Lipid assemblies, phase transitions

Lipid assemblies of the lamellar type, such as lipid bilayers, can feature a true phase transition in which the topology does not change. Upon cooling, the bilayer goes from the fluid phase to the gel phase. In the fluid phase, the acyl chains are disordered, in the sense that there is enough free volume around the chains to allow for chain conformation variations. In the gel phase, the acyl chains are more densely packed and believed to be ordered in an all-trans (straight) configuration. For very pure systems, at temperatures below this sharp gel-to-liquid phase transition, there are several other states and distinct transitions detectable (pre-transition, ripple phase, etc.). These phases will not be reviewed here. In biomembranes, many type of lipids (and other molecules) occur, and it is known that for this reason the gel-to-liquid phase transition is... 

Liposome Formation. The pioneering investigations of Bang-ham (5) have shown that thin films of natural phospholipids form bilayer assemblies if they are lyophilized in excess water by simple handshaking above the phase transition temperature. While this procedure results in the formation of large, multibilayered spherical structures, by ultrasonication of such lipid dispersions small unilamellar liposomes are formed (16), which are schematically shown in Figure 10. Additional metTiods for liposome preparation are described in a number of reviews (17,44,45,46). 

We then investigated the formation of hybrid molecular assemblies in combinations of anionic peptide lipid 9 with cage-type hosts 7 and 8 after a previous method [44], Lamella-type aggregates are observed for a mixture of host 7 and lipid 9 at a 1 20 molar ratio in the dispersion state by negative staining electron microscopy. Phase transition parameters (temperature at peak maximum, T enthalpy change, AH entropy change, dS half-width of an endothermic peak, and hydrodynamic diameters (d,y) for the bilayer... 

The effect of toxins such as melittin (from the honey-bee venom), myotoxin a, and cardiotoxin (from the snake venom) was investigated by vibrational spectroscopy (Pezolet et al., 1982 Faucon et ah, 1983 Liddle and Tu, 1985 Lafleur et ah, 1987). Monitoring the Raman intensity ratio I(1060)/I(1080) indicated that the lipid/melittin assemblies in DPPC are characterized by a high conformational order, little intermolecular chain-chain interaction, and a low cooperativity of the gel-like liquid crystalline phase transition. The effect of ricin, a toxic lectin, on DPPC and DPPC-cerebroside mixtures was studied by Raman and IR spectroscopy. It was suggested that ricin mainly interacts with the interfacial domains of the bilayers (Picquart et ah, 1989). 

This membrane fusion process (outside the brain) is known to involve thousands of single membrane units, previously thought of as vesicles, assembled into units that have been termed "boutons". We have examined the EM texture of the boutons and found that they are in fact a cubic phase. The synaptic signal transmission can take place as frequently as hundreds of times per second. A fusion process involving a hyperbolic membrane can be well controlled, and the calcium ion influx - which induces fusion - is expected to change the conformation of the cubosome surface membrane from its planar bilayer conformation to the fusogenic saddle-saddle conformation. (It is known phase transitions of membrane lipids can occur when exposed to calcium, e.g. [40]). 

Up until 1977, the non-covalent polymeric assemblies found in biological membranes rarely attracted any interest in supramolecular organic chemistry. Pure phospholipids and glycolipids were only synthesized for biophysical chemists who required pure preparations of uniform vesicles, in order to investigate phase transitions, membrane stability and leakiness, and some other physical properties. Only very few attempts were made to deviate from natural membrane lipids and to develop defined artificial membrane systems. In 1977, T. Kunitake published a paper on A Totally Synthetic Bilayer Membrane in which didodecyl dimethylammonium bromide was shown to form stable vesicles. This opened the way to simple and modifiable membrane structures. Since then, organic chemists have prepared numerous monolayer and bilayer membrane structures with hitherto unknown properties and coupled them with redox-active dyes, porous domains and chiral surfaces. Recently, fluid bilayers found in spherical vesicles have also been complemented by crystalline mono-... 

The extruder apparatus must be fully assembled before inserting it in the heating block, otherwise it will be damaged. The liposome suspension should be kept above the phase transition temperature of the lipids during extrusion. 

Figure 2.9a shows the lipid molecule DMPC. Two layers contacted via the hydrophobic tails lead to spontaneous formation of a double-layer biomimetic membrane that can be transferred to a single-crystal ultraplanar electrochemical Au(lll) surface. The hydrophilic head groups contact the electrode surface via an intermediate water film. Due to the structurally very well-defined assembly, not only AFM and in situ STM but also neutron reflectivity. X-ray diffraction, and infrared reflection absorption spectroscopy (IRRAS) have been employed to support the direct visual in situ STM. Electrochemically controlled structural changes, phase transitions, and the effects of the common membrane component cholesterol (Figure 2.9b) and peptide drugs have been investigated in this way. 

Phase Transitions in Lipid Assemblies. The rich polymorphism of amphiphilic systems, of which the multilamellar and the Hn phases are only two structures, was made evident from the seminal work of Luzzati and co-workers. Since that early work, an immense variety of water-induced phase transitions have been observed and rationalized in terms of an apparently systematic connection between water content and polar group molecular area. Therefore, the recent observation of a double transition—Hn to lamellar back to Hn—from continual hydration of dioleoylphosphatidyl-ethanolamine (40) was a surprise. Furthermore, an estimate of the cost of uncurling the monolayer in the formation of bilayers based on the previously described bending modulus far exceeds the osmotic work that actually produced the transition. Although this transition sequence can successfully be accounted for by simple thermodynamical principles, it, in fact, contains many geometry-dependent free energy contributions that we simply do not yet understand (41). 

Faunce, C. A. and Paradies, H. H. (2010). Phase transition, structure, self-assembly and arrangements of lipid A-phosphates in aqueous dispersions. Recent. Res. Devel. Physical Chem. 10, 77-141. Transworld Research Network, (37/661 92) Trivandram-695 023 Kerala, India. 

The first set of experiments involved fluorescence resonance energy transfer (FRET) between the naphthalene and pyrene-laheled polymers. A 5 1 mixture of PNIPAM-Py to PNIPAM-Na was used. When assembled in micelles, the pyrene acts as a quencher to the naphthalene, leading to high pyrene fluorescence and low naphthalene fluorescence. When the mixture is added to DMPC (liquid phase) or DSPC (gel phase) vesicles at room temperature, naphthalene fluorescence is increased, while pyrene fluorescence is dramatically decreased. This effect is not seen with the PNIPAM-Py-Na polymer, so the reduction in FRET is not due to the hydrophobic environment. This means that the hydrophobic anchors of the PNIPAM-Py and the PNIPAM-Na likely enter the membrane and the dyes are moved apart from one another. The fact that the anchor appeared to insert into the gel-phase DSPC membrane was somewhat surprising. The authors attribute the effect to defects between crystalline domains in the membrane. To test if the LCST transition still occurs when the polymers are anchored to the membrane, differential scanning calorimetry (DFC) was used. The LCST transition of the PNIPAM-Py/PNIPAM-Na mixture in solution was observed in the DFC ttace. When combined with DSPC or DMPC vesicles, the same peak was observed, indicating that the transition does indeed stiU occur, even in the presence of the lipid. 

The LB film prepared in the dark shows temperature dependent UV-vis absorption spectra. At lower temperatures, there is an electronic interaction between the fullerene moieties in the LB film. Upon heating over 47 C, which is the subphase transition temperature of the cast films of the fullerene lipid [28, 36], the electronic interaction of the fullerene moieties is loosened. The electronic interaction between the fullerene moieties can be controlled by the phase change of the film. The fundamental property of the self-assembled bilayer membrane film is maintained in the LB film prepared in the dark, indicating that the molecular orientations of the... 

---