稀土配合物荧光探针的合成
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摘要
目的研制可用于时间分辨荧光免疫分析中的稀土配合物荧光探针。方法以6,6'-二溴二甲基-2,2'-联吡啶-4-甲酸甲酯和1,4,10,13-四氧-7,16-二氮环十八烷为反应原料,合成了Na~+-6,6-(二氮杂-18-冠醚-6)-二胺甲基-2,2'-联吡啶-4-甲酸甲酯,并通过核磁氢谱、质谱等分析手段确认了化合物的结构。结果对该化合物与Eu~(3+)连接形成的稀土配合物荧光探针的荧光性质进行研究,结果表明其激发光谱波长范围较宽,最大激发波长为363 nm,特征发射波长为583 nm与621 nm,归属于~5D_0-~7F_(j=1,2)跃迁,Stokes位移为258 nm,荧光寿命为1456μs。结论该稀土配合物荧光探针符合时间分辨荧光分析技术所需要求,具有广泛的应用前景。
Objective To develop the lanthanide complex-based luminescent probes for the time-resolved fluorescence immunoassay. Methods The compound Na~+-6,6'-(diaza-18-crown-6)-bisaminomethyl}-2,2'-bipyridine-4-methyl formate was synthesized with the 6, 6'-dibromo-dimethyl-2,2-bipyridine-4-methyl formate and the 1,4,10,13-tetraoxa-7,16-diaza-cyclooctadecane. The structure was confirmed by proton nuclear magnetic resonance spectroscopy(~1 H NMR) and mass spectrometry(MS). Results The luminescence spectroscopic properties of Eu( Ⅲ) complex-based luminescent probes were as follows: the excitation peak was at 363 nm,and the emission spectrum peaks were at 583 nm(~5 D_0-~7 F_1 transition) and 621 nm(~5 D_0-~7 F_2 transition). The Stokes shift was 258 nm and the luminescence lifetime was 1456 μs. Conclusion The Eu(Ⅲ) complex-based luminescent probes developed in this study conform to the requirements of TRFIA,with an widely applicable prospect.
Objective To develop the lanthanide complex-based luminescent probes for the time-resolved fluorescence immunoassay. Methods The compound Na~+-6,6'-(diaza-18-crown-6)-bisaminomethyl}-2,2'-bipyridine-4-methyl formate was synthesized with the 6, 6'-dibromo-dimethyl-2,2-bipyridine-4-methyl formate and the 1,4,10,13-tetraoxa-7,16-diaza-cyclooctadecane. The structure was confirmed by proton nuclear magnetic resonance spectroscopy(~1 H NMR) and mass spectrometry(MS). Results The luminescence spectroscopic properties of Eu( Ⅲ) complex-based luminescent probes were as follows: the excitation peak was at 363 nm,and the emission spectrum peaks were at 583 nm(~5 D_0-~7 F_1 transition) and 621 nm(~5 D_0-~7 F_2 transition). The Stokes shift was 258 nm and the luminescence lifetime was 1456 μs. Conclusion The Eu(Ⅲ) complex-based luminescent probes developed in this study conform to the requirements of TRFIA,with an widely applicable prospect.
引文
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[15] HAVAS F,LEYGUE N,DANEL M,et al. 6,6'-Dimethyl-2,2'-bipyridine-4-ester:A pivotal synthon for building tethered bipyridine ligands[J]. Tetrahedron,2009,65(36):7673-7686.
[16]王小珠,马淑兰,朱文祥,等.新型二氮冠醚臂式衍生物的合成与表征[J].北京师范大学学报(自然科学版),2006,42(6):597-600.
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[19]田凤云.DTPA-碱基衍生物-Eu配合物在分析与检测碱基化合物中的应用[D].辽宁大学,2017.
[2] ZHU L,HUANG B, ZHANG J, et al. Establishment of TRFIA for anti-thyroglobulin antibody and its clinical application[J]. Lab Med,2013,28(4):305-307.
[3]王泽洲,吴俊清,张永宁,等.时间分辨荧光免疫分析技术的研究进展[J].四川畜牧兽医,2015,42(7):34-37.
[4]祝华彤,祖莉莉.稀土配合物荧光探针用于研究多肽和DNA的相互作用[J].光谱学与光谱分析,2016,36(S1):377-378.
[5]解肖鹏,张雷.时间分辨荧光免疫分析技术的研究进展[J].食品与药品,2012,14(05):203-206.
[6] Zhen Z,Liu J F,Bing S,et al. Time-resolved fluoroimmunoassay as an advantageous approach for highly efficient determination of sulfonamides in environmental waters.[J]. Environmental Science and Technology,2010,44(3):1030-1035.
[7] DEBROYE E,PARAC-VOGT T N. Chemlnform Abstract:Towards Polymetallic Lanthanide Complexes as Dual Contrast Agents forMagnetic Resonance and Optical Imaging[J]. Chem Society Reviews,2014,43(23):8178-8192.
[8] LIU J, YE Y,HU Z,et al. A hypersensitive biotin-avidin-TRFIA for quantitative detection of ANA-Ig(GAM):and its clinical application[J].J Immunoassay Immunochem, 2013,34(2):197-207.
[9] BUENO RIOS M, BUENO RIOS M. Clinical Correlation of a Clostridium difficile Testing Algorithm Reflexing PCR Positive Specimens to Toxin Enzyme Immunoassay(EIA)[J]. Open Forum Infectious Diseases,2017,4(1):395-396.
[10] WEGNER S, BAUER J I, DIETRICH R, et al. A highly specific competitive direct enzyme immunoassay for sterigmatocystin as a tool for rapid immunochemotaxonomic differentiation of mycotoxigenic Aspergillus species[J]. Lett Appl Microbiol, 2017, 64(2):124-130.
[11] YU YQ, WANG J P, ZHAO M, et al. Target-catalyzed hairpin assembly and intramolecular/intermolecular co-reaction for signal amplified electrochemiluminescent detection of microRNA[J].Biosens Bioelectron,2015,77:442-450.
[12] VARGAS E, RUIZ M A, CAMPUZANO S, et al. Implementation of a new integrated d-lactic acid biosensor in a semiautomatic FIA system for the simultaneous determination of lactic acid enantiomers. Application to the analysis of beer samples[J].Talanta,2016,152:147-154.
[13]苏艳,杨朝龙,李又兵,等.长荧光寿命稀土配合物荧光探针的研究进展[J].化工新型材料,2017,45(10):52-54.
[14]邢佩佩,张海燕,李娜,等.稀土配合物荧光探针在活细胞成像研究中的新进展[J].分析科学学报,2009,25(6):721-725.
[15] HAVAS F,LEYGUE N,DANEL M,et al. 6,6'-Dimethyl-2,2'-bipyridine-4-ester:A pivotal synthon for building tethered bipyridine ligands[J]. Tetrahedron,2009,65(36):7673-7686.
[16]王小珠,马淑兰,朱文祥,等.新型二氮冠醚臂式衍生物的合成与表征[J].北京师范大学学报(自然科学版),2006,42(6):597-600.
[17] PETERSON K L,MARGHERIO M J, DOAN P, et al. Basis for sensitive and selective Time-delayed luminescence detection of hydroxyl radical by lanthanide complexes[J]. Inorg Chem,2013,52(16):9390-9398.
[18] ANDOLINA C M,KLEMM P J,FLOYD W C 3rd,et al. Analysis of Lanthanide Complex Dendrimer Conjugates for Bimodal NIR and MRI Imaging[J]. Macromolecules,2014,45(22):8982-8990.
[19]田凤云.DTPA-碱基衍生物-Eu配合物在分析与检测碱基化合物中的应用[D].辽宁大学,2017.