ENTHALPIES OF INTERACTION BETWEEN DIMETHYLDIOCTADECYLAMMONIUM BROMIDE VESICLES IN AQUEOUS-SOLUTION AND EITHER DIPICOLINATE OR SULFATE ANIONS

Injection of small aliquots of dipicolinate anions (sodium salt) into an aqueous solution containing dimethyldioctadecylammonium bromide (DOAB) vesicles is endothermic at 50-degrees-C, becoming first more and then less endothermic. The injection process is effectively athermal for solutions containing more than equimolar amounts of DOAB and dipicolinate anions. A similar pattern is observed when small aliquots of sodium sulfate(aq) are injected into DOAB(aq). The overall patterns of enthalpy changes are attributed to the vesicle-dianion interaction which is exothermic and head-group dehydration with bromide ion displacement which is endothermic. Nevertheless, a complexity emerges if the solutions include a buffer which turns out to play a less than passive role. This conclusion is supported by differential scanning microcalorimetry for DOAB(aq) in the presence and absence of HEPES buffer.