Vesicles accelerate proton transfer from carbon up to 850-fold.
[reaction: see text] We have analyzed the different catalytic effects of surfactant aggregates upon the rate-determining hydroxide ion induced deprotonation reaction of 1. Vesicles are more effective catalysts than micelles, most likely providing a more apolar microenvironment at the substrate binding sites. We suggest that this leads to a catalytic reaction involving less strongly hydrated hydroxide ions. In the case of DODAB and DODAC vesicles, binding of cholesterol to the bilayer further increases the catalytic efficiency.
Pérez-Juste
J
J
Department of Organic and Molecular Inorganic Chemistry, University of Groningen, The Netherlands.
Hollfelder
F
F
Kirby
A J
AJ
Engberts
J B
JB
D000890:Anti-Infective Agents / Q000737:chemistry / Q000494:pharmacology; D002244:Carbon / Q000737:chemistry; D002384:Catalysis / Q000187:drug effects; D002784:Cholesterol / Q000494:pharmacology; D007700:Kinetics; D008081:Liposomes / Q000737:chemistry / Q000494:pharmacology*; D008823:Micelles; D011522:Protons; D000644:Quaternary Ammonium Compounds / Q000737:chemistry / Q000494:pharmacology; D013501:Surface-Active Agents / Q000737:chemistry / Q000494:pharmacology
D000890:Anti-Infective Agents; D008081:Liposomes; D008823:Micelles; D011522:Protons; D000644:Quaternary Ammonium Compounds; D013501:Surface-Active Agents; C046112:didodecyldimethylammonium; C015831:dimethyldioctadecylammonium; D002244:Carbon; D002784:Cholesterol