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Anionic pollutants are widespread in the environment and pose risks to human health. Due to the typically low concentrations of these species, the development of efficient receptors for their detection and removal from aqueous solutions is highly desirable. Here, we report the design and synthesis of a bambusuril receptor with markedly enhanced anion-binding affinity in water, achieved by introducing trifluoromethyl electron-withdrawing groups. The resulting fluorinated receptor is, to date, the most potent known receptor for several charge diffuse anions in aqueous media. The most stable 1:1 host-guest complex in water was observed with iodide, exhibiting a relative dissociation constant of 59 pM. This complex is over three orders of magnitude more stable than any previously reported complex between an artificial receptor and inorganic anion in water.
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http://dx.doi.org/10.1002/anie.202510912 | DOI Listing |
Angew Chem Int Ed Engl
September 2025
Department of Chemistry, Faculty of Science, Masaryk University, Kamenice 5, 625 00, Brno, Czech Republic.
Anionic pollutants are widespread in the environment and pose risks to human health. Due to the typically low concentrations of these species, the development of efficient receptors for their detection and removal from aqueous solutions is highly desirable. Here, we report the design and synthesis of a bambusuril receptor with markedly enhanced anion-binding affinity in water, achieved by introducing trifluoromethyl electron-withdrawing groups.
View Article and Find Full Text PDFOrg Biomol Chem
April 2025
Engineering of Molecular NanoSystems, École Polytechnique de Bruxelles, Université libre de Bruxelles, Avenue F. Roosevelt 50, CP165/64, 1050 Brussels, Belgium.
Anionophores are molecules that can transport ions across membranes. Several structural design criteria must be met for anionophores to be highly active. Fluorinated anionophores are usually more potent than their non-fluorinated analogues due to their higher lipophilicity and increased affinity for anions.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
February 2025
Engineering of Molecular NanoSystems, École Polytechnique de Bruxelles, Université Libre de Bruxelles, Avenue F.D. Roosevelt 50, CP165/64, 1050, Brussels, Belgium.
Artificial anion transporters offer a potential way to treat deficiencies in cellular anion transport of genetic origins. In contrast to the large variety of mobile anion carriers and self-assembled anion channels reported, unimolecular anion channels are less investigated. Herein, we present a unique example of a unimolecular anion channel based on a bambusuril (BU) macrocycle, a well-established anion receptor.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2024
Department of Chemistry, Indiana University Address, 800 East Kirkwood Avenue, Bloomington, Indiana, 47405, United States.
Steric manipulation is a known concept in molecular recognition but there is currently no linear free energy relationship correlating sterics to the stability of receptor-anion complexes nor to the reactivity of the bound anion. By analogy to Tolman cone angles in cation coordination chemistry, we explore how to define and correlate cone angles of organo-trifluoroborates (R-BF ) to the affinities observed for cyanostar-anion binding. We extend the analogy to a rare investigation of the anion's reactivity and how it changes upon binding.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2024
Department of Chemistry, University of Oxford, Oxford, OX1 3TA, UK.
Pores containing molecular adapters provide internal selective binding sites, thereby allowing the stochastic sensing of analytes. Herein, we demonstrate that semiaza-bambusuril (BU) acts as a non-covalent molecular adapter when lodged within the lumen of the wild-type α-hemolysin (WT-αHL) protein pore. Because the bambusurils are recognized as anion receptors, the anion binding site within the adapter-nanopore complex allows the detection of chloride anions, thus converting a non-selective pore into an anion sensor.
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