连续识别Cu^(2+)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 Cu^(2+) and PO_(4)^(3-)

作　　者：闫雪雪 喻艳超 庞树奎 吴绵园 荆军凯 刘其业 YAN Xuexue;YU Yanchao;PANG Shukui;WU Mianyuan;JING Junkai;LIU Qiye(School of Materials Science and Chemical Engineering,Harbin University of Science and Technology,Harbin 150080,Heilongjiang,China;Institute of Petrochemistry Heilongjiang Academy of Sciences,Harbin 150040,Heilongjiang,China)

机构地区：[1]哈尔滨理工大学材料科学与化学工程学院,黑龙江哈尔滨150080 [2]黑龙江省科学院石油化学研究院,黑龙江哈尔滨150040

出　　处：《化工进展》2024年第11期6372-6378,共7页Chemical Industry and Engineering Progress

基　　金：黑龙江省自然科学基金(LH_(2)021H001)。

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Cu^(2+)形成1∶1的络合物L-Cu^(2+),在30s时间内引起荧光淬灭效应,淬灭率近100%,且对Cu^(2+)检测过程中具有良好的特异性,可抵抗Ba^(2+)、Li^(+)、Cu^(+)、Al^(3+)、Zn^(2+)、Cs^(2+)、Mn^(2+)、Ca^(2+)、Hg^(2+)、Cd^(2+)、K^(+)、Mg^(2+)、Na^(+)、Co^(2+)、Ag^(+)、Fe^(^(3+))及Cr^(2+)等金属离子的干扰,检测极限低至1.70×10^(-8)mol/L,具有高度灵敏性。同时,基于配体置换原理,络合物L-Cu^(2+)可作为荧光传感器实现对PO_(3)^(-4)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-)、P_(2)O_(7)^(4)^(-)、Br^(-)、F^(-)、HCO_(3)^(-)、SO_(4)^(2-)、C_(2)O_(4)^(2-)、Cl^(-)、CH_(3)COO^(-))的干扰,检测限低至6.00×10^(-8)mol/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。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-Cu^(2+)with Cu^(2+)which caused a fluorescence quenching effect with a quenching rate of 100%.It had good specificity for Cu^(2+)and could resist the interference of metal ions such as Ba^(2+),Li^(+),Cu^(+),Al^(3+),Zn^(2+),Cs^(2+),Mn^(2+),Ca^(2+),Hg^(2+),Cd^(2+),K^(+),Mg^(2+),Na^(+),Co^(2+),Ag^(+),Fe^(^(3+))and Cr^(2+).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-Cu^(2+)could be used as a fluorescence sensor to achieve fluorescence-enhanced response recognition of PO_(3)^(-4).The process with good selectivity,could resist the interference of common anions(NO_(2)^(-)、CO_(3)^(2-)、SO_(3)^(2-)、HPO_(4)^(2-)、P_(2)O_(7)^(4)^(-)、Br^(-)、F^(-)、HCO_(3)^(-)、SO_(4)^(2-)、C_(2)O_(4)^(2-)、Cl^(-)、CH_(3)COO^(-)),and the detection limit was as low as 6.00×10^(-8)mol/L.In addition,probe L was successfully applied in the fields of pharmaceutical chemistry and chemical environmental protection with excellent experimental results.

关 键 词：香豆素 荧光探针 二阶铜离子 磷酸根 连续识别 

分 类 号：O626.32[理学—有机化学]