Engulfing Behavior of Nanoparticles into Thermoresponsive Microgels: A Mesoscopic Simulation Study

The engulfing of nanoparticles into microgels provides a versatile platform to design nano- and microstructured materials with various shape anisotropies and multifunctional properties. Manipulating the spontaneous engulfment process remains elusive. Herein, we report a mesoscopic simulation study on the engulfing behavior of nanoparticles into thermoresponsive microgels. The effects of the multiple parameters, including binding strength, temperature, and nanoparticle size, are examined systematically. Our simulation results disclose three engulfing states at different temperatures, namely full-engulfing, half-engulfing, and surface contact. The engulfing depth is determined by the complementary balance of interfacial elastocapillarity. Specifically, the van der Waals interaction of hybrid microgel-nanoparticle offers the capillary force while the internally networked structure of microgel reinforces the elasticity repulsion. Our study, validated by relevant experimental results, provides a mechanistic understanding of the interfacial elastocapillarity for nanoparticle-microgels.