Enhanced chemical synthesis at soft interfaces: a universal reaction-adsorption mechanism in microcompartments.
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.
Institut de Sciences et d'Ingénierie Supramoléculaires (ISIS), Université de Strasbourg, CNRS UMR 7006, 8 allée Gaspard Monge, F-67083 Strasbourg Cedex, France.
Ali
A
Fallah-Araghi
Institut de Sciences et d'Ingénierie Supramoléculaires (ISIS), Université de Strasbourg, CNRS UMR 7006, 8 allée Gaspard Monge, F-67083 Strasbourg Cedex, France.
Kamel
K
Meguellati
Max Planck Institute for Dynamics and Self-organization, Am Fassberg 17, D-37077 Goettingen, Germany.
Jean-Christophe
JC
Baret
Raindance Technologies France, 8 allée Gaspard Monge, F-67083 Strasbourg Cedex, France.
Abdeslam
A
El Harrak
Raindance Technologies France, 8 allée Gaspard Monge, F-67083 Strasbourg Cedex, France.
Thomas
T
Mangeat
Institut de Sciences et d'Ingénierie Supramoléculaires (ISIS), Université de Strasbourg, CNRS UMR 7006, 8 allée Gaspard Monge, F-67083 Strasbourg Cedex, France and Department of Chemistry and Chemical Biology, 12 Oxford Street, Harvard University, Cambridge, Massachussets, Massachusetts 02138, USA.
Martin
M
Karplus
Institut de Sciences et d'Ingénierie Supramoléculaires (ISIS), Université de Strasbourg, CNRS UMR 7006, 8 allée Gaspard Monge, F-67083 Strasbourg Cedex, France and Department of Bioengineering, Imperial College London, London SW72AZ, United Kingdom.
Sylvain
S
Ladame
Institut Charles Sadron, Université de Strasbourg, CNRS UPR 22, 23 rue du Loess, F-67034 Strasbourg Cedex, France.
Carlos M
CM
Marques
Institut de Sciences et d'Ingénierie Supramoléculaires (ISIS), Université de Strasbourg, CNRS UMR 7006, 8 allée Gaspard Monge, F-67083 Strasbourg Cedex, France and École Supérieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI ParisTech), CNRS UMR 7084, 10 rue Vauquelin, F-75231 Paris Cedex 05, France.
Andrew D
AD
Griffiths
D000327:Adsorption; D000447:Aldehydes / Q000737:chemistry; D000588:Amines / Q000737:chemistry; D002625:Chemistry, Organic / Q000295:instrumentation / Q000379:methods*; D004058:Diffusion; D007097:Imines / Q000138:chemical synthesis* / Q000737:chemistry; D007700:Kinetics; D008956:Models, Chemical; D013499:Surface Properties; D013816:Thermodynamics
D000447:Aldehydes; D000588:Amines; D007097:Imines