Nolan Elizabeth M, Racine Maryann E, Lippard Stephen J
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
Inorg Chem. 2006 Mar 20;45(6):2742-9. doi: 10.1021/ic052083w.
The syntheses and photophysical properties of mercury sensors 2 and 3 (MS2 and MS3), two asymmetrically derivatized fluorescein-based dyes designed for Hg(II) detection, are described. These sensors each contain a single pyridyl-amine-thiol metal-binding moiety, form 1:1 complexes with Hg(II), and exhibit selectivity for Hg(II) over other Group 12 metals, alkali and alkaline earth metals, and most divalent first-row transition metals. Both dyes display superior brightness (Phi x epsilon) and fluorescence enhancement following Hg(II) coordination in aqueous solution. At neutral pH, the fluorescence turn-on derives from greater brightness due to increased molar absorptivity. At higher pH, photoinduced electron transfer quenching of the free dye is enhanced, and the Hg(II)-induced turn-on also benefits from alleviation of this pathway. MS2 can detect ppb levels of Hg(II) in aqueous solution, demonstrating its ability to identify environmentally relevant concentrations of Hg(II).
本文描述了汞传感器2和3(MS2和MS3)的合成及光物理性质,这两种基于荧光素的不对称衍生化染料用于检测Hg(II)。这些传感器各自包含一个单一的吡啶基胺硫醇金属结合部分,与Hg(II)形成1:1配合物,并且对Hg(II)表现出相对于其他第12族金属、碱金属和碱土金属以及大多数二价第一排过渡金属的选择性。两种染料在水溶液中与Hg(II)配位后均表现出优异的亮度(Phi x epsilon)和荧光增强。在中性pH值下,荧光开启源于摩尔吸光率增加导致的更高亮度。在较高pH值下,游离染料的光致电子转移猝灭增强,并且Hg(II)诱导的开启也受益于该途径的缓解。MS2能够检测水溶液中ppb水平的Hg(II),证明了其识别与环境相关浓度Hg(II)的能力。