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Updated: May 8, 2026

Plasmonic Trapping and Release of Nanoparticles in a Monitoring Environment
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Surface-Selective Molecular Binding and Replacement Selectivity in Plasmonic Nanocavities.

Eric S A Goerlitzer1, Zijia Wu1, Aidan Brzakalik1

  • 1Nanophotonics Centre, Cavendish Laboratory, Department of Physics, University of Cambridge, Cambridge CB3 0US, United Kingdom.

The Journal of Physical Chemistry Letters
|May 7, 2026
PubMed
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Researchers optically tracked molecular self-assembled monolayers (SAMs) in nanocavities. They discovered replacement thiols attach to nanoparticles, offering new ways to control nanoscale chemical assembly.

Area of Science:

  • Nanoscience and nanotechnology
  • Surface chemistry
  • Plasmonics

Background:

  • Molecular self-assembled monolayers (SAMs) are crucial in nanoscience for applications like sensing and molecular electronics.
  • Thiol binding to coinage metals typically forms robust molecular layers on planar surfaces.
  • Understanding SAM behavior at the nanoscale, especially in confined environments, remains limited.

Purpose of the Study:

  • To investigate the replacement dynamics of thiol SAMs within nanocavities under plasmonic confinement.
  • To elucidate the mechanism of thiol SAM replacement when nanoparticles are introduced onto the SAM.
  • To explore methods for controlling these replacement dynamics for tailored nanostructures.

Main Methods:

  • Utilizing strong plasmonic confinement for optical tracking of SAM replacement.

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Last Updated: May 8, 2026

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  • Employing a range of model thiol molecules to study replacement mechanisms.
  • Investigating the role of dithiols in preventing or controlling thiol exchange.

    • Main Results:

    • An unexpected mechanism for thiol SAM replacement was observed in nanocavities when nanoparticles were added.
    • Replacement thiols preferentially attach to the overlying nanoparticle and rotate into the nanogap.
    • Dithiols were found to effectively prevent this replacement by stabilizing metal atoms.

    Conclusions:

    • The study reveals a novel mechanism for thiol SAM replacement driven by nanoparticle interaction in confined plasmonic systems.
    • This mechanism provides a pathway for precise spatial control over molecular assembly at the nanoscale.
    • The findings enable the creation of asymmetric molecular architectures and post-functionalization of plasmonic nanostructures.