Extensive Stable Physical Contacts between a Nanoparticle and a Highly Repulsive Polymeric Layer
SA Etha and TH Pial and S Das, JOURNAL OF PHYSICAL CHEMISTRY B, 126, 5715-5725 (2022).
Interaction between nanoparticles (NPs) and a layer of grafted and solvated polymer molecules has been widely explored for a variety of applications ranging from fabrication of nanocomposites and sensors to developing nanocoating for virus deactivation. In all of these applications, the solvated polymer molecules are necessarily philic to the NPs, and consequently, driven by the favorable NP-polymer interactions, there is the formation of numerous stable direct (i.e., without any intervening solvent molecule) NP-monomer (monomer of the polymer) contact pairs. In this paper, we propose a paradigm shift in this problem: we employ molecular dynamics (MD) simulations and establish that under appropriate conditions, it is possible to develop numerous stable direct contacts between a NP and a solvated polymer layer even when the polymer molecules are extremely phobic to the NP. Here, by "stable" contacts, we refer to the NP-Polymer contacts that remain intact for a finite duration of time; of course, such contacts, after being intact for a finite time duration, might get broken and reformed. In terms of the mechanism of the process, the NP is driven inside a grafted layer of collapsed (in the absence of solvent) and phobic (to the NP) polymer molecules by a liquid drop (polymer is philic to the liquid). Subsequently, the liquid molecules imbibe and diffuse inside the polymer layer, but the NPs, due to the large steric effect imposed by the polymer molecules, remain localized within the polymer layer. This ensures the establishment of several stable direct contacts between the NP and the highly phobic polymer molecules. We quantify these contacts by their numbers, stability, and frequency of occurrences as well as their dependences on the NP-polymer interaction energies and NP sizes. We also quantify the associated NP dynamics inside the polymeric layer. Finally, we argue that our finding will open up avenues for leveraging NP-polymer interactions for a myriad of applications even for cases where the polymer molecules are phobic to the NPs.
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