화학공학소재연구정보센터
Langmuir, Vol.24, No.20, 11851-11859, 2008
X-ray Kinematography of Phase Transformations of Three-Component Lipid Mixtures: A Time-Resolved Synchrotron X-ray Scattering Study Using the Pressure-jump Relaxation Technique
By using the pressure-jump relaxation technique in combination with time-resolved synchrotron small-angle X-ray diffraction (TRSAXS), the kinetics of lipid phase transformations of ternary lipid mixtures serving as model systems of heterogeneous raftlike membranes were investigated. To this end, we first established the temperature-pressure phase diagram of a model lipid raft mixture, 1,2-dioleoyl-sn-glycero-3-phosphatidylcholine (DOPC)/1,2-dipalmitoylsn-glycero-3-phosphatidylcholine (DPPC)/cholesterol (1:2: 1), using Fourier transform infrared spectroscopy and SAXS, covering the pressure range from 1 bar to 10 kbar at temperatures in the range from 7 to 80 degrees C. We then studied the kinetics of interlamellar phase transitions of the ternary lipid system involving transitions from the fluidlike (liquid-disordered, 1(d)) phase to the liquid-ordered (1(o))/liquid-disordered (1(d)) two-phase coexistence region as well as between the two- and three-phase coexistence regions of the system, where also solid-ordered phases (s(o)) are involved. The phase transition from the all-fluid 1(d) phase to the 1(o)+1(d) two-phase coexistence region turns out to be rather rapid. Phases appear or disappear within the 25 ms time resolution of the technique, followed by a slow lattice relaxation process, which, depending on the pressure-jump amplitude, takes several seconds. Contrary to many one-component phospholipid phase transitions, the kinetics of the 1(d) <-> 1(o)+1(d) transition follows a similar time scale and mechanism for the pressurization and depressurization direction. A similar behavior is observed for the phase transition kinetics of the s(o)+1(o)+1(d) <-> 1(0) +1(d) transformation and even for the s(o)+1(o)+1(d) <-> 1d transformation, jumping across the 1(o)+1(d) two-phase region. All transitions are fully reversible, and no intermediate states are populated. As indicated by the complex relaxation profiles observed, the overall rates observed seem to reflect the effect of coupling of various dynamical processes through the transformation, involving fast conformational changes in the sub-millisecond time regime and slow relaxation of the lattices growing, probably being largely controlled by the transport and redistribution of water into and in the new phases of the multilamellar vesicle assemblies.