Intramolecular and Lattice Melting in n-Alkane Monolayers: An Analog of Melting in Lipid Bilayers

URL:http://link.aps.org/doi/10.1103/PhysRevLett.83.2362 DOI:10.1103/PhysRevLett.83.2362Molecular dynamics (MD) simulations and neutron diffraction experiments have been performed on n-dotriacontane ( n-C32D66) monolayers adsorbed on a graphite basal- plane surface. The diffraction experiments show little change in the crystalline monolayer structure up to a temperature of ~350K above which a large thermal expansion and decrease in coherence length occurs. The MD simulations provide evidence that this behavior is due to a phase transition in the monolayer in which intramolecular and translational order are lost simultaneously. This melting transition is qualitatively similar to the gel-to-fluid transition found in bilayer lipid membranes.Acknowledgment is made to the U.S. National Science Foundation under Grants No. DMR-9314235 and No. DMR-9802476, the Missouri University Research Reactor, and to the donors of The Petroleum Research Fund, administered by the ACS, for partial support of this research. We thank L. Criswell for assistance with the figures

Intramolecular diffusive motion in alkane monolayers studied by high-resolution quasielastic neutron scattering and molecular dynamics simulations

URL:http://link.aps.org/doi/10.1103/PhysRevLett.92.046103 DOI:10.1103/PhysRevLett.92.046103Molecular dynamics simulations of a tetracosane (n-C24H50) monolayer adsorbed on a graphite basal-plane surface show that there are diffusive motions associated with the creation and annihilation of gauche defects occurring on a time scale of ~0.1-4 ns. We present evidence that these relatively slow motions are observable by high-energy-resolution quasielastic neutron scattering (QNS) thus demonstrating QNS as a technique, complementary to nuclear magnetic resonance, for studying conformational dynamics on a nanosecond time scale in molecular monolayers.This work was supported by the NSF under Grants No. DMR-9802476 and No. DMR-0109057, by the Chilean government under FONDECYT Grant No. 1010548, and by the U.S. Department of Energy through Grant No. DE-FG02-01ER45912. The neutron scattering facilities in this work are supported in part by the National Science Foundation under Agreement No. DMR-0086210

Key Role of Polyphosphoinositides in Dynamics of Fusogenic Nuclear Membrane Vesicles

The role of phosphoinositides has been thoroughly described in many signalling and membrane trafficking events but their function as modulators of membrane structure and dynamics in membrane fusion has not been investigated. We have reconstructed models that mimic the composition of nuclear envelope precursor membranes with naturally elevated amounts of phosphoinositides. These fusogenic membranes (membrane vesicle 1(MV1) and nuclear envelope remnants (NER) are critical for the assembly of the nuclear envelope. Phospholipids, cholesterol, and polyphosphoinositides, with polyunsaturated fatty acid chains that were identified in the natural nuclear membranes by lipid mass spectrometry, have been used to reconstruct complex model membranes mimicking nuclear envelope precursor membranes. Structural and dynamic events occurring in the membrane core and at the membrane surface were monitored by solid-state deuterium and phosphorus NMR. “MV1-like” (PC∶PI∶PIP∶PIP2, 30∶20∶18∶12, mol%) membranes that exhibited high levels of PtdIns, PtdInsP and PtdInsP2 had an unusually fluid membrane core (up to 20% increase, compared to membranes with low amounts of phosphoinositides to mimic the endoplasmic reticulum). “NER-like” (PC∶CH∶PI∶PIP∶PIP2, 28∶42∶16∶7∶7, mol%) membranes containing high amounts of both cholesterol and phosphoinositides exhibited liquid-ordered phase properties, but with markedly lower rigidity (10–15% decrease). Phosphoinositides are the first lipids reported to counterbalance the ordering effect of cholesterol. At the membrane surface, phosphoinositides control the orientation dynamics of other lipids in the model membranes, while remaining unchanged themselves. This is an important finding as it provides unprecedented mechanistic insight into the role of phosphoinositides in membrane dynamics. Biological implications of our findings and a model describing the roles of fusogenic membrane vesicles are proposed

Restatement of order parameters in biomembranes: calculation of C-C bond order parameters from C-D quadrupolar splittings.

An expression for the C-C bond order parameter, SCC, of membrane hydrocarbon chains has been derived from the observed C-D bond order parameters. It allows calculation of the probability of each of the C-C bond rotamers and, consequently, the number of gauche defects per chain as well as their projected average length onto the bilayer normal, thus affording the calculation of accurate hydrophobic bilayer thicknesses. The effect of temperature has been studied on dilauroyl-, dimyristoyl-, and dipalmitoylphosphatidylcholine (DLPC, DMPC, DPPC) membranes, as has the effect of cholesterol on DMPC. The salient results are as follows: 1) an odd-even effect is observed for the SCC versus carbon position, k, whose amplitude increases with temperature; 2) calculation of SCC, from nonequivalent deuterons on the sn-2 chain of lipids, SCC2, leads to negative values, indicating the tendency for the C1-C2 bond to be oriented parallel to the bilayer surface; this bond becomes more parallel to the surface as the temperature increases or when cholesterol is added; 3) calculation on the sn-2 chain length can be performed from C1 to Cn, where n is the number of carbon atoms in the chain, and leads to 10.4, 12.2, and 13.8 A for DLPC, DMPC, and DPPC close to the transition temperature, TC, of each of the systems and to 9.4, 10.9, and 12.6 for T-TC = 30-40 degrees C, respectively; 4) separation of intra- and intermolecular motions allows quantitation of the number of gauche defects per chain, which is equal to 1.9, 2.7, and 3.5 for DLPC, DMPC, and DPPC near TC and to 2.7, 3.5, and 4.4 at T-TC = 30-40 degrees C, respectively. Finally, the validity of our model is discussed and compared with previously published models

Novel Lipid System Forming Hollow Microtubes at High Yields and Concentration

There is considerable interest in constructing supramolecular hollow tube architectures based on amphiphilic molecules. This can be achieved by using relatively expensive synthetic lipids. Herein, we report on the facile preparation of self-assembled microtubes from a novel low-cost lipid mixture that does not require a previous chemical synthesis step and consists of the ethanolamine salt of 12-hydroxy-stearic acid in water. Tubes of more than 10 ím in length spontaneously form upon cooling from an isotropic solution. They exhibit inner and outer diameters of 400 and 600 nm, respectively, and their walls consist of concentric stacked bilayers of fatty acid salts, each separated by a layer of wate

Self-Assembly and Foaming Properties of Fatty Acid-Lysine Aqueous Dispersions

We report on dispersions of fatty acid-lysine salts in aqueous solutions which are further used to produce foams. The alkyl chain length is varied from dodecyl to stearic. In aqueous solutions, the lysine salt of the dodecyl chain yields an isotropic solution, probably micelles, whereas for longer alkyl chains, vesicles formed but crystallized upon resting at room temperature or when kept at 4 C. Solid stateNMRshowed that in vesicles fatty acids are embedded in a lamellar arrangement passing from a gel to a fluid state upon heating; the transition temperature at which it occurs was determined by DSC. Those results are confirmed by small-angle neutron scattering which also give additional information on the bilayer structure. Incredibly stable foams are obtained using the palmitic acid/Lys salt whereas for other alkyl chain length, poor or no foam is formed. We conclude that the foamability is related to the phase behavior in aqueous solution

Lipid-transfert protein (LTP) from wheat Kernel possesses a weak, specific esterase-like activity towards short chain fatty acid esters

International audience31P nucelar magnetic resonance studies showed that palmityol lysophosphatidyl-choline is slowly hydrolyzed when incubated with LTP from wheat