框架(COF)纳米片,命名为COF-TMP,通过2,3,5,6-四甲基吡嗪(TMP)与对苯二甲醛(TPA)之间的碱催化反应合成。表征表明,COF-TMP具有高孔隙率、显著的荧光以及大量的(E)-2-苯乙烯基吡嗪(SPA)基团。这些特性使其成为用于超高灵敏度检测缺电子ROX分子的优异荧光传感器。通过荧光猝灭滴定实验发现,COF-TMP检测ROX的检测限(LOD)为0.015 ppb,超过了所有先前报道的荧光传感器。实验结果和理论计算相结合表明,COF-TMP对ROX的非凡检测能力源于静态猝灭机制。这项研究不仅为一种新型的基于吡嗪的具有高孔隙率、优异荧光能力和大量SPA基团的荧光COF纳米片铺平了道路,这种纳米片适用于高灵敏度和选择性的ROX检测,而且还暗示了其作为环境污染管理及相关领域荧光传感器的潜在应用。