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Kosmotropic effect leads to LCST decrease in thermoresponsive polymer solutions.

Swaminath Bharadwaj1, P B Sunil Kumar2, Shigeyuki Komura3

  • 1Department of Chemical Engineering, Indian Institute of Technology Madras, Chennai 600036, India.

The Journal of Chemical Physics
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Summary
This summary is machine-generated.

Adding kosmotropic cosolvents decreases the lower critical solution temperature (LCST) in polymer solutions by reducing solvent energy. This effect lessens with increased polymer hydrophilicity, explaining LCST behavior in specific systems.

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Area of Science:

  • Physical Chemistry
  • Polymer Science
  • Computational Chemistry

Background:

  • Thermoresponsive polymers exhibit a lower critical solution temperature (LCST), a key characteristic for their applications.
  • Understanding the influence of cosolvents on polymer solution thermodynamics is crucial for material design.

Purpose of the Study:

  • To investigate the mechanism behind the decrease in LCST upon addition of kosmotropic cosolvents.
  • To elucidate the role of polymer hydrophilicity in modulating the cosolvent effect on LCST.

Main Methods:

  • Employed explicit solvent coarse-grained simulations.
  • Utilized mean-field theory with the Kolomeisky-Widom solvophobic potential.
  • Analyzed the energetic contributions of polymer-solvent and solvent-solvent interactions.

Main Results:

  • Demonstrated that reduced bulk solvent energy, induced by cosolvents, drives the decrease in LCST.
  • Quantified the diminished impact of cosolvents on LCST with increasing polymer hydrophilicity.
  • Explained the absence of LCST decrease in specific polymer-water-methanol systems.

Conclusions:

  • A mean energetic representation is sufficient to understand LCST decrease phenomena in polymer solutions.
  • The study provides insights into tuning polymer solution behavior through cosolvent addition.
  • Findings contribute to the rational design of advanced thermoresponsive materials.