• Vkontakte Social Icon
  • Иконка facebook черного цвета

Chair of Polymer and Crystal Physics, Physics Department, Moscow State University

Laboratory of Microstructured Polymer Systems

Copolymerization on Selective Substrates: Experimental Test and Computer Simulations

Langmuir, 33, (2017), pp. 3548-3555

E.Yu.Kozhunova, A.A.Gavrilov, M.Yu.Zaremski, A.V.Chertovich

We explore the influence of a selective substrate on the composition and sequence statistics during the free radical copolymerization. In particular, we study the radical copolymerization of styrene and acrylic acid in bulk and in silica pores of different sizes. We show that the substrate affects both polymer composition and sequence statistics. We use dissipative particle dynamics simulations to study the polymerization process in detail, trying to pinpoint the parameters responsible for the observed differences in the polymer chain composition and sequences. The magnitude of the observed effect depends on the fraction of adsorbed monomer units, which cannot be described in the framework of the copolymerization theories based on the terminal unit model.

DOI: 10.1021/acs.langmuir.7b00406

Synthesis of amphiphilic copolymers based on acrylic acid, fluoroalkyl acrylates and n-butyl acrylate in organic, aqueous–organic, and aqueous media via RAFT polymerization

RSC advances, 7, (2017), pp. 24522-24536

N.S.Serkhacheva, O.I.Smirnov, A.V.Tolkachev, N.I.Prokopov, A.V.Plutalova, E.V.Chernikova, E.Yu.Kozhunova, A.R.Khokhlov

Amphiphilic narrow dispersed copolymers of acrylic acid and fluoroalkyl acrylates are synthesized via reversible addition–fragmentation chain transfer (RAFT) polymerization using dibenzyl trithiocarbonate in DMF solution. These copolymers and polyacrylic acid containing the trithiocarbonate group within the polymeric chain are used for the synthesis of triblock copolymers in organic, aqueous–organic or aqueous media by chain extension with n-butyl acrylate or its mixture with fluoroalkyl acrylates. Both dispersion polymerization and emulsifier-free emulsion polymerization lead to self-assembling of triblock copolymers in the core–shell particles; the former route provides the formation of microstructured polymer films with a percolated structure.

DOI: 10.1039/c7ra03203j

Electrode/Electrolyte Interface in the Li–O2 Battery: Insight from Molecular Dynamics Study

Journal of Physical Chemistry C, 121 (27), (2017), pp 14463–14469

A.V.Sergeev, A.V. Chertovich, D.M. Itkis, A. Sen, A. Gross, A.R. Khokhlov

In this paper, for the first time, we report the results of molecular dynamics simulation of the electrode/electrolyte interface of a Li–O2 cathode under potentials close to experimental values in 1 M dimethyl sulfoxide (DMSO) solution of LiPF6 salt. Electric potential profiles, solvent structuring near the electrode surface, and salt ion distributions are presented and discussed here as well as potentials of mean force (PMFs) of oxygen and its reduction products. 

DOI: 10.1021/acs.jpcc.7b03861

Copolymerization of Partly Incompatible Monomers: An Insight from Computer Simulations

Macromolecules, 50(12), (2017), pp 4677–4685

A.A. Gavrilov, A.V. Chertovich

We used dissipative particle dynamics simulations to study the copolymerization process in the presence of spatial heterogeneities caused by incompatibility between polymerizing monomers. We performed the model verification with the available literature data on styrene–acrylic acid copolymerization in the bulk, and a very good agreement between experimental and simulated data for both chain average composition and triad fractions was observed. Next, we studied the system properties for five model AB reaction processes with different sets of reactivity ratios at different compositions and Flory–Huggins parameters χ. 

DOI: 10.1021/acs.macromol.7b00180

Complex Curing Pathways and Their Influence on the Phthalonitrile Resin Hardening and Elasticity

Macromolecular Theory and Simulations, 26 (2017), 1700015

V.Yu. Rudyak, A.A. Gavrilov, D.V. Guseva, A.V. Chertovich

Phthalonitrile compounds with siloxane bridges are recently suggested for producing thermosetting polymer composites with expanded processing range, excellent mechanical properties, and increased thermo-oxidative stability. Mesoscale chemistry concept is adopted to describe multipathway curing process in phthalonitriles by adding triple link (triazine) formation into chemical reactions scheme. Coarse-grained dissipative particle dynamics simulations have shown significant changes in matrix topology and mechanical properties with increase of the triazine reaction rate. In contrast to typical changes induced by high functionality crosslinkers, matrices with high content of triazine reach higher conversion degree, are less topologically interconnected, and are softer than ones without triazine.

DOI: 10.1002/mats.201700015

Copolymerization on Selective Substrates: Experimental Test and Computer Simulations

Langmuir, 33 (14), 2017, pp 3548–3555

E.Yu. Kozhunova , A.A. GavrilovM.Yu. Zaremski, and A.V. Chertovich

We explore the influence of a selective substrate on the composition and sequence statistics during the free radical copolymerization. In particular, we study the radical copolymerization of styrene and acrylic acid in bulk and in silica pores of different sizes. We show that the substrate affects both polymer composition and sequence statistics. We use dissipative particle dynamics simulations to study the polymerization process in detail, trying to pinpoint the parameters responsible for the observed differences in the polymer chain composition and sequences. The magnitude of the observed effect depends on the fraction of adsorbed monomer units, which cannot be described in the framework of the copolymerization theories based on the terminal unit model.

DOI: 10.1021/acs.langmuir.7b00406

Microphase separation in random multiblock copolymers

The Journal of Chemical Physics, 146 (2017), pp.034903

E.N.Govorun, A.V.Chertovich

Microphase separation in random multiblock copolymers is studied with the mean-field theory assuming that long blocks of a copolymer are strongly segregated, whereas short blocks are able to penetrate into “alien” domains and exchange between the domains and interfacial layer. A bidisperse copolymer with blocks of only two sizes (long and short) is considered as a model of multiblock copolymers with high polydispersity in the block size. 

DOI: 10.1063/1.4973933

Features of polyelectrolite behavior and structure of sodium polyacrylamido-2-methyl-1-propanesulfonate cryogels

Polymer, 96, (2016), pp. 1-5

S.G. Starodubtsev, I.R. Nasimova, V.V. Volkov

Specific features of polyelectrolyte behavior and structure of the sodium polyacrylamido-2-methyl-1-propanesulfonate cryogels were studied. The cryogels were synthesized in frozen aqueous solutions at −15°С, the reference gels – at 25°С. It was shown that the polyelectrolyte swelling of cryogels is much weaker than that of gels synthesized in solutions. The ethanol-induced collapse of both gels and cryogels occurs stepwise at similar ethanol concentrations. The high-porosity structure of the cryogels is preserved in the collapsed state. The small-angle X-ray scattering (SAXS) spectra show maxima corresponding to ordered inhomogeneities of 0.5–3.0 nm scale. The positions of the observed maxima depend on the conditions of the synthesis and on the concentration of the polymer in the gels and cryogels.

DOI: 10.1016/j.polymer.2016.04.051

Dissipative particle dynamics for systems with high density of charges: Implementation of electrostatic interactions

Journal of Chemical Physics, 145 (2016), pp. 174101(1–10)

A. A. Gavrilov, A. V. Chertovich, and E. Y. Kramarenko

In this work, we study the question of how to introduce electrostatic interactions in dissipative particle dynamics (DPD) method in order to correctly reproduce the properties of systems with high density of charges, including those with inhomogeneous charge distribution. 

DOI: 10.1063/1.4966149

Active chromatin and transcription play a key role in chromosome partitioning into topologically associating domains

Genome Research, 26 (2016), pp. 70–84

S. Ulianov, E. Khrameeva, A. Gavrilov, I. Flyamer, P. Kos, E. Mikhaleva, A. Penin, M. Logacheva, M. Imakaev, A. Chertovich, M. Gelfand, Y. Shevelyov, and S. Razin

Recent advances enabled by the Hi-C technique have unraveled many principles of chromosomal folding that were subsequently linked to disease and gene regulation. In particular, Hi-C revealed that chromosomes of animals are organized into Topologically Associating Domains (TADs), evolutionary conserved compact chromatin domains that influence gene expression. Mechanisms that underlie partitioning of the genome into TADs remain poorly understood. To explore principles of TAD folding in Drosophila melanogaster, we performed Hi-C and PolyA+ RNA-seq in four cell lines of various origins (S2, Kc167, DmBG3-c2, and OSC).

DOI: 10.1101/gr.196006.115

1 / 4

Please reload