基于β-二酮类铕(Ⅲ)配合物的单线态氧比率型荧光探针的合成及细胞成像应用  

Design and Synthesis of aβ-Diketonate-Europium(Ⅲ)Complex-based Ratiometric Fluorescent Probe for Singlet Oxygen and Its Application in Cell Imaging

作　　者：刘威 王华英 车婉萌 吴晶[1] LIU Wei;WANG Hua-Ying;CHE Wan-Meng;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》2024年第7期975-984,共10页Chinese Journal of Analytical Chemistry

摘　　要：将含二甲基蒽基团的β-二酮1,1,1,2,2-五氟-5-(9′,10′-二甲基-2′-蒽)-3,5-戊二酮(Hpfdap)作为识别配位体、罗丹明修饰的5-氨基-1,10-菲咯啉作为辅助配位体(CTMR-Phen-N),设计并合成了一种用于1O2检测的β-二酮类铕(Ⅲ)配合物比率型荧光探针[Eu(Hpfdap)3(CTMR-Phen-N)]。实验结果表明,探针结构中蒽环的存在使铕(Ⅲ)配合物几乎不发荧光,与1O2反应后,蒽环被氧化为内氧化物结构,从而恢复了铕(Ⅲ)配合物在614 nm处的荧光,量子产率由1.60%提高至25.16%;而与1O2反应前后,罗丹明在575 nm处的荧光强度基本保持不变。利用614 nm与575 nm处的荧光强度比值实现了1O2的比率型荧光测定,检出限(S/N=3)低至3μmol/L,并对1O2显示出良好的选择性。荧光成像实验结果表明,探针[Eu(Hpfdap)3(CTMR-Phen-N)]具有细胞毒性低和膜透过性好等优势,可用于Hela细胞中1O2的荧光成像检测。A ratiometric fluorescent probe([Eu(Hpfdap)3(CTMR-Phen-N)])was designed and synthesized for detection of singlet oxygen(1O2)with dimethyl anthracyl-containingβ-diketone compound 1,1,1,2-pentafluoro-5-(9',10'-dimethyl-2'-anthracene)-3,5-pentanedione(Hpfdap)as recognition ligand and 5-amino-1,10-phenanthroline conjugated with Rhodamine as auxiliary ligand(CTMR-Phen-N).The results of spectral analysis showed that the europium(Ⅲ)complex had almost no fluorescence due to the presence of anthracene ring in the probe.After reaction with 1O2,the anthracene ring was oxidized to endoperoxide,and the fluorescence of the europium(Ⅲ)complex at 614 nm was restored,followed by the increase of quantum yield from 1.60%to 25.16%.The fluorescence intensity of Rhodamine at 575 nm remained unchanged before and after the reaction with 1O2.Therefore,the ratio of fluorescence intensity at 614 nm and 575 nm could be used to measure 1O2 by the developed rationmetric fluorescence method.The probe showed good selectivity for 1O2,and the detection limit(S/N=3)was as low as 3μmol/L.The fluorescence imaging results demonstrated that the probe had low cytotoxicity and good membrane permeability,and could be applied to fluorescence imaging of 1O2 in Hela cells.

关 键 词：铕(Ⅲ)配合物 比率荧光探针 单线态氧 荧光成像 

分 类 号：Q2-33[生物学—细胞生物学] O657.3[理学—分析化学]