TY - JOUR

T1 - Molecular thermodynamic modeling of self-assembly into branches and spatial networks in solution

AU - Emelyanova, Ksenia

AU - Gotlib, Igor

AU - Shishkina, Anna

AU - Voznesenskiy, Michail

AU - Victorov, Alexey

N1 - Publisher Copyright: © 2016 American Chemical Society. Copyright: Copyright 2017 Elsevier B.V., All rights reserved.

PY - 2016/9/30

Y1 - 2016/9/30

N2 - Molecular-thermodynamic models are applied to network-forming systems of three types: (1) wormlike micelles of ionic surfactant, (2) water + oil + surfactant mixtures, and (3) mixtures of reversibly associating chainlike molecules. For ionic surfactants, we illustrate the stabilization mechanism for the bilayer perforation that has a toroidal rim and describe the sequence of shape transitions induced by adding salt, including formation of bicontinuous structures and branched versus nonbranched wormlike micelles. For both ionic and nonionic surfactants, we show the zones of stable perforated bilayers and stable branched structures in an extended state diagram of a microemulsion derived from the Helfrich-Safran curvature expansion. For mixtures of reversibly associating sticky chains, our molecular dynamic (MD) simulations demonstrate crowding: an enhancement of association caused by the presence of chains that carry nonsticky monomers. An easy-to-use mean-field correction to the apparent association constant gives a good prediction of this effect. For an equilibrium physical gel formed by sticky chains, our MD data show large presence of cyclic structures.

AB - Molecular-thermodynamic models are applied to network-forming systems of three types: (1) wormlike micelles of ionic surfactant, (2) water + oil + surfactant mixtures, and (3) mixtures of reversibly associating chainlike molecules. For ionic surfactants, we illustrate the stabilization mechanism for the bilayer perforation that has a toroidal rim and describe the sequence of shape transitions induced by adding salt, including formation of bicontinuous structures and branched versus nonbranched wormlike micelles. For both ionic and nonionic surfactants, we show the zones of stable perforated bilayers and stable branched structures in an extended state diagram of a microemulsion derived from the Helfrich-Safran curvature expansion. For mixtures of reversibly associating sticky chains, our molecular dynamic (MD) simulations demonstrate crowding: an enhancement of association caused by the presence of chains that carry nonsticky monomers. An easy-to-use mean-field correction to the apparent association constant gives a good prediction of this effect. For an equilibrium physical gel formed by sticky chains, our MD data show large presence of cyclic structures.

UR - http://www.scopus.com/inward/record.url?scp=85035202071&partnerID=8YFLogxK

U2 - 10.1021/acs.jced.6b00531

DO - 10.1021/acs.jced.6b00531

M3 - Article

AN - SCOPUS:85035202071

VL - 61

SP - 4013

EP - 4022

JO - Journal of Chemical & Engineering Data

JF - Journal of Chemical & Engineering Data

SN - 0021-9568

IS - 12

ER -