Programmable Uniform Gel Networks Amplify Weak Interactions via Multiple Anchoring for In Situ Growth of Gold Nanoparticles
Abstract
Synthesizing ultrasmall thermoresponsive nanoparticles within poly(N-isopropylacrylamide) (PNIPA) hydrogels without the use of strong ligands remains challenging, as intrinsically weak interfacial interactions and structural heterogeneity in conventional networks often lead to poor size control and aggregation. Here, we report a programmable PNIPA-based hydrogel constructed from star-shaped polymers via living radical polymerization, in which a homogeneous network containing locally reinforced crosslinking domains enables ligand-free in situ formation of ultrasmall metal nanoparticles. The uniform network provides a spatially consistent reaction environment, allowing synchronized and controllable particle growth across length scales. Nanoparticle size is governed by network architecture rather than by synthetic conditions, and the resulting hydrogel composites exhibit exceptional stability under thermal cycling and harsh chemical environments, despite relying solely on amide functionalities. Stabilization does not arise from rigid immobilization or strong ligand coordination along the polymer chains; instead, it emerges from the collective engagement of multiple spatially distributed, amide-enriched crosslinking domains. These reinforced domains generate a cooperative multiple-anchoring effect, creating a soft yet adaptive chelation-like confinement. This work establishes a versatile platform for strong-ligand-free yet robust and controllable nanoparticle synthesis, extendable to colloidal dispersions, diverse polymer matrices, and various metal nanoparticles.
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BibTeX
@misc{wang2026programmable,
title = {{Programmable Uniform Gel Networks Amplify Weak Interactions via Multiple Anchoring for In Situ Growth of Gold Nanoparticles}},
author = {Yian Wang and Junjia Zhang and Kazutaka Akiyoshi and Guohao Gao and Yinglu Liu and Kai Kawabata and Taiki Hoshino and Tsukasa Torimoto and Hirokatsu Miyata and Yusuke Yamauchi and Makoto Ogawa and Yukikazu Takeoka},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15001720/v2},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15001720/v2},
note = {CC BY},
}
RIS
TY - UNPB
TI - Programmable Uniform Gel Networks Amplify Weak Interactions via Multiple Anchoring for In Situ Growth of Gold Nanoparticles
AU - Yian Wang
AU - Junjia Zhang
AU - Kazutaka Akiyoshi
AU - Guohao Gao
AU - Yinglu Liu
AU - Kai Kawabata
AU - Taiki Hoshino
AU - Tsukasa Torimoto
AU - Hirokatsu Miyata
AU - Yusuke Yamauchi
AU - Makoto Ogawa
AU - Yukikazu Takeoka
PY - 2026
DA - 2026/10/08
PB - ChemRxiv
DO - 10.26434/chemrxiv.15001720/v2
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15001720/v2
AB - Synthesizing ultrasmall thermoresponsive nanoparticles within poly(N-isopropylacrylamide) (PNIPA) hydrogels without the use of strong ligands remains challenging, as intrinsically weak interfacial interactions and structural heterogeneity in conventional networks often lead to poor size control and aggregation. Here, we report a programmable PNIPA-based hydrogel constructed from star-shaped polymers via living radical polymerization, in which a homogeneous network containing locally reinforced crosslinking domains enables ligand-free in situ formation of ultrasmall metal nanoparticles. The uniform network provides a spatially consistent reaction environment, allowing synchronized and controllable particle growth across length scales. Nanoparticle size is governed by network architecture rather than by synthetic conditions, and the resulting hydrogel composites exhibit exceptional stability under thermal cycling and harsh chemical environments, despite relying solely on amide functionalities. Stabilization does not arise from rigid immobilization or strong ligand coordination along the polymer chains; instead, it emerges from the collective engagement of multiple spatially distributed, amide-enriched crosslinking domains. These reinforced domains generate a cooperative multiple-anchoring effect, creating a soft yet adaptive chelation-like confinement. This work establishes a versatile platform for strong-ligand-free yet robust and controllable nanoparticle synthesis, extendable to colloidal dispersions, diverse polymer matrices, and various metal nanoparticles.
ER -