Phosphorescent sensor for biological mobile zinc.
Phosphorescent sensor for biological mobile zinc.
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DOI：
10.1021/ja207163r
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发表时间：
2011-11-16
影响因子：
15
通讯作者：
Lippard, Stephen J.
中科院分区：
文献类型：
--
作者：
You, Youngmin;Lee, Sumin;Kim, Taehee;Ohkubo, Kei;Chae, Weon-Sik;Fukuzumi, Shunichi;Jhon, Gil-Ja;Nam, Wonwoo;Lippard, Stephen J.
以2-（2，4-二氟苯基）吡啶（dfppy）环化配体和1，10-邻菲咯啉（phen）为配体的Ir（III）配合物为基础，构建了一种新型的锌磷光传感器（ZIrF）.锌特异性二（2-吡啶甲基）氨基（DPA）受体通过亚甲基接头引入phen配体的4-位。该阳离子铱（III）配合物在CH 3CN溶液中表现出双磷光带，分别来自dfppy和phen配体的蓝色和黄色发射。锌配位选择性地增强后者，提供磷光比率响应。电化学技术，量子化学计算，稳态和飞秒光谱，建立一个光物理机制，这种磷光响应。研究表明，锌的配位干扰了DPA和phen之间的光诱导电子转移（PeT）和配体内电荷转移（ILCT）的非发光过程。ZIrF可以在缓冲溶液（pH 7.0，25 mM PIPES）中以可逆和选择性的方式检测锌离子，Kd = 11 nM，pKa = 4.16。增强的信号噪声比，实现了长寿命的磷光信号的时间门控采集。应用该传感器对A549细胞中游离锌离子进行共聚焦激光扫描显微镜成像。荧光寿命成像显微镜（FLIM）检测到锌处理的A549细胞的光致发光寿命增加相比，控制。ZIrF是第一个成功检测生物样品中锌离子的磷光传感器。
A new phosphorescent zinc sensor (ZIrF) was constructed based on an Ir(III) complex bearing two 2-(2,4-difluorophenyl)pyridine (dfppy) cyclometalating ligands and a neutral 1,10-phenanthroline (phen) ligand. A zinc-specific di(2-picolyl)amino (DPA) receptor was introduced at the 4-position of the phen ligand via a methylene linker. The cationic Ir(III) complex exhibited dual phosphorescence bands in CH3CN solutions originating from blue and yellow emission of the dfppy and phen ligands, respectively. Zinc coordination selectively enhanced the latter, affording a phosphorescence ratiometric response. Electrochemical techniques, quantum chemical calculations, and steady-state and femtosecond spectroscopy were employed to establish a photophysical mechanism for this phosphorescence response. The studies revealed that zinc coordination perturbs nonemissive processes of photoinduced electron transfer (PeT) and intraligand charge transfer (ILCT) transition occurring between DPA and phen. ZIrF can detect zinc ions in a reversible and selective manner in buffered solution (pH 7.0, 25 mM PIPES) with Kd = 11 nM and pKa = 4.16. Enhanced signal-to-noise ratios were achieved by time-gated acquisition of long-lived phosphorescence signals. The sensor was applied to image biological free zinc ions in live A549 cells by confocal laser scanning microscopy. A fluorescence lifetime imaging microscope (FLIM) detected an increase in photoluminescence lifetime for zinc-treated A549 cells as compared to controls. ZIrF is the first successful phosphorescent sensor that detects zinc ions in biological samples.
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影响因子：
37.3
作者：
Costello, Leslie C;Franklin, Renty B
通讯作者：
Franklin, Renty B
影响因子：
2.5
作者：
Canani, Roberto Berni;Buccigrossi, Vittoria;Passariello, Annalisa
通讯作者：
Passariello, Annalisa
影响因子：
4.6
作者：
Chang, CJ;Nolan, EM;Lippard, SJ
通讯作者：
Lippard, SJ
影响因子：
56.9
作者：
BUSH, AI;PETTINGELL, WH;TANZI, RE
通讯作者：
TANZI, RE
影响因子：
--
作者：
Chang, CJ;Nolan, EM;Lippard, SJ
通讯作者：
Lippard, SJ