基于β-二酮类铕(Ⅲ)配合物的一氧化氮荧光探针的设计、合成及应用研究  

Design and Synthesis of A β-Diketonate-Europium(Ⅲ) Complex-based Fluorescent Probe for Nitric Oxide Detection and Its Application in Bioimaging

作　　者：闵盼 郑德泽 车婉萌 邢月 吴晶[1] MIN Pan;ZHENG De-Ze;CHE Wan-Meng;XING Yue;WU Jing(School of Chemistry and Chemical Engineering,Liaoning Normal University,Dalian 116029,China)

机构地区：[1]辽宁师范大学化学化工学院,大连116029

出　　处：《分析化学》2021年第10期1704-1712,I0020-I0026,共16页Chinese Journal of Analytical Chemistry

基　　金：2019年国家大学生创新训练计划项目(No.201910165118)资助。

摘　　要：以含一氧化氮(NO)识别基团邻二氨基苯基的联三吡啶衍生物4-(4-[2,2′:6′,2″]三联吡啶-4′-基-苯氧基)-苯-1,2-二胺(TPBD)为配位体,β-二酮类化合物5-(1′,1″-二苯基-4′-基)-1,1,1,2,2,3,3-七氟-4,6-己二酮(DHH)为共配体,设计并合成了一种用于检测NO的β-二酮类铕(Ⅲ)配合物荧光探针[Eu(DHH)_(3)(TPBD)],采用质谱和元素分析确证其结构。光谱研究结果表明,探针[Eu(DHH)_(3)(TPBD)]本身仅发出微弱的光,与NO反应后荧光强度增强近10倍,定量检测NO的线性浓度范围为0.017~0.83μmol/L,检出限为7.4 nmol/L。探针[Eu(DHH)_(3)(TPBD)]对几种常见的活性氧/氮物种基本上不响应,对NO显示出良好的选择性。荧光成像实验表明,探针[Eu(DHH)_(3)(TPBD)]具有低细胞毒性和线粒体靶向定位性能,并成功实现对RAW 264.7活细胞和斑马鱼体内的NO的时间分辨荧光成像检测。By using NO-recognizable o-diaminophenyl-substituted terpyridine derivative ligand 4-(4-[(2,2′:6′,2″-terpyridin)-4′-yl]phenoxy)benzene-1,2-diamine(TPBD)as the ligand,and β-diketone 6-(1′,1″-diphenyl-4′-yl)-1,1,1,2,2,3,3-heptafluoro-4,6-hexanedione(DHH)as the coligand,a new β-diketonate-Eu^(3+) complex-based fluorescent probe,[Eu(DHH)_(3)(TPBD)],was designed and synthesized for detection of NO,and its structure was characterized by mass spectrum and elemental analysis methods.The spectral results indicated that the probe[Eu(DHH)_(3)(TPBD)]had only weak fluorescence,and its fluorescence intensity was increased by nearly 10 times after reacting with NO.The probe could be used to quantitatively detect NO at concentrations ranging from 0.017-0.83μmol/L with a detection limit of 7.4 nmol/L.Meanwhile,[Eu(DHH)_(3)(TPBD)]showed approximately no response to other common reactive oxygen/nitrogen species,which demonstrated the good NO sensitivity of the probe.The fluorescence imaging experiments proved that the probe[Eu(DHH)_(3)(TPBD)]had low cytotoxicity and mitochondria targetability,and was successfully applied to the time-gated fluorescence imaging of NO in living cells and zebrafish.

关 键 词：铕(Ⅲ)配合物 一氧化氮 荧光探针 时间分辨荧光成像 

分 类 号：O657.3[理学—分析化学] O641.4[理学—化学]