title: The role of water coordination in binary mixtures. A study of two model amphiphilic molecules in aqueous solutions by molecular dynamics and NMR.
abstract: Two binary aqueous mixtures which contain the small amphiphilic molecules TMAO (trimethylamine-N-oxide) and TBA (tert-butyl alcohol) have been investigated by molecular dynamics simulations and NMR chemical shift and self-diffusion measurements. TMAO is an osmolyte, while TBA is a monohydrate alcohol. Both possess bulky hydrophobic groups and polar heads, namely, NO in TMAO and OH in TBA. The hydrophilic/hydrophobic content of these isosteric molecules strongly modulates the structure and dynamics of the hydration shell, which is thought to be responsible for the effects observed on proteins and phospholipids. Simulation results, especially on hydrogen-bond networking, spatial correlations, and self-diffusivity, are consistent with NMR data and agree well with previous numerical studies on similar solutions. The methods employed allow the elucidation of the microscopic features of the solutions. For TBA solutions, the hydration shell is found to have a low density and a large spatial spread, and thus, above the molar fraction of 0.03, reduction of hydrophobic hydration drives self-aggregation of the solute. This effect does not take place in TMAO solutions, where the hydration shell is more compact and stable, maintaining its structure over a wider range of solute concentrations.
authors.affiliation: SOFT-INFM-CNR Research Center and Dipartimento di Fisica, Università La Sapienza, I-00185 Roma, Italy.
authors.forename: R
authors.initials: R
authors.lastname: Sinibaldi
authors.forename: C
authors.initials: C
authors.lastname: Casieri
authors.forename: S
authors.initials: S
authors.lastname: Melchionna
authors.forename: G
authors.initials: G
authors.lastname: Onori
authors.forename: A L
authors.initials: AL
authors.lastname: Segre
authors.forename: S
authors.initials: S
authors.lastname: Viel
authors.forename: L
authors.initials: L
authors.lastname: Mannina
authors.forename: F
authors.initials: F
authors.lastname: De Luca
mesh_terms: D003198:Computer Simulation; D009682:Magnetic Resonance Spectroscopy / Q000379:methods* / Q000592:standards; D008744:Methylamines / Q000737:chemistry*; D008956:Models, Chemical; D012015:Reference Standards; D012680:Sensitivity and Specificity; D012996:Solutions / Q000737:chemistry; D013501:Surface-Active Agents / Q000737:chemistry*; D014867:Water / Q000737:chemistry; D020002:tert-Butyl Alcohol / Q000737:chemistry*
chemical_list: D008744:Methylamines; D012996:Solutions; D013501:Surface-Active Agents; D014867:Water; C005855:trimethyloxamine; D020002:tert-Butyl Alcohol