title: Fructose-water-dimethylsulfoxide interactions by vibrational spectroscopy and molecular dynamics simulations.
abstract: The solvation of fructose in dimethyl sulfoxide (DMSO) and DMSO-H(2)O (or DMSO-D(2)O) mixtures was investigated using vibrational spectroscopy (Raman, ATR/FTIR) and molecular dynamics (MD) simulations. The analysis of the fructose hydroxyl hydrogen-DMSO oxygen radial distribution function showed that the coordination number of DMSO around the furanose form of fructose is ~3.5. This number is smaller than the number of hydroxyl groups of fructose because one DMSO molecule is shared between two hydroxyl groups and because intramolecular hydrogen bonds are formed. In the case of fructose-DMSO mixtures, a red shift of the Raman S═O asymmetric stretch is observed, which indicates that fructose breaks the DMSO clusters through strong hydrogen bonding between the hydrogen atoms of its hydroxyl groups and the oxygen atom of DMSO. The Raman scattering cross sections of the DMSO S═O stretch when a DMSO molecule interacts with another DMSO molecule, a fructose molecule, or a water molecule were estimated from the spectra of the binary mixtures using the coordination numbers from MD simulations. It was also possible to use these values together with the MD-estimated coordination numbers to satisfactorily predict the effect of the water fraction on the Raman scattering intensity of the S═O stretching band in ternary mixtures. MD simulations also showed that, with increasing water content, the DMSO orientation around fructose changed, with the sulfur atom moving away from the carbohydrate. The deconvolution of the fructose IR OH stretching region revealed that the hydroxyls of fructose can be separated into two groups that participate in hydrogen bonds of different strengths. MD simulations showed that the three hydroxyls of the fructose ring form stronger hydrogen bonds with the solvent than the remaining hydroxyls, providing an explanation for the experimental observations. Finally, analysis of ATR/FTIR spectra revealed that, with increasing water content, the average hydrogen-bond enthalpy of the fructose hydroxyls decreases by ~2.5 kJ/mol.
authors.affiliation: Department of Chemical and Biomolecular Engineering, Catalysis Center for Energy Innovation, University of Delaware, 150 Academy Street, Newark, Delaware 19716, USA. vlad@udel.edu
authors.forename: Vladimiros
authors.initials: V
authors.lastname: Nikolakis
authors.forename: Samir H
authors.initials: SH
authors.lastname: Mushrif
authors.forename: Bryon
authors.initials: B
authors.lastname: Herbert
authors.forename: Karl S
authors.initials: KS
authors.lastname: Booksh
authors.forename: Dionisios G
authors.initials: DG
authors.lastname: Vlachos
mesh_terms: D004121:Dimethyl Sulfoxide / Q000737:chemistry*; D005632:Fructose / Q000737:chemistry*; D006860:Hydrogen Bonding; D056004:Molecular Dynamics Simulation; D017550:Spectroscopy, Fourier Transform Infrared; D013059:Spectrum Analysis, Raman; D014867:Water / Q000737:chemistry*
chemical_list: D014867:Water; D005632:Fructose; D004121:Dimethyl Sulfoxide