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Probing the bilayer-monolayer switching of capping agents on Au nanorods and its interaction with guest molecules\(^{\S }\)

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Abstract

The anisotropic features of Au nanorods make them an attractive nanoscale precursor for the design of higher order nanostructured materials. However, the mode of interaction of various molecular systems on Au nanorods is not well-understood. In the present study, we have employed isothermal titration calorimetry and surface-enhanced Raman scattering for understanding various types of interactions of functional molecules on the surface of gold nanorods. The binding of thiol-bearing analyte molecules is effective with the surface of gold nanorods in acetonitrile-rich solvents and found to be weak in an aqueous medium. The effective interaction of thiol-bearing analyte molecules on nanorods is facilitated by the breakdown of cetyltrimethylammonium bromide bilayer to a monolayer in organic-rich solvent systems, thereby resulting in appreciable signals in isothermal titration calorimetry and surface-enhanced Raman spectra. The electrostatic interaction of analyte molecule is mainly driven by the charge reversal on the surface of Au nanorods on switching the solvent from aqueous to organic medium. Thus, based on isothermal titration calorimetry and surface-enhanced Raman scattering investigations, it is established that the microheterogeneous environment around the Au nanorods plays a crucial role in driving the interaction of analyte molecules.

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SYNOPSIS Cetyltrimethylammonium bromide on Au nanorod exists as a bilayer in water and as a monolayer in aqueous-organic medium, which in turn influences the surface charge and plays a crucial role in driving the substrate-analyte interactions.

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Acknowledgements

JK acknowledges the Council of Scientific & Industrial Research (CSIR), India, for the fellowship. KGT acknowledges the Department of Science and Technology (DST Nanomission Project; SR/NM/NS-23/2016), Government of India for financial support and the J. C. Bose National Fellowship of DST.

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Authors and Affiliations

  1. School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram (IISER-TVM), Vithura, Thiruvananthapuram, Kerala, 695 551, India

    Jatish Kumar & K George Thomas

  2. CSIR –National Institute for Interdisciplinary Science and Technology, Thiruvananthapuram, Kerala, 695 019, India

    Jatish Kumar

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  1. Jatish Kumar
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  2. K George Thomas
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Correspondence to K George Thomas.

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$$^{\S }$$ § Dedicated to Professor M V George on the occasion of his 90 $$^\mathrm{th}$$ th Birth Anniversary.

Special Issue on Photochemistry, Photophysics and Photobiology

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Kumar, J., Thomas, K.G. Probing the bilayer-monolayer switching of capping agents on Au nanorods and its interaction with guest molecules\(^{\S }\). J Chem Sci 130, 138 (2018). https://doi.org/10.1007/s12039-018-1550-0

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  • DOI: https://doi.org/10.1007/s12039-018-1550-0

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