Kinetic asymmetry in the gel-liquid crystalline state transitions of DDAB vesicles studied by differential scanning calorimetry.

Didodecyldimethylammonium bromide (DDAB) (1.0 mM) vesicles in water were investigated by differential scanning calorimetry (DSC) to highlight the existing kinetic asymmetry in the gel-liquid crystalline (LC) state transitions. The experiments were performed in the range of temperature, scan rate and pre-scanning time 5-45 degrees C, 15-90 degrees C/h and 0-16 h, respectively, in the up- and down-scanning modes. Depending on the input parameters and number of heating-cooling cycles, the DSC thermograms exhibit a sharp peak, a broad band or a flat shape. A melting temperature T(m)=15.6-16.0 degrees C, given by the peak position, was obtained independently of the scan rate used in the up-scanning mode. The data reveal that DDAB vesicles exhibit much slower kinetics for the LC to gel state than for the opposite transition. Such an asymmetry is supported by: (a) the absence of peak for shorter pre-scanning times but longer scan rates, (b) the increasing intensity of the DSC peak with increasing pre-scanning time and decreasing scan rate, and (c) the complete absence of peak in the down-scan mode. Longer pre-scanning time, however, yields crystal precipitates due to a Krafft phenomenon, which also reduces the peak intensity. The overall results depend on whether the sample is fresh or not, that is, after some heating-cooling cycles, the melting peak requires a longer pre-scanning time to be detected. The kinetic asymmetry explains, for example, the lack of any DSC melting peak reported for "non-fresh" DDAB vesicles, which was as yet unexplained.