A fluorogenic probe for the copper(I)-catalyzed azide-alkyne ligation reaction:: Modulation of the fluorescence emission via 3(n,π*)-1(π,π*) inversion
A fluorogenic probe for the copper(I)-catalyzed azide-alkyne ligation reaction:: Modulation of the fluorescence emission via 3(n,π*)-1(π,π*) inversion
复制标题
DOI：
10.1021/ja049684r
复制
发表时间：
2004-07-28
影响因子：
15
通讯作者：
Fahrni, CJ
中科院分区：
文献类型：
--
作者：
Zhou, Z;Fahrni, CJ
化学选择性连接反应是在生物环境中标记蛋白质或小分子的有效方法。我们在此报告了一种通过点击化学激活的荧光探针，点击化学是一种基于叠氮部分作为官能团的高度通用的生物正交和化学选择性连接反应。在偶联反应过程中形成的三唑环的给电子特性被有效地利用来调节电子偶联香豆素荧光团的荧光输出。在生理条件下，探针基本上是非荧光的，并且在与叠氮化物连接时经历明亮的发射增强。时间分辨发射光谱和半经验量子力学计算表明，荧光切换是由于发射 1(π,π*) 和非发射 3(n,π*) 激发态的能量顺序反转所致。连接反应的快速动力学使得该探针在生物学、分析化学或材料科学领域的广泛应用中具有吸引力。
Chemoselective ligation reactions represent a powerful approach for labeling of proteins or small molecules in a biological environment. We report here a fluorogenic probe that is activated by click chemistry, a highly versatile bio-orthogonal and chemoselective ligation reaction which is based on the azide moiety as the functional group. The electron-donating properties of the triazole ring that is formed in the course of the coupling reaction was effectively utilized to modulate the fluorescence output of an electronically coupled coumarin fluorophore. Under physiological conditions the probe is essentially nonfluorescent and undergoes a bright emission enhancement upon ligation with an azide. Time-resolved emission spectroscopy and semiempirical quantum-mechanical calculations suggest that the fluorescence switching is due to an inversion of the energy ordering of the emissive1(π,π*) and nonemissive3(n,π*) excited states. The rapid kinetics of the ligation reaction render the probe attractive for a wide range of applications in biology, analytical chemistry, or material science.