RESUMO
Electrostatic interaction is an important factor for phase transitions between lamellar liquid-crystalline (Lα) and inverse bicontinuous cubic (QII) phases. We investigated the effect of temperature on the low-pH-induced Lα to double-diamond cubic (QII(D)) phase transition in dioleoylphosphatidylserine (DOPS)/monoolein (MO) using time-resolved small-angle X-ray scattering with a stopped-flow apparatus. Under all conditions of temperature and pH, the Lα phase was directly transformed into an intermediate inverse hexagonal (HII) phase, and subsequently the HII phase slowly converted to the QII(D) phase. We obtained the rate constants of the initial step (i.e., the Lα to HII phase transition) and of the second step (i.e., the HII to QII(D) phase transition) using the non-negative matrix factorization method. The rate constant of the initial step increased with temperature. By analyzing this result, we obtained the values of its apparent activation energy, Ea (Lα â HII), which did not change with temperature but increased with an increase in pH. In contrast, the rate constant of the second step decreased with temperature at pH 2.6, although it increased with temperature at pH 2.7 and 2.8. These results indicate that the value of Ea (HII â QII(D)) at pH 2.6 increased with temperature, but the values of Ea (HII â QII(D)) at pH 2.7 and 2.8 were constant with temperature. The values of Ea (HII â QII(D)) were smaller than those of Ea (Lα â HII) at the same pH. We analyzed these results using a modified quantitative theory on the activation energy of phase transitions of lipid membranes proposed initially by Squires et al. (Squires, A. M.; Conn, C. E.; Seddon, J. M.; Templer, R. H. Soft Matter 2009, 5, 4773). On the basis of these results, we discuss the mechanism of this phase transition.
Assuntos
Glicerídeos/química , Fosfatidilserinas/química , Concentração de Íons de Hidrogênio , Cinética , Lipossomos/química , Transição de Fase , Espalhamento de Radiação , Temperatura , Termodinâmica , Difração de Raios XRESUMO
Electrostatic interactions (EI) are an important factor for phase transitions between lamellar liquid-crystalline (L(α)) and inverse bicontinuous cubic (Q(II)) phases. We investigated the low pH-induced L(α) to double-diamond cubic (Q(II)(D)) phase transition in dioleoylphosphatidylserine (DOPS)/monoolein (MO) using time-resolved small-angle X-ray scattering. Using a stopped-flow apparatus, a suspension of liposomes (multilamellar vesicles (MLVs) or large unilamellar vesicles (LUVs)) of 20%-DOPS/80%-MO membrane at neutral pH was rapidly mixed with a low pH buffer, and then the structural change of the membranes in the resultant suspension was observed as a function of time (i.e., pH-jump experiment). At the initial step, the L(α) phase was directly transformed into the hexagonal II (H(II)) phase, and subsequently, the H(II) phase slowly converted into the Q(II)(D) phase. We obtained the rate constants of the initial step (i.e., the L(α) to H(II) phase transition) and of the second step (i.e., the H(II) to Q(II)(D) phase transition) using the non-negative matrix factorization method. The rate constant of the initial step was independent of the MLV concentration, indicating that single MLVs can convert into the HII phase without any interaction with other MLVs. On the other hand, the rate constant of the initial step increased with a decrease in pH, 0.041 s(-1) at pH 2.6 and 0.013 s(-1) at pH 2.8, and also exhibited a size dependence; for smaller vesicles such as LUVs and smaller MLVs with diameters of ~1 µm, the rate constant was smaller. They were reasonably explained by the classical nucleation theory. These results provide the first experimental evidence of the total kinetics of EI-induced L(α)/Q(II) phase transitions.
Assuntos
Glicerídeos/química , Transição de Fase , Fosfatidilserinas/química , Lipossomas Unilamelares/química , Concentração de Íons de Hidrogênio , Eletricidade EstáticaRESUMO
Visual object recognition is facilitated by contextually consistent scenes in which the object is embedded. Scene gist representations extracted from the scenery backgrounds yield this scene consistency effect. Here we examined whether the scene consistency effect is specific to the visual domain or if it is crossmodal. Through four experiments, the accuracy of the naming of briefly presented visual objects was assessed. In each trial, a 4-s sound clip was presented and a visual scene containing the target object was briefly shown at the end of the sound clip. In a consistent sound condition, an environmental sound associated with the scene in which the target object typically appears was presented (e.g., forest noise for a bear target object). In an inconsistent sound condition, a sound clip contextually inconsistent with the target object was presented (e.g., city noise for a bear). In a control sound condition, a nonsensical sound (sawtooth wave) was presented. When target objects were embedded in contextually consistent visual scenes (Experiment 1: a bear in a forest background), consistent sounds increased object-naming accuracy. In contrast, sound conditions did not show a significant effect when target objects were embedded in contextually inconsistent visual scenes (Experiment 2: a bear in a pedestrian crossing background) or in a blank background (Experiments 3 and 4). These results suggested that auditory scene context has weak or no direct influence on visual object recognition. It seems likely that consistent auditory scenes indirectly facilitate visual object recognition by promoting visual scene processing.