title: Rigid-rod anion-pi slides for multiion hopping across lipid bilayers.
abstract: Shape-persistent oligo-p-phenylene-N,N-naphthalenediimide (O-NDI) rods are introduced as anion-pi slides for chloride-selective multiion hopping across lipid bilayers. Results from end-group engineering and covalent capture as O-NDI hairpins suggested that self-assembly into transmembrane O-NDI bundles is essential for activity. A halide topology VI (Cl > F > Br approximately I, Cl/Br approximately Cl/I > 7) implied strong anion binding along the anion-pi slides with relatively weak contributions from size exclusion (F >or= OAc). Anomalous mole fraction effects (AMFE) supported the occurrence of multiion hopping along the pi-acidic O-NDI rods. The existence of anion-pi interactions was corroborated by high-level ab initio and DFT calculations. The latter revealed positive NDI quadrupole moments far beyond the hexafluorobenzene standard. Computational studies further suggested that anion binding occurs at the confined, pi-acidic edges of the sticky NDI surface and is influenced by the nature of the phenyl spacer between two NDIs. With regard to methods development, a detailed analysis of the detection of ion selectivity with the HPTS assay including AMFE in vesicles is provided.
authors.affiliation: Department of Organic Chemistry, University of Geneva, Geneva, Switzerland.
authors.forename: Virginie
authors.initials: V
authors.lastname: Gorteau
authors.forename: Guillaume
authors.initials: G
authors.lastname: Bollot
authors.forename: Jiri
authors.initials: J
authors.lastname: Mareda
authors.forename: Stefan
authors.initials: S
authors.lastname: Matile
mesh_terms: D007477:Ions; D008051:Lipid Bilayers; D015394:Molecular Structure
chemical_list: D007477:Ions; D008051:Lipid Bilayers