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Through-space transfer of chiral information mediated by a plasmonic nanomaterial

Nature Chemistry volume 7, pages 591–596 (2015)Cite this article

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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.

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Figure 1: Schematic of the silver nanotag.
Figure 2: SERRS spectra and SERROA spectra.
Figure 3: SERRS spectra and SERROA spectra.
Figure 4: Model system and its Raman and ROA spectra, generated by matrix perturbation theory.

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Acknowledgements

This work was supported by the UK Engineering and Physical Sciences Research Council (EP/P504325/1 and GR/S75727/01), the Royal Society of Chemistry Analytical Sciences Division Studentship Scheme (GR/T05554/01), the Academy of Sciences (M200551205), and the Grant Agency (P208/11/0105, 13-03978S) of the Czech Republic. The authors thank E. Smith, M. Kadodwala, E. Hendry, C. Johannessen, S. Webb and A. Doig for discussions and D.G. acknowledges the Royal Society for support from a Wolfson research merit award.

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Authors and Affiliations

  1. Faculty of Life Sciences and Manchester Institute of Biotechnology, University of Manchester, 131 Princess Street, Manchester, M1 7DN, UK

    Saeideh Ostovar pour & Ewan W. Blanch

  2. Department of Pure and Applied Chemistry, Centre for Molecular Nanometrology, WestCHEM, University of Strathclyde, Glasgow, G1 1XL, UK

    Louise Rocks, Karen Faulds & Duncan Graham

  3. Department of Analytical Chemistry, University of Chemistry and Technology, Technická 5, Prague, 16628, Czech Republic

    Václav Parchaňský & Petr Bouř

  4. Institute of Organic Chemistry and Biochemistry, Academy of Sciences, Flemingovo náměstí 2, Prague, 16610, Czech Republic

    Václav Parchaňský & Petr Bouř

  5. School of Applied Sciences, RMIT University, GPO Box 2476, Melbourne, VIC 3001, Australia

    Ewan W. Blanch

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  1. Saeideh Ostovar pour
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Contributions

E.B. directed the project. D.G. and K.F. led the nanoparticle preparation and characterization. P.B. led the computational modelling. S.O.P. performed the SERROA studies. S.O.P. and L.R. performed SERS and characterization experiments. V.P. performed computational modelling. All authors contributed to preparing the manuscript, with E.B. and S.O.P. being the main authors.

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Correspondence to Petr Bouř or Ewan W. Blanch.

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Ostovar pour, S., Rocks, L., Faulds, K. et al. Through-space transfer of chiral information mediated by a plasmonic nanomaterial. Nature Chem 7, 591–596 (2015). https://doi.org/10.1038/nchem.2280

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