Spatial, Hysteretic, and Adaptive Host–Guest Chemistry in a Metal–Organic Framework with Open Watson–Crick Sites

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.

Water‐stable Adenine‐based MOFs with Polar Pores for Selective CO2 Capture

“…[19] In-dependently, [20] Rosi and co-workerss howed that adeninate MOFs could have high CO 2 capacity,w ith ah igh heat of adsorptionf or CO 2 (33.1 KJ mol À1 ). The Lewis basic N-sites of amino and pyrimidine groups played ak ey role in gaining CO 2 selectivity.L ia nd co-workersr eported an Zn-adeninate MOF, [21] in whichn itrogens are positioned uniformly along the pore. But, they did not show any gas captureo rs eparation ability of the Zn-adeninate MOF.A sa denine is N-rich, nontoxic, easily-available, and inexpensive havingi ta saco-ligand in the framework of MOF will be highly advantageous.…”

Tandem Förster Resonance Energy Transfer Induced Luminescent Ratiometric Thermometry in Dye‐Encapsulated Biological Metal–Organic Frameworks

“…For example, lanthanide ions, luminescent dyes, and quantum dots could be encapsulated in MOFs for applications in color control and temperature sensing. [4d,e,f,9b] Many cases of LRT‐MOFs based on lanthanide ions have received much attention for their interesting temperature‐dependent luminescence properties. [3a,4b,5b,6,7] More recently, LRT‐MOFs constructed with mixed lanthanide ions (usually Tb 3+ and Eu 3+ ) have been reported by Qian and Chen et al with improved sensing performance and sensitivity.…”

“…[4d,e,f,9b] Many cases of LRT‐MOFs based on lanthanide ions have received much attention for their interesting temperature‐dependent luminescence properties. [3a,4b,5b,6,7] More recently, LRT‐MOFs constructed with mixed lanthanide ions (usually Tb 3+ and Eu 3+ ) have been reported by Qian and Chen et al with improved sensing performance and sensitivity. [1b,c,3a,4b,7] However, scarcity of rare earth metals could limit their extensive applications of any kind.…”

Enhanced anti-cancer activities of a gold(III) pyrrolidinedithiocarbamato complex incorporated in a biodegradable metal-organic framework

“…The zinc-based metal-organic frameworks ZnBTCA (BTCA represents benzene-1,3,5-tricarboxyl-adenine) [47], Bio-MOF-1 [48] and PCN-530 (PCN represents porous coordination network) [49] were prepared according to the reported procedures and their phase purities were confirmed by using PXRD.…”

“…All of these contain zinc ions and a biocompatible substance adenine (ad). ZnBTCA is biodegradable (can be decompose in aqueous solutions) and is composed of a benzene-1,3,5-tricarboxylic acid (BTC) linker having a unit-cell formula of Zn 3 (ad)(BTC) 2 (H 2 O)·(CH 3 ) 2 NH 2 ·xDMF·yH 2 O [47]. The framework host of ZnBTCA contains one-dimensional channels with window dimension of ~8.0 × 11.0 Å (Fig.…”