锌离子介导的草甘膦荧光探针的合成及应用

Synthesis and Application of Fluorescent Probe for Detection of Glyphosate Based on Zinc Ion

摘要

设计合成了一种新型苯并噻唑类荧光探针DHB, 并利用核磁共振波谱(NMR)、 傅里叶变换红外光谱(FTIR)、 质谱(MS)和高分辨质谱(HRMS)对DHB进行了结构表征. 研究结果表明, 探针DHB与Zn²⁺形成了1∶1配合物, 表现出较强的荧光发射, 可实现对Zn²⁺的专一识别, 且不受其它共存金属离子和阴离子的干扰, 检出限为4.01×10⁻⁸ mol/L. 当继续向配合物DHB-Zn²⁺中加入草甘膦后, 体系表现出显著的荧光猝灭效应, 响应时间为18 s, 且不受其它有机磷农药和常见阴离子的干扰, 检出限低至3.81×10⁻⁸ mol/L. FTIR 和HRMS 测试结果揭示了探针DHB连续识别Zn²⁺和草甘膦的反应机理, 即探针DHB结构中的C=O发生了烯醇式互变, 形成的烯醇式羟基、 探针结构中的O-H及C=N的氮杂原子共同参与和Zn²⁺的配位, 而草甘膦分子中氨基、 羧基和磷酸基的协同配位使其能与Zn²⁺发生更强的络合作用, 导致Zn²⁺从配合物DHB-Zn²⁺中被置换出来. 此外, 探针DHB及配合物DHB-Zn²⁺可分别应用于环境中Zn²⁺和草甘膦的分析检测, 具有一定的实用价值.

Abstract

A novel benzothiazole-based fluorescent probe (DHB) was designed and synthesized, and its structure was characterized using means of nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FTIR), mass spectrometry (MS) and high-resolution mass spectrometry (HRMS). The research results indicate that probe DHB forms a 1∶1 complex with Zn²⁺, exhibiting strong fluorescence emission and achieving specific recognition of Zn²⁺ without interference from other coexisting metal ions and anions. The detection limit was 4.01×10⁻⁸ mol/L. When glyphosate was further added to the complex DHB-Zn²⁺, the system exhibited a significant fluorescence quenching effect with a response time of 18 s, and was not affected by other organophosphorus pesticides and common anions. The detection limit was as low as 3.81×10⁻⁸ mol/L. Meanwhile, the reaction mechanism of probe DHB continuously recognizing Zn²⁺ and glyphosate was revealed by FTIR and HRMS. That is, the C=O in the structure of probe DHB underwent enol tautomerism, and the enol hydroxyl formed thereby, along with the O-H and the nitrogen heteroatom of C=N in the probe structure, jointly participated in the coordination with Zn²⁺. The synergistic coordination of amino, carboxyl and phosphate groups in the glyphosate molecule enabled it to form a stronger complex with Zn²⁺, resulting in the displacement of Zn²⁺ from the complex DHB-Zn²⁺. Furthermore, probe DHB and the complex DHB-Zn²⁺ can be applied to the analysis and detection of Zn²⁺ and glyphosate in the environment, which has a certain practical value.

关键词

苯并噻唑 / 荧光探针 / 草甘膦 / 二价锌离子

Key words

Benzothiazole / Fluorescent probe / Glyphosate / Zn²⁺

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基金资助

河南省自然科学基金青年项目(252300420811)

河南省高等学校重点科研项目(25B550017)

河南省大学生创新创业训练计划项目(S202510480027)