Local structure of dilute aqueous DMSO solutions, as seen from molecular dynamics simulations

Abdenacer Idrissi, Bogdan A. Marekha, Mohammed Barj, François Alexandre Miannay, Toshiyuki Takamuku, Vasilios Raptis, Jannis Samios, P. Jedlovszky

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

The information about the structure of dimethyl sulfoxide (DMSO)-water mixtures at relatively low DMSO mole fractions is an important step in order to understand their cryoprotective properties as well as the solvation process of proteins and amino acids. Classical MD simulations, using the potential model combination that best reproduces the free energy of mixing of these compounds, are used to analyze the local structure of DMSO-water mixtures at DMSO mole fractions below 0.2. Significant changes in the local structure of DMSO are observed around the DMSO mole fraction of 0.1. The array of evidence, based on the cluster and the metric and topological parameters of the Voronoi polyhedra distributions, indicates that these changes are associated with the simultaneous increase of the number of DMSO-water and decrease of water-water hydrogen bonds with increasing DMSO concentration. The inversion between the dominance of these two types of H-bonds occurs around XDMSO = 0.1, above which the DMSO-DMSO interactions also start playing an important role. In other words, below the DMSO mole fraction of 0.1, DMSO molecules are mainly solvated by water molecules, while above it, their solvation shell consists of a mixture of water and DMSO. The trigonal, tetrahedral, and trigonal bipyramidal distributions of water shift to lower corresponding order parameter values indicating the loosening of these orientations. Adding DMSO does not affect the hydrogen bonding between a reference water molecule and its first neighbor hydrogen bonded water molecules, while it increases the bent hydrogen bond geometry involving the second ones. The close-packed local structure of the third, fourth, and fifth water neighbors also is reinforced. In accordance with previous theoretical and experimental data, the hydrogen bonding between water and the first, the second, and the third DMSO neighbors is stronger than that with its corresponding water neighbors. At a given DMSO mole fraction, the behavior of the intensity of the high orientational order parameter values indicates that water molecules are more ordered in the vicinity of the hydrophilic group while their structure is close-packed near the hydrophobic group of DMSO.

Original languageEnglish
Article number234507
JournalJournal of Chemical Physics
Volume146
Issue number23
DOIs
Publication statusPublished - Jun 21 2017

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Dimethyl Sulfoxide
Molecular dynamics
molecular dynamics
Computer simulation
Water
water
simulation
Hydrogen bonds
Molecules
molecules
Solvation
solvation
hydrogen
hydrogen bonds
polyhedrons
amino acids
Free energy
free energy

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Local structure of dilute aqueous DMSO solutions, as seen from molecular dynamics simulations. / Idrissi, Abdenacer; Marekha, Bogdan A.; Barj, Mohammed; Miannay, François Alexandre; Takamuku, Toshiyuki; Raptis, Vasilios; Samios, Jannis; Jedlovszky, P.

In: Journal of Chemical Physics, Vol. 146, No. 23, 234507, 21.06.2017.

Research output: Contribution to journalArticle

Idrissi, A, Marekha, BA, Barj, M, Miannay, FA, Takamuku, T, Raptis, V, Samios, J & Jedlovszky, P 2017, 'Local structure of dilute aqueous DMSO solutions, as seen from molecular dynamics simulations', Journal of Chemical Physics, vol. 146, no. 23, 234507. https://doi.org/10.1063/1.4985630
Idrissi A, Marekha BA, Barj M, Miannay FA, Takamuku T, Raptis V et al. Local structure of dilute aqueous DMSO solutions, as seen from molecular dynamics simulations. Journal of Chemical Physics. 2017 Jun 21;146(23). 234507. https://doi.org/10.1063/1.4985630
Idrissi, Abdenacer ; Marekha, Bogdan A. ; Barj, Mohammed ; Miannay, François Alexandre ; Takamuku, Toshiyuki ; Raptis, Vasilios ; Samios, Jannis ; Jedlovszky, P. / Local structure of dilute aqueous DMSO solutions, as seen from molecular dynamics simulations. In: Journal of Chemical Physics. 2017 ; Vol. 146, No. 23.
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