一种具有识别Hg^(2+)和ClO^(-)荧光探针的设计和应用  

Design and Application of A Fluorescent Probe with Recognition of Hg^(2+)and ClO^(-)

作　　者：廖元淏 王帅[1] 陈婉慧 冯华杰[2] 陈光英[1] 何文英[2] LIAO Yuanhao;WANG Shuai;CHEN Wanhui;FENG Huajie;CHEN Guangying;HE Wenying(Key Laboratory of Tropical Medicinal Plant Chemistry of Ministry of Education,Haikou 571158,China;College of Chemistry and Chemical Engineering,Hainan Normal University,Haikou 571158,China)

机构地区：[1]热带药用植物化学教育部重点实验室,海南海口571158 [2]海南师范大学化学与化工学院,海南海口571158

出　　处：《发光学报》2024年第2期351-363,共13页Chinese Journal of Luminescence

基　　金：海南省科技计划重点研发项目(ZDYF2022XDNY197);海南省自然科学基金(224RC506)。

摘　　要：设计合成了一种含双酯基的1,2,3-三氮唑化合物,与罗丹明B酰肼结合生成了具有“开-关”性质的荧光探针(简称L_(2)),应用光谱学表征了L_(2)的物理化学参数。L_(2)分别在DMF/Tris-HCl(1:1,v/v,pH=6.0,20μmol/L)和MeOH(20μmol/L)溶液中对Hg^(2+)和ClO^(-)显示出高选择性和灵敏性;利用荧光和紫外光谱分别测定了L_(2)对19种金属离子和14种阴离子的光学性能。实验表明,Hg^(2+)和ClO^(-)的存在使得L_(2)在585 nm和576 nm均有一个新的发射峰出现;同时伴随着荧光强度明显的增强,溶液体系发生了裸眼能识别的显色变化,表明Hg^(2+)可以将罗丹明分子的酰肼闭环结构转换为开环结构,并以1:2的比例方式生成了一种新配合物,这也被质谱、工作曲线、核磁滴定和TD-DFT计算的结果所证实;L_(2)对Hg^(2+)和ClO^(-)的检测限分别为7.45 nmol/L和0.67μmol/L。此外,生物活性测定显示L_(2)对HeLa细胞有非常低的毒性,并且可用于HeLa细胞中Hg^(2+)和ClO^(-)的细胞成像,表明L_(2)在体内可进行微测定Hg^(2+)和ClO^(-)的巨大潜力。A compound of 1,2,3-triazole containing dicarboxylate group was designed and synthesized,and combined with rhodamine B hydrazine to produce an on-off fluorescence probe(L_(2)).The physicochemical parameters of L_(2) were characterized by spectroscopy and the computational chemistry methods.The probe L_(2) showed high selectivity and sensitivity to Hg^(2+)and ClO^(-)in DMF/Tris-HCl(1∶1,v/v,pH 6.0,20µmol/L)and MeOH(20µmol/L)solutions,respectively.The optical properties of L_(2) to 19 metal ions and 14 anions were measured by fluorescence and ultraviolet spectra,respectively.The experimental results showed that the presence of Hg^(2+)and ClO^(-)made L_(2) have a new emission peak at 585 nm and 576 nm,respectively.Simultaneously,the color change of the solution system can be recognized by the naked eye with the obvious enhancement of fluorescence intensity,indicating that Hg^(2+)can convert the closed-loop structure of hydrazide rhodamine molecule into an open-loop structure.A new complex is generated in the ratio of 1∶2,which is also confirmed by the results of mass spectrometry,Jobs plot,nuclear magnetic titration,and TD-DFT calculation.The detection limits of L_(2) for Hg^(2+)and ClO^(-)were 7.45 nmol/L and 0.67µmol/L,respectively.In addition,bioactivity assays showed that L2 has very low toxicity to HeLa cells and can be used for cell imaging of Hg^(2+)and ClO^(-)in HeLa cells,suggesting the great potential of L_(2) for micro-determination of Hg^(2+)and ClO^(-)in vivo.

关 键 词：1 2 3-三氮唑 罗丹明B Hg^(2+) ClO^(-) 细胞成像 

分 类 号：O657[理学—分析化学]