Three gemini and two bolaform bisphosphate surfactants of the type 12-
s-12, with s = 6, 8, 12, 18, and 24 carbon atoms, have been synthesize
d and their aggregation behavior has been studied. The bolaform surfac
tants 12-18-12 and 12-24-12 were found to form vesicles in aqueous sol
ution, as indicated by electron microscopy. The geminis 12-6-12, 12-8-
12, and 12-12-12 form micellar structures. The cmc's of the geminis, o
btained from conductivity measurements, spectroscopic methods, and mic
rocalorimetry, are very low, on the order of 10(-4) to 10(-5) M. The c
me decreases with increasing spacer length. For the bolaform amphiphil
es 12-18-12 and 12-24-12 noncooperative phase transitions are detected
using fluorescence depolarization and DSC. NMR line-broadening studie
s display unusual behavior. The spacer within the 12-24-12 vesicles ha
s been found to be membrane spanning, as confirmed by X-ray powder dif
fraction.