Chiral Seeded Growth of Gold Nanorods Into 4-Fold Twisted Nanoparticles with Plasmonic Optical Activity

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2023
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Mychinko, Mikhail
Gómez-Graña, Sergio
Morales-Vidal, Jordi
Obelleiro-Liz, Manuel
Heyvaert, Wouter
Bals, Sara
Liz-Marzán, Luis M.
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Advanced Materials ; 35 (2023), 1. - 2208299. - Wiley. - ISSN 0935-9648. - eISSN 1521-4095
Abstract
A robust and reproducible methodology to prepare stable inorganic nanoparticles with chiral morphology might hold the key to the practical utilization of these materials. We describe herein an optimized chiral growth method to prepare 4-fold twisted gold nanorods, where the amino acid cysteine is used as a dissymmetry inducer. Four tilted ridges were found to develop on the surface of single-crystal nanorods upon repeated reduction of HAuCl4 , in the presence of cysteine as the chiral inducer and ascorbic acid as a reducing agent. From detailed electron microscopy analysis of the crystallographic structures, we propose that dissymmetry results from the development of chiral facets in the form of protrusions (tilted ridges) on the initial nanorods, eventually leading to a twisted shape. The role of cysteine is attributed to assisting enantioselective facet evolution, which is supported by density functional theory simulations of the surface energies, modified upon adsorption of the chiral molecule. The development of R-type and S-type chiral structures (small facets, terraces, or kinks) would thus be non-equal, removing the mirror symmetry of the Au NR and in turn resulting in a markedly chiral morphology with high plasmonic optical activity. This article is protected by copyright. All rights reserved.
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540 Chemistry
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twisted nanoparticles, Au nanorods, chiral seeded growth, plasmonic optical activity, atomic resolution tomography, Wulff construction, DFT
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ISO 690NI, Bing, Mikhail MYCHINKO, Sergio GÓMEZ-GRAÑA, Jordi MORALES-VIDAL, Manuel OBELLEIRO-LIZ, Wouter HEYVAERT, Guillermo GONZALEZ-RUBIO, Helmut CÖLFEN, Sara BALS, Luis M. LIZ-MARZÁN, 2023. Chiral Seeded Growth of Gold Nanorods Into 4-Fold Twisted Nanoparticles with Plasmonic Optical Activity. In: Advanced Materials. Wiley. 35(1), 2208299. ISSN 0935-9648. eISSN 1521-4095. Available under: doi: 10.1002/adma.202208299
BibTex
@article{Ni2023Chira-59108,
  year={2023},
  doi={10.1002/adma.202208299},
  title={Chiral Seeded Growth of Gold Nanorods Into 4-Fold Twisted Nanoparticles with Plasmonic Optical Activity},
  number={1},
  volume={35},
  issn={0935-9648},
  journal={Advanced Materials},
  author={Ni, Bing and Mychinko, Mikhail and Gómez-Graña, Sergio and Morales-Vidal, Jordi and Obelleiro-Liz, Manuel and Heyvaert, Wouter and Gonzalez-Rubio, Guillermo and Cölfen, Helmut and Bals, Sara and Liz-Marzán, Luis M.},
  note={Article Number: 2208299}
}
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    <dcterms:abstract xml:lang="eng">A robust and reproducible methodology to prepare stable inorganic nanoparticles with chiral morphology might hold the key to the practical utilization of these materials. We describe herein an optimized chiral growth method to prepare 4-fold twisted gold nanorods, where the amino acid cysteine is used as a dissymmetry inducer. Four tilted ridges were found to develop on the surface of single-crystal nanorods upon repeated reduction of HAuCl4 , in the presence of cysteine as the chiral inducer and ascorbic acid as a reducing agent. From detailed electron microscopy analysis of the crystallographic structures, we propose that dissymmetry results from the development of chiral facets in the form of protrusions (tilted ridges) on the initial nanorods, eventually leading to a twisted shape. The role of cysteine is attributed to assisting enantioselective facet evolution, which is supported by density functional theory simulations of the surface energies, modified upon adsorption of the chiral molecule. The development of R-type and S-type chiral structures (small facets, terraces, or kinks) would thus be non-equal, removing the mirror symmetry of the Au NR and in turn resulting in a markedly chiral morphology with high plasmonic optical activity. This article is protected by copyright. All rights reserved.</dcterms:abstract>
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