Effect of ethanol-induced lipid interdigitation on the membrane solubility of Prodan, Acdan, and Laurdan.

The effect of ethanol-induced lipid interdigitation on the partition coefficient (Kp) of 6-propionyl-2-(dimethylamino)naphthalene (Prodan) and its two derivatives, 6-acetyl-2-(dimethylamino)naphthalene (Acdan) and 6-lauroyl-2-(dimethylamino)naphthalene (Laurdan), in L-alpha-dipalmitoylphosphatidylcholine (DPPC) vesicles has been examined by a precipitation method over the ethanol concentration range of 0-1.8 M. At 20 degrees C and in the absence of ethanol, the Kp values for Acdan, Prodan, and Laurdan are 2.0 x 10(3), 2.8 x 10(4), and 4.7 x 10(6), respectively. This result suggests that the Kp of Prodan and its derivatives is not simply a linear function of the polymethylene units. As DPPC undergoes the ethanol-induced phase transition from the noninterdigitated to the fully interdigitated gel state, Kp for Prodan and Acdan decreases by a factor of 5 and 2, respectively, whereas Kp for Laurdan exhibits no detectable changes with ethanol. The differences in Kp are in parallel with the differences in the fluorescence emission spectra of these probes over the ethanol concentration range examined. Previous fluorescence and infrared data indicated that membrane perturbation caused by the probes increases in the order: Laurdan > Prodan > Acdan. Thus, the degree of membrane perturbation also seems to be in parallel with Kp. Among these three probes, Prodan fluorescence reflects most correctly the ethanol-induced lipid interdigitation. In conclusion, the partitioning of small solutes in lipid membranes is significantly reduced by ethanol-induced lipid interdigitation, probably as a result of an increased membrane surface density due to the increased intramolecular lipid acyl chain ordering and a tighter overall intermolecular packing.