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Molecular Vise Approach to Create Metal‐Binding Sites in MOFs and Detection of Biomarkers
Author(s) -
Wang Yang,
Liu Qi,
Zhang Qin,
Peng Bosi,
Deng Hexiang
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201803201
Subject(s) - chemistry , carboxylate , metal ions in aqueous solution , metal organic framework , linker , metal , ligand (biochemistry) , benzoic acid , binding site , inorganic chemistry , crystallography , stereochemistry , organic chemistry , adsorption , biochemistry , receptor , computer science , operating system
Abstract We report a new approach to create metal‐binding site in a series of metal–organic frameworks (MOFs), where tetratopic carboxylate linker, 4′,4′′,4′′′,4′′′′‐methanetetrayltetrabiphenyl‐4‐carboxylic acid, is partially replaced by a tritopic carboxylate linker, tris(4‐carboxybiphenyl)amine, in combination with monotopic linkers, formic acid, trifluoroacetic acid, benzoic acid, isonicotinic acid, 4‐chlorobenzoic acid, and 4‐nitrobenzoic acid, respectively. The distance between these paired‐up linkers can be precisely controlled, ranging from 5.4 to 10.8 Å, where a variety of metals, Mg 2+ , Al 3+ , Cr 3+ , Mn 2+ , Fe 3+ , Co 2+ , Ni 2+ , Cu 2+ , Zn 2+ , Ag + , Cd 2+ and Pb 2+ , can be placed in. The distribution of these metal‐binding sites across a single crystal is visualized by 3D tomography of laser scanning confocal microscopy with a resolution of 10 nm. The binding affinity between the metal and its binding‐site in MOF can be varied in a large range (observed binding constants, K obs from 1.56×10 2 to 1.70×10 4 L mol −1 ), in aqueous solution. The fluorescence of these crystals can be used to detect biomarkers, such as cysteine, homocysteine and glutathione, with ultrahigh sensitivity and without the interference of urine, through the dissociation of metal ions from their binding sites.