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PreprintCC BY-NC-NDChemRxiv

Macromolecular Size Matching in Stabilizing Corrugated Chiral Plasmonic Nanostructures

  • Yingying Cai1,2,3,4,5
  • Anjana Kannan6,7,8
  • Jessica Ma1,2,3,5
  • Qun Song9,10
  • Yuwen Peng11,10
  • Kai Zhang9,10
  • Sara Bals6,7,8
  • Nicholas A. Kotov1,2,3,5,12
12 affiliations
  1. 1Biointerfaces Institute
  2. 2University of Michigan
  3. 3Department of Chemical Engineering
  4. 4Leibniz Institut für Polymerforschung Dresden e.V.
  5. 5Center of Complex Particle Systems (COMPASS
  6. 6EMAT
  7. 7University of Antwerp
  8. 8NANOlight Center of Excellence
  9. 9Sustainable Materials and Chemistry, Department of Wood Technology and Wood-based Composites
  10. 10Georg-August-Universität Göttingen
  11. 11Institute of Physical Chemistry
  12. 12Department of Materials Science and Engineering
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Abstract

Chiral plasmonic nanoparticles derive strong chiroptical responses sensitive from their corrugated, high-curvature surfaces, but these same features are thermodynamically unstable. Surface functionalization using macromolecules could broaden their utility by enabling improved colloidal compatibility, secondary functionalization, stimuli responsiveness and and assembly into higher-order structures. However, as the chiroptically active surface feactures are often only a few nanometer in size, inadequate size matching leads to structural instability, causing particle surfaces to flatten and consequently diminishing their chiroptical properties. Here, we show that chain-length-selective polymer functionalization stabilizes the fine groove structures of chiral gold nanorods. We identify a threshold behavior of hydrodynamic diameter below which polymer coils can penetrate and anchor within the grooves, preserving structural integrity and chiroptical activities. Guided by this principle, we establish a sequential functionalization strategy using polymers of two distinct sizes to produce chiral AuNRs with stable chiroptical performance. Our results establish a general design rule for integrating versatile macromolecular architectures with chiral nanoparticles and expand the engineering space for nano-optical applications.

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Cite

BibTeXRIS
BibTeX
@misc{cai2026macromolecular,
  title = {{Macromolecular Size Matching in Stabilizing Corrugated Chiral Plasmonic Nanostructures}},
  author = {Yingying Cai and Anjana Kannan and Jessica Ma and Qun Song and Yuwen Peng and Kai Zhang and Sara Bals and Nicholas A. Kotov},
  howpublished = {ChemRxiv},
  year = {2026},
  month = sep,
  doi = {10.26434/chemrxiv.15009141/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009141/v1},
  note = {CC BY-NC-ND},
}
RIS
TY  - UNPB
TI  - Macromolecular Size Matching in Stabilizing Corrugated Chiral Plasmonic Nanostructures
AU  - Yingying Cai
AU  - Anjana Kannan
AU  - Jessica Ma
AU  - Qun Song
AU  - Yuwen Peng
AU  - Kai Zhang
AU  - Sara Bals
AU  - Nicholas A. Kotov
PY  - 2026
DA  - 2026/09/21
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15009141/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009141/v1
AB  - Chiral plasmonic nanoparticles derive strong chiroptical responses sensitive from their corrugated, high-curvature surfaces, but these same features are thermodynamically unstable. Surface functionalization using macromolecules could broaden their utility by enabling improved colloidal compatibility, secondary functionalization, stimuli responsiveness and and assembly into higher-order structures. However, as the chiroptically active surface feactures are often only a few nanometer in size, inadequate size matching leads to structural instability, causing particle surfaces to flatten and consequently diminishing their chiroptical properties. Here, we show that chain-length-selective polymer functionalization stabilizes the fine groove structures of chiral gold nanorods. We identify a threshold behavior of hydrodynamic diameter below which polymer coils can penetrate and anchor within the grooves, preserving structural integrity and chiroptical activities. Guided by this principle, we establish a sequential functionalization strategy using polymers of two distinct sizes to produce chiral AuNRs with stable chiroptical performance. Our results establish a general design rule for integrating versatile macromolecular architectures with chiral nanoparticles and expand the engineering space for nano-optical applications.
ER  -