title: Through-space transfer of chiral information mediated by a plasmonic nanomaterial.
abstract: The ability to detect chirality gives stereochemically attuned nanosensors the potential to revolutionize the study of biomolecular processes. Such devices may structurally characterize the mechanisms of protein-ligand binding, the intermediates of amyloidogenic diseases and the effects of phosphorylation and glycosylation. We demonstrate that single nanoparticle plasmonic reporters, or nanotags, can enable a stereochemical response to be transmitted from a chiral analyte to an achiral benzotriazole dye molecule in the vicinity of a plasmon resonance from an achiral metallic nanostructure. The transfer of chirality was verified by the measurement of mirror image surface enhanced resonance Raman optical activity spectra for the two enantiomers of both ribose and tryptophan. Computational modelling confirms these observations and reveals the novel chirality transfer mechanism responsible. This is the first report of colloidal metal nanoparticles in the form of single plasmonic substrates displaying an intrinsic chiral sensitivity once attached to a chiral molecule.
authors.affiliation: Faculty of Life Sciences and Manchester Institute of Biotechnology, University of Manchester, 131 Princess Street, Manchester M1 7DN, UK.
authors.forename: Saeideh
authors.initials: S
authors.lastname: Ostovar pour
authors.affiliation: Centre for Molecular Nanometrology, WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow G1 1XL, UK.
authors.forename: Louise
authors.initials: L
authors.lastname: Rocks
authors.affiliation: Centre for Molecular Nanometrology, WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow G1 1XL, UK.
authors.forename: Karen
authors.initials: K
authors.lastname: Faulds
authors.affiliation: Centre for Molecular Nanometrology, WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow G1 1XL, UK.
authors.forename: Duncan
authors.initials: D
authors.lastname: Graham
authors.affiliation: 1] Department of Analytical Chemistry, University of Chemistry and Technology, Technická 5, Prague 16628, Czech Republic [2] Institute of Organic Chemistry and Biochemistry, Academy of Sciences, Flemingovo náměstí 2, Prague 16610, Czech Republic.
authors.forename: Václav
authors.initials: V
authors.lastname: Parchaňský
authors.affiliation: 1] Department of Analytical Chemistry, University of Chemistry and Technology, Technická 5, Prague 16628, Czech Republic [2] Institute of Organic Chemistry and Biochemistry, Academy of Sciences, Flemingovo náměstí 2, Prague 16610, Czech Republic.
authors.forename: Petr
authors.initials: P
authors.lastname: Bouř
authors.affiliation: 1] Faculty of Life Sciences and Manchester Institute of Biotechnology, University of Manchester, 131 Princess Street, Manchester M1 7DN, UK [2] School of Applied Sciences, RMIT University, GPO Box 2476, Melbourne VIC 3001, Australia.
authors.forename: Ewan W
authors.initials: EW
authors.lastname: Blanch
mesh_terms: D002942:Circular Dichroism; D003198:Computer Simulation; D008958:Models, Molecular; D049329:Nanostructures / Q000737:chemistry*; D013237:Stereoisomerism; D020349:Surface Plasmon Resonance / Q000379:methods*