Spatial, Hysteretic, and Adaptive Host–Guest Chemistry in a Metal–Organic Framework with Open Watson–Crick Sites*
This research is financially supported by the National Basic Research Program of China (973 Program, 2012CB821706 and 2013CB834803) and the National Natural Science Foundation of China (91222202 and 21171114). We are grateful for constructive criticism and suggestions from the reviewers and Prof. Jie‐Peng Zhang (Sun Yat‐Sen University).
Abstract
Biological and artificial molecules and assemblies capable of supramolecular recognition, especially those with nucleobase pairing, usually rely on autonomous or collective binding to function. Advanced site‐specific recognition takes advantage of cooperative spatial effects, as in local folding in protein–DNA binding. Herein, we report a new nucleobase‐tagged metal–organic framework (MOF), namely ZnBTCA (BTC=benzene‐1,3,5‐tricarboxyl, A=adenine), in which the exposed Watson–Crick faces of adenine residues are immobilized periodically on the interior crystalline surface. Systematic control experiments demonstrated the cooperation of the open Watson–Crick sites and spatial effects within the nanopores, and thermodynamic and kinetic studies revealed a hysteretic host–guest interaction attributed to mild chemisorption. We further exploited this behavior for adenine–thymine binding within the constrained pores, and a globally adaptive response of the MOF host was observed.
Number of times cited: 4
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