连续识别Cu2+及PO43-香豆素类荧光探针合成与应用

doi:10.16085/j.issn.1000-6613.2023-1759

摘要/Abstract

摘要：

以4-二乙氨基水杨醛和肼基甲酸甲酯为原料制备一种新型双功能香豆素荧光探针L，并通过NMR、FTIR及HRMS对其结构表征。荧光发射光谱表明，在甲醇溶液中，探针L与Cu²⁺形成1∶1的络合物L-Cu²⁺，在30s时间内引起荧光淬灭效应，淬灭率近100%，且对Cu²⁺检测过程中具有良好的特异性，可抵抗Ba²⁺、Li⁺、Cu⁺、Al³⁺、Zn²⁺、Cs²⁺、Mn²⁺、Ca²⁺、Hg²⁺、Cd²⁺、K⁺、Mg²⁺、Na⁺、Co²⁺、Ag⁺、Fe³⁺及Cr²⁺等金属离子的干扰，检测极限低至1.70×10^-8mol/L，具有高度灵敏性。同时，基于配体置换原理，络合物L-Cu²⁺可作为荧光传感器实现对PO $4 3 -$ 的荧光增强响应识别，且检测过程具有良好的选择性，可抵抗常见阴离子（NO $2 -$ 、CO $3 2 -$ 、SO $3 2 -$ 、HPO $4 2 -$ 、P₂O $7 4 -$ 、Br^-、F^-、HCO $3 -$ 、SO $4 2 -$ 、C₂O $4 2 -$ 、Cl^-、CH₃COO^-）的干扰，检测限低至6.00×10^-8mol/L。此外，探针L成功应用于医药化工及化工环境保护领域，得到良好实验效果。

关键词: 香豆素, 荧光探针, 二阶铜离子, 磷酸根, 连续识别

Abstract:

A novel dual-function coumarin based fluorescent probe was prepared from 4-(diethylamino)salicylaldehyde with methyl hydrazinecarboxylate, and its structure was characterized by NMR, FTIR, and HRMS. Fluorescence emission spectra showed that in methanol solution, within 30 seconds, probe L formed a 1∶1 complex L-Cu²⁺ with Cu²⁺ which caused a fluorescence quenching effect with a quenching rate of 100%. It had good specificity for Cu²⁺ and could resist the interference of metal ions such as Ba²⁺, Li⁺, Cu⁺, Al³⁺, Zn²⁺, Cs²⁺, Mn²⁺, Ca²⁺, Hg²⁺, Cd²⁺, K⁺, Mg²⁺, Na⁺, Co²⁺, Ag⁺, Fe³⁺and Cr²⁺. And the detection limit was as low as 1.70×10^-8mol/L with high sensitivity. Meanwhile, based on the ligand substitution principle, complex L-Cu²⁺ could be used as a fluorescence sensor to achieve fluorescence-enhanced response recognition of PO $4 3 -$ . The process with good selectivity, could resist the interference of common anions (NO $2 -$ , CO $3 2 -$ , SO $3 2 -$ , HPO $4 2 -$ , P₂O $7 4 -$ ,Br^-, F^-, HCO $3 -$ , SO $4 2 -$ , C₂O $4 2 -$ , Cl^- and CH₃COO^-), and the detection limit was as low as 6.00×10^-8mol/L. In addition, probe L was successfully applied in the fields of pharmaceutical chemistry and chemical environmental protection with excellent experimental results.

Key words: coumarin, fluorescent probe, Cu²⁺, PO $4 3 -$ , sequential recognition

中图分类号:

O626.32

闫雪雪, 喻艳超, 庞树奎, 吴绵园, 荆军凯, 刘其业. 连续识别Cu²⁺及PO $4 3 -$ 香豆素类荧光探针合成与应用[J]. 化工进展, 2024, 43(11): 6372-6378.

YAN Xuexue, YU Yanchao, PANG Shukui, WU Mianyuan, JING Junkai, LIU Qiye. Synthesis and application of coumarin based fluorescent probe for sequential recognition of Cu²⁺and PO $4 3 -$ [J]. Chemical Industry and Engineering Progress, 2024, 43(11): 6372-6378.

图/表 13

图1 荧光探针L合成路线

图2 探针L在不同溶剂中识别Cu2+前后荧光强度变化

图3 探针L与Cu2+作用时间考察

图4 探针L对Cu2+特异性检测

图5 探针L在509nm处荧光强度与Cu2+浓度的线性关系

图6 探针L与Cu2+的Job’s plot曲线图[c(L+Cu2+)=10μmol/L]

图7 探针L和络合物L-Cu2+的红外对比谱图

图8 络合物L-Cu2+对PO43-特异性识别

图9 络合物L-Cu2+在509nm处荧光强度与PO43-浓度的线性关系

图10 络合物L-Cu2+与PO43-的Job’s plot曲线[c(PO43-+L-Cu2+)=10μmol/L]

图11 探针L中交替添加Cu2+和PO43-的紫外吸收光谱

图12 探针L连续识别Cu2+和PO43-可能作用机制

表1 实际样品中检测Cu2+/PO43-

样品	添加量 /μmol·L^-1	检出量 /μmol·L^-1	回收率/%	RSD （n=3）/%
西洋参	3.00	2.98	99.3	1.98
西洋参	5.00	5.19	103.8	3.00
西洋参	7.00	6.91	98.7	1.76
西洋参	9.00	9.05	100.6	2.46
松花江水	0.20	0.204	102.0	1.23
松花江水	0.30	0.301	100.3	0.95
松花江水	0.40	0.403	100.8	0.91
松花江水	0.50	0.509	101.8	1.69

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连续识别Cu²⁺及PO $4 3 -$ 香豆素类荧光探针合成与应用

Synthesis and application of coumarin based fluorescent probe for sequential recognition of Cu²⁺and PO $4 3 -$

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