Articles producció científica> Enginyeria Química

Universal Scaling for the Exit Dynamics of Block Copolymers from Micelles at Short and Long Time Scales

  • Identification data

    Identifier: imarina:9244729
  • Authors:

    Pantelidou, Maria S
    Daza, Fabian A Garcia
    Bonet Avalos, Josep
    Mackie, Allan D
  • Others:

    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 / 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: 2024-07-20
    Papper version: info:eu-repo/semantics/publishedVersion
    Link to the original source: https://pubs.acs.org/doi/abs/10.1021/acs.macromol.1c02387
    Funding program: Marie Skłodowska-Curie Actions - European Union's Horizon 2020 research and innovation programme
    Licence document URL: http://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
    Article's DOI: 10.1021/acs.macromol.1c02387
    Entity: Universitat Rovira i Virgili
    Journal publication year: 2022
    Funding program action: Martí i Franquès COFUND Doctoral Programme
    Publication Type: Journal Publications
  • Keywords:

    Inorganic Chemistry,Materials Chemistry,Organic Chemistry,Polymer Science,Polymers and Plastics
    Chain exchange kinetics
    simulation
    relaxation
    polymeric micelles
    model
    micellization
    mean-field theory
    length
    equilibrium
    adsorption
    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
  • Documents:

  • Cerca a google

    Search to google scholar