Electrostatic micellar effects on the rate of spontaneous decomposition of m-nitrophenyl 9-fluorenecarboxylate

Article abstract of DOI:10.1021/ja00032a031

The effects of neutral, ionic, and zwitterionic micelles on the rate of the spontaneous decomposition of m-nitrophenyl 9-fluorenecarboxylate (I) were determined. Neutral micelles of a poly(oxyethylene) detergent produce a small increase in the decomposition rate. Negatively charged micelles of sodium dodecyl sulfate catalyze the reaction 2-fold while positively charged micelles of hexadecyltrimethylammonium bromide (CTAB) inhibit by a similar factor. Micelles of N-hexadecyl-N,N-dimethylammonium 3-propanesulfonate inhibit the decomposition of I to a larger extent than those of O-hexadecyl-phosphorylcholine while lysolecithin micelles do not affect the reaction rate. Thus, charge orientation of the monomer does not determine the kinetic effects of zwitterionic micelles on the rate of decomposition of I. The rate modifications produced by micelles on this reaction are consistent with electrostatic effects on the relative energies of initial and transition states.