Author, as appears in the article.: Pantelidou, Maria S; Daza, Fabian A Garcia; Bonet Avalos, Josep; Mackie, Allan D
Department: Enginyeria Química
URV's Author/s: Bonet Avalos, José / GARCIA DAZA, FABIÁN ALONSO / Mackie Walker, Allan Donald / Pantelidou, Maria
Project code: Grant agreement No. 713679
Keywords: Chain exchange kinetics simulation relaxation polymeric micelles model micellization mean-field theory length equilibrium adsorption
Abstract: The correlation function for the exit of poloxamer copolymers from equilibrated micelles is found to show up to four regimes depending on the chain flexibility: an initial fast reorganization, a logarithmic intermediate regime, followed by an exponential intermediate regime, and a final exponential decay. The logarithmic intermediate regime has been observed experimentally and attributed to the polydispersity of the polymer samples. However, we present dynamic single-chain mean-field theory simulations with chains of variable flexibility which show the same logarithmic relaxation but with strictly monodisperse systems. In agreement with our previous studies, we propose that this logarithmic response arises from a degeneracy of energy states of the hydrophobic block in the micelle core. For this to occur, a sufficiently large number of degenerate conformational states are required, which depend on the polymer flexibility and therefore should not be present for rigid polymers. Experimental results for monodisperse polymeric samples claiming the absence of such a logarithmic response may also lack a sufficient number of hydrophobic blocks for the required number of configurational states for this type of response to be seen. The insight gained from analyzing the simulation results allows us to propose a modified Eyring equation capable of reproducing the observed dynamic behavior. On scaling experimental results from different sources and systems according to this equation, we find a unique master curve showing a universal nature of the intermediate regimes: the logarithmic regime together with the secondary exponential decay. The terminal exponential regime at long times proposed by the standard Halperin and Alexander model is beyond the range of the data analyzed in this article. The universality observed suggests an entropic origin of the short-time dynamic response of this class of systems rather than the polydispersity.
Thematic Areas: Química Polymers and plastics Polymer science Organic chemistry Medicina veterinaria Materials chemistry Materiais Interdisciplinar Inorganic chemistry Farmacia Engenharias iii Engenharias ii Ciências biológicas i Biotecnología Astronomia / física
licence for use: https://creativecommons.org/licenses/by/3.0/es/
Author's mail: allan.mackie@urv.cat josep.bonet@urv.cat
Author identifier: 0000-0002-1819-7820 0000-0002-7339-9564
Record's date: 2024-09-28
Papper version: info:eu-repo/semantics/publishedVersion
Funding program: Marie Skłodowska-Curie Actions - European Union's Horizon 2020 research and innovation programme
Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
Papper original source: Macromolecules. 55 (3): 914-927
APA: Pantelidou, Maria S; Daza, Fabian A Garcia; Bonet Avalos, Josep; Mackie, Allan D (2022). Universal Scaling for the Exit Dynamics of Block Copolymers from Micelles at Short and Long Time Scales. Macromolecules, 55(3), 914-927. DOI: 10.1021/acs.macromol.1c02387
Acronym: MFP
Entity: Universitat Rovira i Virgili
Journal publication year: 2022
Funding program action: Martí i Franquès COFUND Doctoral Programme
Publication Type: Journal Publications
Repositori URV