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Coarsening Kinetics of Complex Macromolecular Architectures in Bad Solvent

This study reports a general scenario for the out-of-equilibrium features of collapsing polymeric architectures. We use molecular dynamics simulations to characterize the coarsening kinetics, in bad solvent, for several macromolecular systems with an increasing degree of structural complexity. In pa...

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Autores principales: Paciolla, Mariarita, Arismendi-Arrieta, Daniel J., Moreno, Angel J.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7182883/
https://www.ncbi.nlm.nih.gov/pubmed/32121665
http://dx.doi.org/10.3390/polym12030531
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author Paciolla, Mariarita
Arismendi-Arrieta, Daniel J.
Moreno, Angel J.
author_facet Paciolla, Mariarita
Arismendi-Arrieta, Daniel J.
Moreno, Angel J.
author_sort Paciolla, Mariarita
collection PubMed
description This study reports a general scenario for the out-of-equilibrium features of collapsing polymeric architectures. We use molecular dynamics simulations to characterize the coarsening kinetics, in bad solvent, for several macromolecular systems with an increasing degree of structural complexity. In particular, we focus on: flexible and semiflexible polymer chains, star polymers with 3 and 12 arms, and microgels with both ordered and disordered networks. Starting from a powerful analogy with critical phenomena, we construct a density field representation that removes fast fluctuations and provides a consistent characterization of the domain growth. Our results indicate that the coarsening kinetics presents a scaling behaviour that is independent of the solvent quality parameter, in analogy to the time–temperature superposition principle. Interestingly, the domain growth in time follows a power-law behaviour that is approximately independent of the architecture for all the flexible systems; while it is steeper for the semiflexible chains. Nevertheless, the fractal nature of the dense regions emerging during the collapse exhibits the same scaling behaviour for all the macromolecules. This suggests that the faster growing length scale in the semiflexible chains originates just from a faster mass diffusion along the chain contour, induced by the local stiffness. The decay of the dynamic correlations displays scaling behavior with the growing length scale of the system, which is a characteristic signature in coarsening phenomena.
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spelling pubmed-71828832020-05-01 Coarsening Kinetics of Complex Macromolecular Architectures in Bad Solvent Paciolla, Mariarita Arismendi-Arrieta, Daniel J. Moreno, Angel J. Polymers (Basel) Article This study reports a general scenario for the out-of-equilibrium features of collapsing polymeric architectures. We use molecular dynamics simulations to characterize the coarsening kinetics, in bad solvent, for several macromolecular systems with an increasing degree of structural complexity. In particular, we focus on: flexible and semiflexible polymer chains, star polymers with 3 and 12 arms, and microgels with both ordered and disordered networks. Starting from a powerful analogy with critical phenomena, we construct a density field representation that removes fast fluctuations and provides a consistent characterization of the domain growth. Our results indicate that the coarsening kinetics presents a scaling behaviour that is independent of the solvent quality parameter, in analogy to the time–temperature superposition principle. Interestingly, the domain growth in time follows a power-law behaviour that is approximately independent of the architecture for all the flexible systems; while it is steeper for the semiflexible chains. Nevertheless, the fractal nature of the dense regions emerging during the collapse exhibits the same scaling behaviour for all the macromolecules. This suggests that the faster growing length scale in the semiflexible chains originates just from a faster mass diffusion along the chain contour, induced by the local stiffness. The decay of the dynamic correlations displays scaling behavior with the growing length scale of the system, which is a characteristic signature in coarsening phenomena. MDPI 2020-03-02 /pmc/articles/PMC7182883/ /pubmed/32121665 http://dx.doi.org/10.3390/polym12030531 Text en © 2020 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Paciolla, Mariarita
Arismendi-Arrieta, Daniel J.
Moreno, Angel J.
Coarsening Kinetics of Complex Macromolecular Architectures in Bad Solvent
title Coarsening Kinetics of Complex Macromolecular Architectures in Bad Solvent
title_full Coarsening Kinetics of Complex Macromolecular Architectures in Bad Solvent
title_fullStr Coarsening Kinetics of Complex Macromolecular Architectures in Bad Solvent
title_full_unstemmed Coarsening Kinetics of Complex Macromolecular Architectures in Bad Solvent
title_short Coarsening Kinetics of Complex Macromolecular Architectures in Bad Solvent
title_sort coarsening kinetics of complex macromolecular architectures in bad solvent
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7182883/
https://www.ncbi.nlm.nih.gov/pubmed/32121665
http://dx.doi.org/10.3390/polym12030531
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