title: Synthetic multifunctional pores with external and internal active sites for ligand gating and noncompetitive blockage.
abstract: Design, synthesis, and multifunctionality of p-octiphenyl beta-barrel pores with external LRL triads and internal HH dyads are described. Molecular recognition of anionic fullerenes > calixarenes > pyrenes by guanidinium arrays at the outer pore surface is shown to result in pore opening, whereas alpha-helix recognition within the topologically matching internal space is shown to result in noncompetitive pore blockage. This experimental evidence for multifunctionality is supported by comparison with pertinent control pores and blockers, by structural studies using FRET from p-octiphenyl donors in the pore to BODIPY acceptors in the bilayer, and by molecular mechanics simulations. Practical usefulness of ligand-gated synthetic multifunctional pores is exemplified with the continuous detection of chemical processes.
authors.affiliation: Department of Organic Chemistry, University of Geneva, Geneva, Switzerland.
authors.forename: Virginie
authors.initials: V
authors.lastname: Gorteau
authors.forename: Florent
authors.initials: F
authors.lastname: Perret
authors.forename: Guillaume
authors.initials: G
authors.lastname: Bollot
authors.forename: Jiri
authors.initials: J
authors.lastname: Mareda
authors.forename: Adina N
authors.initials: AN
authors.lastname: Lazar
authors.forename: Anthony W
authors.initials: AW
authors.lastname: Coleman
authors.forename: Duy-Hien
authors.initials: DH
authors.lastname: Tran
authors.forename: Naomi
authors.initials: N
authors.lastname: Sakai
authors.forename: Stefan
authors.initials: S
authors.lastname: Matile
mesh_terms: D000818:Animals; D001665:Binding Sites; D001896:Boron Compounds / Q000737:chemistry; D004950:Esterases / Q000737:chemistry / Q000378:metabolism; D031541:Fluorescence Resonance Energy Transfer; D008024:Ligands; D008051:Lipid Bilayers / Q000737:chemistry*; D008099:Liver / Q000201:enzymology; D008567:Membranes, Artificial; D008958:Models, Molecular; D010455:Peptides / Q000737:chemistry*; D011099:Polyglutamic Acid / Q000737:chemistry*; D013552:Swine
chemical_list: C095489:4,4-difluoro-4-bora-3a,4a-diaza-s-indacene; D001896:Boron Compounds; D008024:Ligands; D008051:Lipid Bilayers; D008567:Membranes, Artificial; D010455:Peptides; C015462:polyarginine; D011099:Polyglutamic Acid; D004950:Esterases