Characterization of bromide ions in charge-stacked zwitterionic micellar systems.
A novel zwitterionic surfactant, N-dodecyl-N,N,N',N'-tetra-methyl-ethylene-di-ammonio-propane-sulfonate bromide (DEPB), has been synthesized, and Br(-) involved in the micellar system has been characterized by potentiometry, NMR, and X-ray absorption fine structure (XAFS). Although the dissociation degree of Br(-) from the micelle evaluated by potentiometry almost agrees with that determined by NMR, the former is significantly smaller than the latter over the entire range of concentrations of DEPB. This is explained by assuming that the bromide ions in the micellar system have several different peripheral structures. XAFS has given significant insight into the hydration structures of Br(-) involved in the system. Some of the bromide ions partitioned into the micelle are dehydrated and are directly bound by the ammonium groups in the DEP molecules. However, some of the bromide ions are still completely hydrated even when they are partitioned into the micelles. The average hydration number of the bromide ions directly bound by the ammonium groups was determined to be approximately 3.3. The partial dehydration of Br(-) is possibly facilitated by the characteristic hydration circumstances provided by the charge-stacked structure of the surfactant and by the resulting thick palisade layer of the DEP micelle.
Aoki
Takeshi
T
Department of Chemistry, Tokyo Institute of Technology, Meguro-ku, Tokyo 152-8551, Japan.
Harada
Makoto
M
Okada
Tetsuo
T