Kemp Elimination in Membrane Mimetic Reaction Media:  Probing Catalytic Properties of Catanionic Vesicles Formed from Double-Tailed Amphiphiles

The rate-determining deprotonation of 5-nitrobenzisoxazole (Kemp elimination) by hydroxide is efficiently catalyzed by vesicles formed from dimethyldioctadecylammonium chloride (C(18)()C(18)()(+)()). Gradual addition of sodium didecyl phosphate (C(10)()C(10)()(-)()) leads to the formation of catanionic vesicles, which were characterized by cryo-electron microscopy, and their main phase transition temperatures (DSC) and zeta-potentials. Increasing percentages of C(10)()C(10)()(-)() in the vesicular bilayers decrease the catalysis of the Kemp elimination. A detailed kinetic analysis, supported by consideration of substrate binding site polarities and counterion binding percentages, suggest that the catalytic effects of C(18)()C(18)()(+)()/C(10)()C(10)()(-)() catanionic vesicles are primarily determined by the binding of catalytically active hydroxide ions to the vesicular surface area. The formation of neutral microdomains between 10 and 30 mol % of C(10)()C(10)()(-)() in the bilayer, as revealed by DSC, is not apparent from the catalytic effects found for these vesicles. Interestingly, the catalytic effects observed for 50 mol % C(10)()C(10)()(-)() in the catanionic vesicles indicate an asymmetric distribution of C(18)()C(18)()(+)() and C(10)()C(10)()(-)() over the bilayer leaflets. The overall kinetic results illustrate the highly complex mix of factors which determines catalytic effects on reactions occurring in biological cell membranes.