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A cosolvent surfactant mechanism affects polymer collapse in miscible good solvents

Bharadwaj, Swaminath ; Nayar, Divya ; Dalgicdir, Cahit ; Vegt, Nico F. A. van der (2020)
A cosolvent surfactant mechanism affects polymer collapse in miscible good solvents.
In: Communications Chemistry, 3 (1)
doi: 10.1038/s42004-020-00405-x
Artikel, Bibliographie

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Kurzbeschreibung (Abstract)

The coil–globule transition of aqueous polymers is of profound significance in understanding the structure and function of responsive soft matter. In particular, the remarkable effect of amphiphilic cosolvents (e.g., alcohols) that leads to both swelling and collapse of stimuli-responsive polymers has been hotly debated in the literature, often with contradictory mechanisms proposed. Using molecular dynamics simulations, we herein demonstrate that alcohols reduce the free energy cost of creating a repulsive polymer–solvent interface via a surfactant-like mechanism which surprisingly drives polymer collapse at low alcohol concentrations. This hitherto neglected role of interfacial solvation thermodynamics is common to all coil–globule transitions, and rationalizes the experimentally observed effects of higher alcohols and polymer molecular weight on the coil-to-globule transition of thermoresponsive polymers. Polymer–(co)solvent attractive interactions reinforce or compensate this mechanism and it is this interplay which drives polymer swelling or collapse.

Typ des Eintrags: Artikel
Erschienen: 2020
Autor(en): Bharadwaj, Swaminath ; Nayar, Divya ; Dalgicdir, Cahit ; Vegt, Nico F. A. van der
Art des Eintrags: Bibliographie
Titel: A cosolvent surfactant mechanism affects polymer collapse in miscible good solvents
Sprache: Englisch
Publikationsjahr: 11 November 2020
Ort: London
Verlag: Springer Nature
Titel der Zeitschrift, Zeitung oder Schriftenreihe: Communications Chemistry
Jahrgang/Volume einer Zeitschrift: 3
(Heft-)Nummer: 1
Kollation: 7 Seiten
DOI: 10.1038/s42004-020-00405-x
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Kurzbeschreibung (Abstract):

The coil–globule transition of aqueous polymers is of profound significance in understanding the structure and function of responsive soft matter. In particular, the remarkable effect of amphiphilic cosolvents (e.g., alcohols) that leads to both swelling and collapse of stimuli-responsive polymers has been hotly debated in the literature, often with contradictory mechanisms proposed. Using molecular dynamics simulations, we herein demonstrate that alcohols reduce the free energy cost of creating a repulsive polymer–solvent interface via a surfactant-like mechanism which surprisingly drives polymer collapse at low alcohol concentrations. This hitherto neglected role of interfacial solvation thermodynamics is common to all coil–globule transitions, and rationalizes the experimentally observed effects of higher alcohols and polymer molecular weight on the coil-to-globule transition of thermoresponsive polymers. Polymer–(co)solvent attractive interactions reinforce or compensate this mechanism and it is this interplay which drives polymer swelling or collapse.

Freie Schlagworte: Chemical physics, Polymers
ID-Nummer: Artikel-ID: 165
Sachgruppe der Dewey Dezimalklassifikatin (DDC): 500 Naturwissenschaften und Mathematik > 540 Chemie
Fachbereich(e)/-gebiet(e): 07 Fachbereich Chemie
07 Fachbereich Chemie > Eduard Zintl-Institut
07 Fachbereich Chemie > Eduard Zintl-Institut > Fachgebiet Physikalische Chemie
Hinterlegungsdatum: 26 Sep 2024 07:35
Letzte Änderung: 26 Sep 2024 07:35
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