title: 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.
authors.affiliation: Department of Chemistry and Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province, Shantou University, Guangdong 515063 (China).|Department of Chemistry, Hanshan Normal University, Chaozhou, Guangdong 521041 (China).
authors.forename: Hong
authors.initials: H
authors.lastname: Cai
authors.affiliation: Department of Chemistry and Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province, Shantou University, Guangdong 515063 (China).
authors.forename: Mian
authors.initials: M
authors.lastname: Li
authors.affiliation: Department of Chemistry and Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province, Shantou University, Guangdong 515063 (China).
authors.forename: Xiao-Rong
authors.initials: XR
authors.lastname: Lin
authors.affiliation: Department of Chemistry and Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province, Shantou University, Guangdong 515063 (China).
authors.forename: Wei
authors.initials: W
authors.lastname: Chen
authors.affiliation: Department of Chemistry and Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province, Shantou University, Guangdong 515063 (China).
authors.forename: Guang-Hui
authors.initials: GH
authors.lastname: Chen
authors.affiliation: Department of Chemistry and Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province, Shantou University, Guangdong 515063 (China).
authors.forename: Xiao-Chun
authors.initials: XC
authors.lastname: Huang
authors.affiliation: Department of Chemistry and Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province, Shantou University, Guangdong 515063 (China). dli@stu.edu.cn.
authors.forename: Dan
authors.initials: D
authors.lastname: Li
mesh_terms: D004247:DNA / Q000737:chemistry*; D007700:Kinetics; D008670:Metals / Q000737:chemistry*; D009930:Organic Chemicals / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D013059:Spectrum Analysis, Raman; D013816:Thermodynamics
chemical_list: D008670:Metals; D009930:Organic Chemicals; D004247:DNA
keywords: Watson-Crick base pairing; adaptive chemistry; host-guest chemistry; metal-organic frameworks; supramolecular recognition