Zhou Xiang-Yu, Liu Ji-Chun, Sun Xiao-Qing, Zhan Zhi-Hao, Yan Wen-Yu, Zhang Xing-Yu, Wei Jia-Xing, Cai Yuan-Qi, Zhang Hua-Xin
Guangxi Key Laboratory of Electrochemical Energy Materials, School of Chemistry and Chemical Engineering, Guangxi University, No. 100, Daxue East Road, Nanning, Guangxi, 530004, China.
J Fluoresc. 2025 Jan 13. doi: 10.1007/s10895-024-04109-6.
Two dipicolylamine (DPA) derivatives with the pyrene and anthracene groups, 1-(pyren-1-yl)-N, N-bis-(pyridine-2-ylmethyl)benzylamine (L1) and 1-(anthracen-9-yl)-N, N-bis-(pyridine-2-ylmethyl)benzylamine (L2) were synthesized, characterized, and their affinitive properties for metal ions were studied. The mass spectroscopy and Job's plots showed that L1 and L2 reacted with Cu and formed complexes [Cu(L1)(solvent)] (L1-Cu) and [Cu(L2)(solvent)] (L2-Cu), respectively. Both L1 and L2 were fluorescent probes recognizing Cu via the emission quenching and further detecting HS via the emission revival. The probes L1 and L2 displayed high sensitivity and selectivity as well as rapid response in the detection of Cu and HS. The limit of detection (LOD) values of L1 and L2 for Cu were 16 nM and 17 nM, respectively, and those of complexes L1-Cu and L2-Cu for S were 18 nM and 19 nM, respectively. The response time of L1 and L2 was within 10 s for Cu and 20 s for S. Furthermore, L1 and L2 were applicable to the detection of Cu in actual water samples with good recovery. The efficient response of L1 and L2 to Cu and S benefited from the strong electron transfer ability of the benzyl group between the DPA and the pyrene (or anthrence) groups. It showed that the judicious combination of the linker, the dipicolylamine and the chromophore group could offer molecular systems that were promising candidates for the detection of both metal ions and anions.
合成并表征了两种带有芘基和蒽基的二吡啶甲胺（DPA）衍生物，即1-(芘-1-基)-N,N-双-(吡啶-2-基甲基)苄胺（L1）和1-(蒽-9-基)-N,N-双-(吡啶-2-基甲基)苄胺（L2），并研究了它们对金属离子的亲和性质。质谱分析和乔布氏曲线表明，L1和L2与铜反应并分别形成配合物[Cu(L1)(溶剂)]（L1-Cu）和[Cu(L2)(溶剂)]（L2-Cu）。L1和L2均为荧光探针，通过发射猝灭识别铜，并通过发射恢复进一步检测硫化氢。探针L1和L2在检测铜和硫化氢时表现出高灵敏度、高选择性以及快速响应。L1和L2对铜的检测限（LOD）值分别为16 nM和17 nM，配合物L1-Cu和L2-Cu对硫的检测限分别为18 nM和19 nM。L1和L2对铜的响应时间在10 s以内，对硫的响应时间在20 s以内。此外，L1和L2适用于实际水样中铜的检测，回收率良好。L1和L2对铜和硫的高效响应得益于二吡啶甲胺与芘基（或蒽基）之间苄基的强电子转移能力。结果表明，连接基团、二吡啶甲胺和发色团的合理组合可以提供有望用于检测金属离子和阴离子的分子体系。
