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一种新型铽(III)螯合物作为高效单线态氧荧光探针。

A new terbium(III) chelate as an efficient singlet oxygen fluorescence probe.

作者信息

Tan Mingqian, Song Bo, Wang Guilan, Yuan Jingli

机构信息

Department of Analytical Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Graduate School of the Chinese Academy of Sciences, Dalian 116023, People's Republic of China.

出版信息

Free Radic Biol Med. 2006 May 1;40(9):1644-53. doi: 10.1016/j.freeradbiomed.2005.12.030. Epub 2006 Jan 20.

DOI:10.1016/j.freeradbiomed.2005.12.030
PMID:16632124
Abstract

A terbium(III) chelate fluorescence probe for detection of singlet oxygen (1O2) in aqueous media, N,N,N1,N1-[2,6-bis(3'-aminomethyl-1'-pyrazolyl)-4-(9''-anthryl)pyridine] tetrakis (acetate)-Tb3+ (PATA-Tb3+), was designed and synthesized. The new chelate is highly water soluble, is almost nonfluorescent, and can specifically react with 1O2 to yield a strongly fluorescent chelate, the endoperoxide of PATA-Tb3+, accompanied by a remarkable increase in the fluorescence quantum yield from 0.46 to 10.5%. The long fluorescence lifetime of the endoperoxide (2.76 ms) allows the probe to be used favorably for time-resolved fluorescence detection of 1O2. The studies of fluorescence property and reaction specificity indicate that the new probe is highly sensitive and selective for 1O2. The probe was used for quantitative detection of 1O2 generated from a MoO4(2-) -H2O2 system to give a detection limit of 10.8 nM. In addition, the good applicability of the probe was demonstrated by the real-time monitoring of the kinetic process of 1O2 generation in a horseradish peroxidase-catalyzed oxidation system of indole-3-acetic acid in a weakly acidic buffer.

摘要

设计并合成了一种用于检测水介质中单线态氧(¹O₂)的铽(III)螯合物荧光探针N,N,N1,N1-[2,6-双(3'-氨甲基-1'-吡唑基)-4-(9''-蒽基)吡啶]四乙酸铽(PATA-Tb³⁺)。这种新型螯合物具有高度水溶性,几乎无荧光,并且能与¹O₂特异性反应生成强荧光螯合物,即PATA-Tb³⁺的内过氧化物,同时荧光量子产率从0.46%显著提高到10.5%。内过氧化物的长荧光寿命(2.76毫秒)使得该探针有利于用于¹O₂的时间分辨荧光检测。荧光性质和反应特异性研究表明,这种新型探针对¹O₂具有高度敏感性和选择性。该探针用于定量检测由MoO₄²⁻-H₂O₂体系产生的¹O₂,检测限为10.8 nM。此外,通过在弱酸性缓冲液中实时监测吲哚-3-乙酸在辣根过氧化物酶催化氧化体系中¹O₂生成的动力学过程,证明了该探针具有良好的适用性。

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