稀土穴状荧光配合物的合成与光谱性质

doi:10.11944/j.issn.1000-0518.2016.03.160232

摘要/Abstract

摘要：

以2,6-二甲基吡啶-3,5-二甲酸二乙酯为起始原料,经N-溴代丁二酰亚胺(NBS)溴代、亲电取代反应合成了时间分辨荧光免疫分析双功能螯合剂2,6-{N,N',N,N'-[二(2,2'-联吡啶-6,6'-二甲基)]二(氨甲基)}-吡啶-3,5-二羧酸二乙酯。经差热分析仪(DTA)、傅里叶变换红外光谱仪(FTIR)、核磁共振波谱仪(¹H NMR)、质谱仪(MS)等技术手段表征确认了化合物结构和性能。对该化合物与铕离子形成螯合物的荧光性质研究表明:激发光谱波长范围较宽,激发峰值为322 nm;荧光发射峰为597 nm(⁵D₀-⁷F₁)、618 nm(⁵D₀-⁷F₂);荧光寿命为918 μs;量子产率Φ=0.249。

关键词: 均相时间分辨荧光免疫分析, 螯合剂, 合成, 穴状联吡啶衍生物

Abstract:

A bifuntional cryptate chelate 2,6-{N,N',N,N'-[bis(2,2'-bipyridine-6,6'-dimethyl)]bis(aminomethyl)}-pyridine-3,5-diethyl diester for homogeneous time-resolved fluorimmunoassay product was synthesized from the raw material diethyl 2,6-dimethylpyridine-3,5-dicarboxylate through N-bromobutanimide(NBS) bromination, electrophilic substitution. The structure and property were confirmed by differential thermal analysis(DTA) Fourier transform infrared spectroscopy(FTIR), proton nuclear magnetic resonance spectroscopy(¹H NMR) and mass spectrometry(MS). Also, the spectral properties of the Eu(Ⅲ)-cryptate chelate, such as absorption spectra, emission spectra, and fluorescence lifetime, were discussed. The fluorescence spectroscopic properties of Eu(Ⅲ)-cryptate are as follows: the excitation peak is at 322 nm, the narrow emission spectrum peaks are at 597 nm(⁵D₀-⁷F₁) and 618 nm(⁵D₀-⁷F₂), respectively, the Stokes shift is 290 nm, the fluorescence lifetime is 918 μs, and the fluorescence quantum yield is Φ=0.249.

Key words: homogeneous time-resolved fluorescence immunoassay, chelate, synthesis, cryptate bipyridine derivative

常宇, 谢文兵, 周誓红, 李俊玲, 刘宝峰, 潘利华. 稀土穴状荧光配合物的合成与光谱性质[J]. 应用化学, 2017, 34(3): 361-366.

CHANG Yu, XIE Wenbing, ZHOU Shihong, LI Junling, LIU Baofeng, PAN Lihua. Synthesis and Spectroscopic Properties of a Cryptate Rare Earth Fluorescence Complex[J]. Chinese Journal of Applied Chemistry, 2017, 34(3): 361-366.

参考文献

[1]	Kuo J E,Milby K H,Hinsberg W D,et al.Direct Measurement of Antigens in Serum by Time-resolved Fluoroimmunoassay[J]. Clin Chem,1985,31(1):50-53.
[2]	Diamandis E P. Immunoassays with Time-resolved Fluorescence Spectroscopy:Principles and Applications[J]. Clin Biochem,1988,21(2):139-150.
[3]	NIU Qianqian,PAN Lihua,LI Zhen,et al.Preparation of 2,6-Dibromo-4-aminopyridine[J]. J Mol Sci,2006,22(6):401-404(in Chinese). 钮倩倩,潘利华,李珍,等. 2,6-二溴-4-氨基吡啶的合成[J]. 分子科学学报,2006,22(6):401-404.
[4]	Jiang L,Wu J,Wang G L,et al.Development of a Visible-light-sensitized Europium Complex for Time-resolved Fluorometric Application[J]. Anal Chem,2010,82(6):2529-2535.
[5]	Bazin H,Preaudat M,Trinquet E,et al.Homogeneous Time Resolved Fluorescence Resonance Energy Transfer Using Rare Earth Cryptates as a Tool for Probing Molecular Interactions in Biology[J]. Spectrochim Acta A,2001,57(11):2197-2211.
[6]	Smeulders L,Bunkens L,Vereycken I,et al.A Homogeneous Time-resolved Fluorescence Assay to Identify Inhibitors of HIV-1 Fusion[J]. Methods Mol Biol,2013,1030(6):11-17.
[7]	Degorce F,Card A,Soh S,et al.HTRF: A Technology Tailored for Drug Discovery-A Review of Theoretical Aspects and Recent Applications[J]. Curr Chem Genomics,2009,3(1):22-32.
[8]	Rossant C J,Mattews C,Neal F,et al.Versatility of Homogeneous Time-resolved Fluorescence Resonance Energy Transfer Assays for Biologics Drug Discovery[J]. J Biomol Screen,2015,20(4):508-518.
[9]	Moore E G, Samuel A P S,Raymond K N. From Antenna to Assay:Lessons Learned in Lanthanide Luminescence[J]. Acc Chem Res,2009,42(4):542-552.
[10]	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.
[11]	Shi L F,Li Y W,Cao H R,et al.Synthesis of Novel Europium Complexes and Their Photoluminescence Properties[J]. J Rare Earths,2012,30(1):17-20.
[12]	CAO Xijie,XIE Wenbing,PAN Lihua,et al.Synthesis and Characterization of 4,4'-Di(p-aminophenylethynyl)-6,6'-bis[N,N-bis(ethoxycarbonylmethyl)amino methyl]-2,2'-bipyridine[J]. Chem J Chinese Univ,2012,33(7):1462-1465(in Chinese). 曹熙杰,谢文兵,潘利华,等. 4,4'-二(对氨基苯乙炔基)-6,6'-二[N,N-二(乙氧基羰甲基)氨甲基]-2,2'-联吡啶的合成与表征[J]. 高等学校化学学报,2012,33(7):1462-1465.
[13]	XIE Wenbing,CHANG Yu,ZHANG Yongli,et al.Synthesis and Characterization of Rare Earth Fluorescent Compound for Biomolecules-labeling[J]. Chinese J Anal Chem,2013,41(11):1749-1753(in Chinese). 谢文兵,常宇,张永利,等. 稀土荧光化合物的合成与表征[J]. 分析化学,2013,41(11):1749-1753.
[14]	Yang X Y,Dang D D,Zhu W,et al.Synthesis and Characterization of 4,4'-Di(p-aminophenylethynyl)-6,6'-bis(N,N-bis(t-butoxycarbonylmethyl)amino methyl)-2,2'-bipyridine[J]. Asian J Chem,2014,26(8):2256-2258.

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