Kinetics of glycolipid phase transitions: ms laser T‐jump synchrotron studies

Abstract

The kinetics of the lamellar gel (Lp) to inverse hexagonal (Hll) phase transition as well as the L,+La phase change of aqueous suspensions of glycolipids were characterized using ms laser T-jump techniques in combination with synchrotron X-ray diffraction. The glycolipids employed were 1,2-di-O-alkyl-3-0-P-D-glucosyl-snglycerols with identical alkyl chains of 16 and 18 carbon atoms, respectively, and 1,2-di-O-alky1-3-O-P-D-galactosyl-sn-glycerol with C,, chains. The time course of the Lc-+La phase transition was probed using 1,2-di-O-hexadecyl-3-O-~-D-lactosyl-sn-glycerol, whose head group consists of the disaccharide P-D-galactopyranosyl-(1 -4)-P-D-glucopyranoside. Surprisingly the phase change from the lamellar to the inverse hexagonal topology is very fast despite the major structural changes involved in the lipid-water interface. The overall phase change of both glucolipids can be quantitatively described by a sequential mechanism of the type Lp A I A HIl.The intermediate I is thinner than both the Lp and the HI, phases. It has a relatively broad distribution of d-spacings and relaxes into the HI, phase with half times of approximately 125 ms (16-1,Z-Glc) and 244 ms (18-1,2-Glc), respectively. Both rate constants, k, and k,, are chain length dependent.The galactolipid transforms into the HI, phase following a sequential mechanism of the type Lg & I' % I & HII. The additional intermediate I' can be assigned to a lamellar phase bearing similarity to a thin La phase. The specific features of the galactose head group compared to glucose as head group that have been previously observed in equilibrium studies are also evident in the kinetic mechanism in that comparative structural changes in the intermediates are slower in the galactolipid than in the chain-homologous glucolipid.There is evidence from the X-ray data that the general transition mechanism is identical for gluco-and galactolipids. However, the first intermediate I' disappears too fast in the glucolipid phase change to be detectable with the present time resolution of the X-ray measurements.The kinetics of the phase change of the lactolipid is characterized within the resolution of the X-ray sequence (5ms) by a strict two-state mechanism L, --t La with transient coexistence of the initial and final phase during the kinetic phase transformation. The relaxation time has been found to be highly temperature dependent, being 57 ms at 79.1 "C and 14 ms at 81.1 "C.It is worth noting that there appears to be a principal difference in the phase change mechanism between glycolipids with mono-or disaccharide head groups in that the latter (16-1.2-Lac) shows no sign of any kinetic intermediate state. k k k k arrangements of the lipids, as seen in the HI, phase formed by a variety of lipids [8 -101. Prominent members of these lipids that form readily non-bilayer structures are glycolipids, both synthetic and natural, provided they have head groups that are small in surface area in comparison to the hydrophobic part of the molecule [l I]. Glycolipids show the most s...

Pressure effects on the structure of lyotropic lipid mesophases and model biomembrane systems

“…Generally, as has also been found in studies of pressure-and temperature-jump induced phase transitions of other systems (Caffrey, 1987;Caffrey et al, 1990;Rapp et al, 1993;Clerc et al, 1995;Ko Èberl et al, 1997), these results show that the relaxation behaviour and the kinetics of pressure-induced lipid phase transformations depend drastically on the topology of the lipid mesophase, and also on the temperature and the driving force, i.e., the applied pressure-jump amplitude Dp. Often multicomponent kinetic behavior is observed, with short relaxation times (probably on the nanosecond to microsecond time-scale) in a burst phase referring to the relaxation of the lipid acyl chain conformation in response to the pressure change, which leads to the small changes in the observed lattice constants right after the pressure-jump.…”

Self-Organisation, Thermotropic and Lyotropic Properties of Glycolipids Related to their Biological Implications

“…The phase transitions of glycolipids are often kinetically hindered. Rapp and colleagues have used X-ray to inves-tigate the glycolipid phase kinetics [ 108 , 109 ], which is quite complex depending on the history of the sample preparation as well as storage conditions and the presence of additional components.…”

Kinetics and Mechanisms of the Sphere-to-Rod and Rod-to-Sphere Transitions in the Ternary System PS310-b-PAA52/Dioxane/Water

“…Although much is known about the kinetics and mechanism of the formation of surfactant and block copolymer aggregates, only a few studies have examined the details involved in the transition from one aggregate morphology to another. Most of these studies deal with structural transformations in surfactant aggregates. − Some of the morphological transitions that have been investigated in surfactant systems include the sphere-to-vesicle, the vesicle-to-sphere, the sphere-to-rod, and the lamellar-to-inverted hexagonal transition 35 as well as the fusion of two vesicles to form one large vesicle …”