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Issue 45, 2017
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Statistical description of co-nonsolvency suppression at high pressures

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We present an application of Flory-type theory of a flexible polymer chain dissolved in a binary mixture of solvents to theoretical description of co-nonsolvency. We show that our theoretical predictions are in good quantitative agreement with the recently published MD simulation results for the conformational behavior of a Lennard-Jones flexible chain in a binary mixture of the Lennard-Jones fluids. We show that our theory is able to describe co-nonsolvency suppression through pressure enhancement to extremely high values recently discovered in experiments and reproduced by full atomistic MD simulations. By analysing the co-solvent concentration in the internal polymer volume at different pressure values, we speculate that this phenomenon is caused by the suppression of the co-solvent preferential solvation of the polymer backbone at the rather high pressure imposed. We show that when the co-solvent-induced coil–globule transition takes place, the entropy and enthalpy contributions to the solvation free energy abruptly decrease, while the solvation free energy remains continuous.

Graphical abstract: Statistical description of co-nonsolvency suppression at high pressures

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The article was received on 14 Aug 2017, accepted on 25 Oct 2017 and first published on 26 Oct 2017

Article type: Communication
DOI: 10.1039/C7SM01637A
Citation: Soft Matter, 2017,13, 8362-8367
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    Statistical description of co-nonsolvency suppression at high pressures

    Yu. A. Budkov and A. L. Kolesnikov, Soft Matter, 2017, 13, 8362
    DOI: 10.1039/C7SM01637A

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