Enhanced chemical synthesis at soft interfaces: a universal reaction-adsorption mechanism in microcompartments

Phys Rev Lett. 2014 Jan 17;112(2):028301. doi: 10.1103/PhysRevLett.112.028301. Epub 2014 Jan 13.

Abstract

A bimolecular synthetic reaction (imine synthesis) was performed compartmentalized in micrometer-diameter emulsion droplets. The apparent equilibrium constant (Keq) and apparent forward rate constant (k1) were both inversely proportional to the droplet radius. The results are explained by a noncatalytic reaction-adsorption model in which reactants adsorb to the droplet interface with relatively low binding energies of a few kBT, react and diffuse back to the bulk. Reaction thermodynamics is therefore modified by compartmentalization at the mesoscale--without confinement on the molecular scale--leading to a universal mechanism for improving unfavorable reactions.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Adsorption
  • Aldehydes / chemistry
  • Amines / chemistry
  • Chemistry, Organic / instrumentation
  • Chemistry, Organic / methods*
  • Diffusion
  • Imines / chemical synthesis*
  • Imines / chemistry
  • Kinetics
  • Models, Chemical*
  • Surface Properties
  • Thermodynamics

Substances

  • Aldehydes
  • Amines
  • Imines