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Influence of polymer flexibility on nanoparticle dynamics in semidilute solutions

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Abstract

The hierarchical structure and dynamics of polymer solutions control the transport of nanoparticles (NPs) through them. Here, we perform multi-particle collision dynamics simulations of solutions of semiflexible polymer chains with tunable persistence length lp to investigate the effect of chain stiffness on NP transport. The NPs exhibit two distinct dynamical regimes – subdiffusion on short time scales and diffusion on long time scales. The long-time NP diffusivities are compared with predictions from the Stokes–Einstein relation (SER), mode-coupling theory (MCT), and a recent polymer coupling theory (PCT). Increasing deviations from the SER as the polymer chains become more rigid (i.e. as lp increases) indicate that the NP motions become decoupled from the bulk viscosity of the polymer solution. Likewise, polymer stiffness leads to deviations from PCT, which was developed for fully flexible chains. Independent of lp, however, the long-time diffusion behavior is well-described by MCT, particularly at high polymer concentration. We also observed that the short-time subdiffusive dynamics are strongly dependent on polymer flexibility. As lp is increased, the NP dynamics become more subdiffusive and decouple from the dynamics of the polymer chain center-of-mass. We posit that these effects are due to differences in the segmental mobility of the semiflexible chains.

Graphical abstract: Influence of polymer flexibility on nanoparticle dynamics in semidilute solutions

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Publication details

The article was received on 08 Sep 2018, accepted on 07 Nov 2018 and first published on 08 Nov 2018


Article type: Paper
DOI: 10.1039/C8SM01834K
Citation: Soft Matter, 2019, Advance Article
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    Influence of polymer flexibility on nanoparticle dynamics in semidilute solutions

    R. Chen, R. Poling-Skutvik, M. P. Howard, A. Nikoubashman, S. A. Egorov, J. C. Conrad and J. C. Palmer, Soft Matter, 2019, Advance Article , DOI: 10.1039/C8SM01834K

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