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镧系中心水中的阴离子键合:从结构和选择性到信号转导和传感。

Anion binding in water at lanthanide centres: from structure and selectivity to signalling and sensing.

机构信息

Department of Chemistry, Durham University, South Road, Durham DH1 3LE, UK.

出版信息

Chem Soc Rev. 2013 Feb 21;42(4):1652-66. doi: 10.1039/c2cs35144g. Epub 2012 Jul 3.

Abstract

Reversible anion binding at lanthanide centres in aqueous media has emerged as an effective means of signalling and sensing the presence of selected anions. The constitution and configuration of a wide range of anion adducts has been defined by X-ray analyses and NMR methods, and both chelating and monodentate binding modes characterised. Variation of the lanthanide ion modulates charge density, and ligand modification allows alteration of both the peripheral electrostatic gradient and the local steric demand at the metal centre. Thus, selectivity for a target anion can be engineered, and the affinity constant modulated to target the desired concentration range. Changes in anion concentration can be monitored rapidly, accurately and with high spatial resolution using optical emission spectroscopy and microscopy, facilitating the measurement of anions such as bicarbonate, lactate, citrate and urate in a variety of bio-fluids.

摘要

在水相介质中,镧系中心的阴离子可逆结合已成为一种有效信号传递和检测特定阴离子的方法。通过 X 射线分析和 NMR 方法已经确定了广泛的阴离子加合物的组成和构型,并且已经对螯合和单齿配位模式进行了特征描述。镧系离子的变化调节了电荷密度,并且配体的修饰允许改变金属中心的外围静电梯度和局部空间位阻。因此,可以设计针对特定阴离子的选择性,并调节亲和常数以针对所需的浓度范围。使用光学发射光谱和显微镜可以快速、准确和高空间分辨率地监测阴离子浓度的变化,从而促进了在各种生物流体中对碳酸氢盐、乳酸盐、柠檬酸盐和尿酸盐等阴离子的测量。

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