Phase behavior of thermoresponsive colloids drives re-entrant plasmon coupling

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Auteurs principaux: Capocefalo, Angela, Brasili, Francesco, Pérez, Javier, Chauveau, Edouard, Casciardi, Stefano, Militello, Andrea, Sciortino, Francesco, Zaccarelli, Emanuela, Bordi, Federico, Truzzolillo, Domenico, Sennato, Simona
Format: Preprint
Publié: 2026
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author Capocefalo, Angela
Brasili, Francesco
Pérez, Javier
Chauveau, Edouard
Casciardi, Stefano
Militello, Andrea
Sciortino, Francesco
Zaccarelli, Emanuela
Bordi, Federico
Truzzolillo, Domenico
Sennato, Simona
author_facet Capocefalo, Angela
Brasili, Francesco
Pérez, Javier
Chauveau, Edouard
Casciardi, Stefano
Militello, Andrea
Sciortino, Francesco
Zaccarelli, Emanuela
Bordi, Federico
Truzzolillo, Domenico
Sennato, Simona
contents Plasmonic nanoparticles (NPs) integrated within thermoresponsive polymeric microgels provide a versatile platform for the realization of stimuli-responsive optical materials, where the microgel volume phase transition enables dynamic control of plasmon coupling. This study uncovers a counter-intuitive re-entrant behavior with increasing NP loading in which plasmon coupling initially strengthens and subsequently weakens beyond a critical NP-to-microgel number ratio. By combining light and X-ray scattering techniques with optical spectroscopy and electrophoretic mobility measurements, it is demonstrated that plasmon coupling is governed not only by the interparticle distance between NPs confined within individual microgels, but also by the colloidal stability of the hybrid complexes. At intermediate NP loadings, surface charge inhomogeneities induced by NP adsorption promote aggregation of microgel-NPs complexes, resulting in enhanced plasmon coupling. In contrast, when the complexes remain colloidally stable, coupling is dictated solely by NP organization within the corona of individual microgels. A quantitative relationship between plasmon coupling and interparticle distance reveals two distinct coupling regimes. This behavior is rationalized through a phase diagram linking colloidal stability to optical response. These findings identify colloidal stability as a key parameter for designing soft plasmonic systems with programmable optical properties.
format Preprint
id arxiv_https___arxiv_org_abs_2604_15860
institution arXiv
publishDate 2026
record_format arxiv
spellingShingle Phase behavior of thermoresponsive colloids drives re-entrant plasmon coupling
Capocefalo, Angela
Brasili, Francesco
Pérez, Javier
Chauveau, Edouard
Casciardi, Stefano
Militello, Andrea
Sciortino, Francesco
Zaccarelli, Emanuela
Bordi, Federico
Truzzolillo, Domenico
Sennato, Simona
Soft Condensed Matter
Plasmonic nanoparticles (NPs) integrated within thermoresponsive polymeric microgels provide a versatile platform for the realization of stimuli-responsive optical materials, where the microgel volume phase transition enables dynamic control of plasmon coupling. This study uncovers a counter-intuitive re-entrant behavior with increasing NP loading in which plasmon coupling initially strengthens and subsequently weakens beyond a critical NP-to-microgel number ratio. By combining light and X-ray scattering techniques with optical spectroscopy and electrophoretic mobility measurements, it is demonstrated that plasmon coupling is governed not only by the interparticle distance between NPs confined within individual microgels, but also by the colloidal stability of the hybrid complexes. At intermediate NP loadings, surface charge inhomogeneities induced by NP adsorption promote aggregation of microgel-NPs complexes, resulting in enhanced plasmon coupling. In contrast, when the complexes remain colloidally stable, coupling is dictated solely by NP organization within the corona of individual microgels. A quantitative relationship between plasmon coupling and interparticle distance reveals two distinct coupling regimes. This behavior is rationalized through a phase diagram linking colloidal stability to optical response. These findings identify colloidal stability as a key parameter for designing soft plasmonic systems with programmable optical properties.
title Phase behavior of thermoresponsive colloids drives re-entrant plasmon coupling
topic Soft Condensed Matter
url https://arxiv.org/abs/2604.15860