Micellar Control of the Nitrous Acid Deamination Reaction

Micellar catalysis of ester hydrolysis. Influence of chirality and head group structure in simple surfactants

“…From duplicate runs, and from the scatter of the k values in the plateau region, we estimate that the rate constants are reproducible to ±3%. 6 See Table I for surfactant abbreviations.c The difference in rate constants at 8.0 and 7.0 is recorded as a reflection of the base-catalyzed process at pH 8.0. d Reference 8 gives -~4.9 X 10-2 sec-1 in 0.01 M sodium borate buffer. The discrepancy may have to do with differing buffer concentration and quality; this is amplified in the Discussion.…”

“…Water was distilled from KMn04. 6 A solvent polarity parameter based on the transition energy (kcal/mol) of the intramolecular charge-transfer band of a pyridinium phenol betaine; see ref were prepared. The rate constant for hydrolysis of dl-1 was determined for each solution as a function of the amount of added 0.05 M pH 9 buffer (0.2-0.8 ml).…”

“…Note, especially, the bathochromic shift of Xmax, which accompanies increasing solvent polarity, as well as the general parallel of Xmax with £T(30)21 and Z22 parameters.23 CBzDA-Br4 3540 0 0.56 M surfactant and 3 X 10~i III in 99:1. waterdioxane (by volume). 6 See Table I for surfactant abbreviations. 0 An identical maximum was observed with Z-16.26 d We thank Mr. C. E. Powell for this experiment.…”