Thermodynamics of hydration of fullerols [C60(OH)n] and hydrogen bond dynamics in their hydration shells

Molecular dynamics simulations of fullerene and fullerols [C60(OH)n, where n = 2–30] in aqueous solutions have been performed for the purpose of obtaining a detailed understanding of the structural and dynamic properties of these nanoparticles in water. The structures, dynamics and hydration free energies of the solute molecules in water have been analysed. Radial distribution functions, spatial density distribution functions and hydrogen bond analyses are employed to characterize the solvation shells of water around the central solute molecules. We have found that water molecules form two solvation shells around the central solute molecule. Hydrogen bonding in the bulk solvent is unaffected by increasing n. The large decrease in solvation enthalpies of these solute molecules for n > 14 enhances solubilisation. The diffusion constants of solute molecules decrease with increasing n. The solvation free energy of C60 in water is positive (52.8 kJ/mol), whereas its value for C60(OH)30 is highly negative (−427.1 kJ/mol). The effects of surface hydroxylation become more dominant once the fullerols become soluble.