TY - JOUR

T1 - Association Equilibrium for Cross-Associating Chains in a Good Solvent: Crowding and Other Nonideality Effects

AU - Gotlib, Igor Yu.

AU - Malov, Ivan K.

AU - Victorov, Alexey I.

AU - Voznesenskiy, Mikhail A.

PY - 2016

Y1 - 2016

N2 - Association equilibrium has been studied by molecular dynamics (MD) for mixtures of cross-associating molecules (n-decamer+p-dimer and n-decamer+p-decamer) in a good solvent. Each monomer of n-decamers carries an associative site (n-sticker); each molecule of the second component contains two terminal associative sites (p-stickers). To model the univalent association between the n-sticker and the p-sticker, a technique based on introduction of dummy atoms has been used. We report MD data on the effects of temperature, chain flexibility, and location of the sticker within the chain on the association equilibrium. We find that the presence of nonassociating monomer units of p-chain has a substantial effect on the association equilibrium. This effect is similar to “crowding” in reactive mixtures known to be caused by the presence of inert molecules. Widely used mean field theories of associating chains (e.g., SAFT or Semenov–Rubinstein theory) do not account for the effect of crowding caused by the inert fragmen

AB - Association equilibrium has been studied by molecular dynamics (MD) for mixtures of cross-associating molecules (n-decamer+p-dimer and n-decamer+p-decamer) in a good solvent. Each monomer of n-decamers carries an associative site (n-sticker); each molecule of the second component contains two terminal associative sites (p-stickers). To model the univalent association between the n-sticker and the p-sticker, a technique based on introduction of dummy atoms has been used. We report MD data on the effects of temperature, chain flexibility, and location of the sticker within the chain on the association equilibrium. We find that the presence of nonassociating monomer units of p-chain has a substantial effect on the association equilibrium. This effect is similar to “crowding” in reactive mixtures known to be caused by the presence of inert molecules. Widely used mean field theories of associating chains (e.g., SAFT or Semenov–Rubinstein theory) do not account for the effect of crowding caused by the inert fragmen

U2 - 10.1021/acs.jpcb.5b12530

DO - 10.1021/acs.jpcb.5b12530

M3 - Article

VL - 120

SP - 7234

EP - 7243

JO - Journal of Physical Chemistry B

JF - Journal of Physical Chemistry B

SN - 1520-6106

IS - 29

ER -