Salting-in of neopentane in the aqueous solutions of urea and glycine-betaine

Abstract

The effects of urea and glycine-betaine (GB) osmolytes on the hydrophobic interactions of neopentane in water have been studied using molecular dynamics simulations. From the study of the potentials of mean force, it is observed that both urea and GB decrease the association and solvation of neopentane. The calculated equilibrium constants show that urea and GB decrease the population of solvent-separated minima of neopentane. The hydrophobic association as well as solvation of neopentane molecules are stabilised by entropy and enthalpy in the mixtures. The radial distribution functions (RDFs) and running coordination numbers of water, urea and GB molecules show that neopentane shows salting-in behaviour in aqueous-GB, aqueous-urea and aqueous-urea-GB mixtures. Neopentane is preferentially solvated by GB in aqueous-GB and preferentially solvated by urea in aqueous-urea-GB solutions. The preferential solvation of neopentane by GB suggests that GB decreases the interaction between neopentane molecules i.e. salting-in of neopentane. The calculated solvation free energies and radial density profiles of neopentane also support the salting-in behaviour of neopentane in the mixtures of these osmolytes.

Keywords:

• Osmolytes
• hydrophobic interactions
• potentials of mean force (PMFs)
• preferential solvation
• running coordination numbers

Acknowledgements

We would like to express our gratitude to IIT Bombay for providing us with the High Performance Computing Facility and the Department of Chemistry, IIT Bombay for providing research facilities. Manjunath D. Meti thanks IITB, for a Post Doctoral Fellowship. MD thanks UGC fellowship, government of India.