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PreprintCC BYChemRxiv

Growth and Postsynthetic Modulation of Morphology-Encoded Plasmonic Chirality

  • Shubhangi Sharma1,2
  • Susmita Pradhan1,2
  • Arun Pratap Singh1,2
  • Satyajit Patra1,2
  1. 1Department of Chemistry
  2. 2Birla Institute of Technology and Science Pilani, Pilani Campus
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Abstract

Establishing how nanoscale morphology gives rise to plasmonic chirality requires understanding both its development during nanoparticle growth and its response to subsequent structural modification. Here, we investigate these complementary processes within a single nanoparticle platform through cysteine-directed Au growth followed by Ag overgrowth. Initially achiral Au bipyramids evolve into irregular, faceted nanoparticles displaying strong bisignate circular dichroism (CD), with L- and D-cysteine producing approximately mirror-related responses. Varying the relative proportions of the cysteine enantiomers systematically controls the sign and magnitude of the CD response, with near cancellation for the racemic mixture. Time-resolved measurements reveal that the positive and negative CD bands develop with comparable sigmoidal Avrami-type kinetics, quantitatively capturing the emergence of plasmonic chirality during growth. Once chirality is established, subsequent Ag deposition without additional cysteine progressively blue-shifts the plasmonic response and attenuates the CD of both enantiomeric nanoparticles without sign reversal. This attenuation accompanies the transformation of the irregular, faceted Au exterior into a smoother and more rounded Ag-rich outer morphology. Together, these observations connect the emergence and postsynthetic attenuation of plasmonic chirality and highlight the importance of the asymmetric nanoparticle exterior in sustaining morphology-encoded chiroptical activity.

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Cite

BibTeXRIS
BibTeX
@misc{sharma2026growth,
  title = {{Growth and Postsynthetic Modulation of Morphology-Encoded Plasmonic Chirality}},
  author = {Shubhangi Sharma and Susmita Pradhan and Arun Pratap Singh and Satyajit Patra},
  howpublished = {ChemRxiv},
  year = {2026},
  month = sep,
  doi = {10.26434/chemrxiv.15009103/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009103/v1},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - Growth and Postsynthetic Modulation of Morphology-Encoded Plasmonic Chirality
AU  - Shubhangi Sharma
AU  - Susmita Pradhan
AU  - Arun Pratap Singh
AU  - Satyajit Patra
PY  - 2026
DA  - 2026/09/20
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15009103/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009103/v1
AB  - Establishing how nanoscale morphology gives rise to plasmonic chirality requires understanding both its development during nanoparticle growth and its response to subsequent structural modification. Here, we investigate these complementary processes within a single nanoparticle platform through cysteine-directed Au growth followed by Ag overgrowth. Initially achiral Au bipyramids evolve into irregular, faceted nanoparticles displaying strong bisignate circular dichroism (CD), with L- and D-cysteine producing approximately mirror-related responses. Varying the relative proportions of the cysteine enantiomers systematically controls the sign and magnitude of the CD response, with near cancellation for the racemic mixture. Time-resolved measurements reveal that the positive and negative CD bands develop with comparable sigmoidal Avrami-type kinetics, quantitatively capturing the emergence of plasmonic chirality during growth. Once chirality is established, subsequent Ag deposition without additional cysteine progressively blue-shifts the plasmonic response and attenuates the CD of both enantiomeric nanoparticles without sign reversal. This attenuation accompanies the transformation of the irregular, faceted Au exterior into a smoother and more rounded Ag-rich outer morphology. Together, these observations connect the emergence and postsynthetic attenuation of plasmonic chirality and highlight the importance of the asymmetric nanoparticle exterior in sustaining morphology-encoded chiroptical activity.
ER  -