Jump to main content
Jump to site search

Issue 31, 2013
Previous Article Next Article

Effects of hydrophobic hydration on polymer chains immersed in supercooled water

Author affiliations

Abstract

A multiscale simulation of a hydrophobic polymer chain immersed in water including the supercooled region is presented. Solvent effects on the polymer conformation were taken into account via liquid–state density functional theory in which a free-energy functional model was constructed using a density response function of bulk water, determined from a molecular dynamics (MD) simulation. This approach overcomes sampling problems in simulations of high-viscosity polymer solutions in the deeply supercooled region. Isobars determined from the MD simulations of 4000 water molecules suggest a liquid–liquid transition in the deeply supercooled region. The multiscale simulation reveals that a hydrophobic polymer chain exhibits swelling upon cooling along isobars below a hypothesized second critical pressure; no remarkable swelling is observed at higher pressures. These observations agree with the behavior of a polymer chain in a Jagla solvent model that qualitatively reproduces the thermodynamics and dynamics of liquid water. A theoretical analysis of the results obtained from the multiscale simulation show that a decrease in entropy due to the swelling arises from the formation of a tetrahedral hydrogen bond network in the hydration shell.

Graphical abstract: Effects of hydrophobic hydration on polymer chains immersed in supercooled water

Back to tab navigation

Publication details

The article was received on 19 Mar 2013, accepted on 03 May 2013 and first published on 07 May 2013


Article type: Paper
DOI: 10.1039/C3RA41320A
RSC Adv., 2013,3, 12743-12750

  •   Request permissions

    Effects of hydrophobic hydration on polymer chains immersed in supercooled water

    T. Sumi and H. Sekino, RSC Adv., 2013, 3, 12743
    DOI: 10.1039/C3RA41320A

Search articles by author

Spotlight

Advertisements