title: Hydrophobic collapse of foldamer capsules drives picomolar-level chloride binding in aqueous acetonitrile solutions.
abstract: Aqueous media are competitive environments in which to perform host-guest chemistry, particularly when the guest is highly charged. While hydrophobic binding is a recognized approach to this challenge in which apolar pockets can be designed to recognize apolar guests in water, complementary strategies are required for hydrophilic anions like chloride. Here, we present evidence of such an alternative mechanism, used everyday by proteins yet rare for artificial receptors, wherein hydrophobic interactions are shown to be responsible for organizing and stabilizing an aryl-triazole foldamer to help extract hydrophilic chloride ions from increasingly aqueous solutions. Therein, a double-helical complex gains stability upon burial of ∼80% of the π surfaces that simultaneously creates a potent, solvent-excluding microenvironment for hydrogen bonding. The chloride's overall affinity to the duplex is substantial in 25% water v/v in acetonitrile (log β2 = 12.6), and it remains strong (log β2 = 13.0) as the water content is increased to 50%. With the rise in predictable designs of abiological foldamers, this water-assisted strategy can, in principle, be utilized for binding other hydrophilic guests.
authors.affiliation: Department of Chemistry, Indiana University , 800 East Kirkwood Avenue, Bloomington, Indiana 47405, United States.
authors.forename: Yuran
authors.initials: Y
authors.lastname: Hua
authors.forename: Yun
authors.initials: Y
authors.lastname: Liu
authors.forename: Chun-Hsing
authors.initials: CH
authors.lastname: Chen
authors.forename: Amar H
authors.initials: AH
authors.lastname: Flood
mesh_terms: D000097:Acetonitriles / Q000737:chemistry*; D000838:Anions; D001391:Azo Compounds / Q000737:chemistry; D002712:Chlorides / Q000737:chemistry*; D057927:Hydrophobic and Hydrophilic Interactions; D008968:Molecular Conformation; D062165:Receptors, Artificial / Q000737:chemistry; D012996:Solutions; D013816:Thermodynamics; D014230:Triazoles / Q000737:chemistry*; D014867:Water / Q000737:chemistry*
chemical_list: D000097:Acetonitriles; D000838:Anions; D001391:Azo Compounds; D002712:Chlorides; D062165:Receptors, Artificial; D012996:Solutions; D014230:Triazoles; D014867:Water; C009850:azobenzene; C032159:acetonitrile