Turn-on fluorescence sensing of nucleoside polyphosphates using a xanthene-based Zn(II) complex chemosensor
Turn-on fluorescence sensing of nucleoside polyphosphates using a xanthene-based Zn(II) complex chemosensor
复制标题
DOI：
10.1021/ja803262w
复制
发表时间：
2008-09-10
影响因子：
15
通讯作者：
Hamachi, Itaru
中科院分区：
文献类型：
--
作者：
Ojida, Akio;Takashima, Ippei;Hamachi, Itaru
小分子化学传感器的荧光传感技术是一种多功能的生物活性物质功能分析技术。我们现在报告一种新的荧光化学传感器的核苷多磷酸，如ATP使用金属阴离子配位化学。化学传感器1- 2 Zn（II）由作为结合基序的2，2 '-吡啶二甲基胺（Dpa）-Zn（II）和作为多磷酸核苷的荧光传感单元的咕吨两个位点组成。化学传感器1- 2 Zn（II）选择性地感测具有大的荧光增强（F/F-o > 15）和强的结合亲和力（K-app接近1 × 10（6）M-1）的核苷多磷酸，而单磷酸物种和各种其他阴离子没有引起可检测的荧光变化。1- 2 Zn（II）的“开启”荧光是基于一种新的机制，该机制涉及结合诱导的氧杂蒽环的共轭形式从其非荧光的cleconjugated状态的恢复，该状态是由锌结合水的前所未有的亲核攻击形成的。1- 2 Zn（II）检测核苷多磷酸的选择性和高灵敏度的能力使其在活细胞中ATP颗粒储存的荧光可视化中的生物分析应用成为可能，证明了1- 2 Zn（II）的潜在效用。
Fluorescence sensing with small molecular chemosensors is a versatile technique for elucidation of function of various biological substances. We now report a new fluorescent chemosensor for nucleoside polyphosphates such as ATP using metal-anion coordination chemistry. The chemosensor 1-2Zn(II) is comprised of the two sites of 2,2'-dipicolylamine (Dpa)-Zn(II) as the binding motifs and xanthene as a fluorescent sensing unit for nucleoside polyphosphates. The chemosensor 1-2Zn(II) selectively senses nucleoside polyphosphates with a large fluorescence enhancement (F/F-o > 15) and strong binding affinity (K-app approximate to 1 x 10(6) M-1), whereas no detectable fluorescence change was induced by monophosphate species and various other anions. The 'turn-on,' fluorescence of 1-2Zn(II) is based on a new mechanism, which involves the binding-induced recovery of the conjugated form of the xanthene ring from its nonfluorescent cleconjugated state which was formed by an unprecedented nucleophilic attack of zinc-bound water. The selective and highly sensitive ability of 1-2Zn(II) to detect nucleoside polyphosphates enables its bioanalytical applications in fluorescence visualization of ATP particulate stores in living cells, demonstrating the potential utility of 1-2Zn(II).