Receptacle model of salting-in by tetramethylammonium ions

J Phys Chem B. 2010 Nov 25;114(46):15085-91. doi: 10.1021/jp108052r. Epub 2010 Oct 28.

Abstract

Water is a poor solvent for nonpolar solutes. Water containing ions is an even poorer solvent. According to standard terminology, the tendency of salts to precipitate oils from water is called salting-out. However, interestingly, some salt ions, such as tetramethylammonium (TMA), cause instead the salting-in of hydrophobic solutes. Even more puzzling, there is a systematic dependence on solute size. TMA causes the salting-out of small hydrophobes and the salting-in of larger nonpolar solutes. We study these effects using NPT Monte Carlo simulations of the Mercedes-Benz (MB) + dipole model of water, which was previously shown to account for hydrophobic effects and ion solubilities in water. The present model gives a structural interpretation for the thermodynamics of salting-in. The TMA structure allows deep penetration by a first shell of waters, the dipoles of which interact electrostatically with the ion. This first water shell sets up a second water shell that is shaped to act as a receptacle that binds the nonpolar solute. In this way, a nonpolar solute can actually bind more tightly to the TMA ion than to another hydrophobe, leading to the increased solubility and salting-in. Such structuring may also explain why molecular ions do not follow the same charge density series as atomic ions do.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't

MeSH terms

  • Computer Simulation
  • Hydrophobic and Hydrophilic Interactions
  • Ions / chemistry*
  • Monte Carlo Method
  • Quaternary Ammonium Compounds / chemistry*
  • Salts / chemistry*
  • Solutions / chemistry
  • Solvents / chemistry
  • Thermodynamics

Substances

  • Ions
  • Quaternary Ammonium Compounds
  • Salts
  • Solutions
  • Solvents
  • tetramethylammonium