卟啉-吡啶基共轭寡聚物荧光纳米探针用于次氯酸的灵敏检测  

Sensitive Detection of Hypochlorous Acid Using Porphyrin-pyridyl Conjugated Oligomer-based Fluorescent Nanoprobe

作　　者：黄际艳 陈米雪 李金玲 肖毅[1] 黄红梅[1] 张友玉[1] HUANG Ji-Yan;CHEN Mi-Xue;LI Jin-Ling;XIAO Yi;HUANG Hong-Mei;ZHANG You-Yu(Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research(Ministry of Education),College of Chemistry and Chemical Engineering,Hunan Normal University,Changsha 410081,China)

机构地区：[1]湖南师范大学化学化工学院,化学生物学及中药分析教育部重点实验室,长沙410081

出　　处：《分析化学》2024年第8期1132-1140,共9页Chinese Journal of Analytical Chemistry

基　　金：国家自然科学基金(No.21475042);湖南省自然科学基金(No.2023JJ30389);湖南省教育厅科学研究基金项目(No.22C0030)资助。

摘　　要：共轭寡聚物作为共轭聚合物的类似物,具有更精准的分子结构及更小的分子尺寸,有利于构建超小荧光纳米粒子,从而提高传感的灵敏度。本研究通过Sonogashira偶联反应合成了一种新的卟啉-吡啶基荧光共轭寡聚物Zn-TPP-OMe,经纳米沉淀法制备了超小尺寸(~2.0 nm)的水溶性荧光纳米探针Zn-TPP-OMe NPs。由于次氯酸(HClO)会引起卟啉环上的氯原子加成,使得反应性荧光纳米探针在619~660 nm处的荧光随着HClO浓度增大而显著降低;同时,小尺寸Zn-TPP-OMe NPs发生明显聚集,其团聚导致的猝灭效应进一步提高了检测的灵敏度。通过透射电子显微镜(TEM)、核磁共振氢谱(1H NMR)和高分辨质谱(HRMS)确证了共轭寡聚物纳米探针Zn-TPP-OMe NPs的荧光检测机理。此卟啉-吡啶基共轭寡聚物纳米体系用于HClO检测具有高灵敏度(LOD=0.005μmol/L)和高选择性,并成功应用于实际水样中HClO的检测。Conjugated oligomers,as analogues of conjugated polymers,allow for constructing ultrafine fluorescent nanoparticles with improved sensing sensitivity due to their more precisely defined molecular structure and smaller size.Herein,a new porphyrin-pyridyl conjugated oligomer,i.e.,Zn-TPP-OMe,was designed and synthesized via Sonogashira coupling strategy and a super-small(~2.0 nm)water-soluble fluorescent nanoprobe(Zn-TPP-OMe nanoparticles(NPs))was subsequent obtained by nanoprecipitation method.Due to the addition reaction of chlorine atom to porphyrin ring,the fluorescence intensity of Zn-TPP-OMe NPs at 619–660 nm significantly decreased with increasing HCLO concentration.Meanwhile,Zn-TPP-OMe NPs aggregated obviously after adding HClO,achieving enhanced fluorescence quenching.The fluorescence detection mechanism was verified by transmission electron microscopy(TEM),proton nuclear magnetic resonance(1H NMR)and high resolution mass spectrometry(HRMS)analyses.The experimental results indicated that the porphyrin-pyridyl conjugated oligomer nanosystem had high sensitivity(LOD=0.005μmol/L)and excellent selectivity in detection of HClO,and was successfully applied to the sensing of HClO in actual water samples.

关 键 词：共轭寡聚物 反应性荧光探针 次氯酸 卟啉 荧光传感 

分 类 号：O657.3[理学—分析化学] X832[理学—化学]