Incoherent Neutron Spin-Echo Spectroscopy as an Option to Study Long-Range Lipid Diffusion

Diffusion is the fundamental mechanism for lipids and other molecules to move in a membrane. It is an important process to consider in modelling the formation of membrane structures, such as rafts. Lipid diffusion is mainly studied by two different techniques: incoherent neutron scattering and fluorescence microscopy. Both techniques access distinctly different length scales. While neutron scattering measures diffusion over about 3 lipid diameters, microscopic techniques access motions of lipids over micrometer distances. The diffusion constants which are determined by these two methods often differ by about an order of magnitude, with the neutrons usually seeing a faster lipid diffusion. Different theories are used to describe lipid diffusion in the two experiments. In order to close the “gap” between these two techniques, we propose to study lipid diffusion at mesoscopic length scales using a neutron spin-echo (NSE) spectrometer. We have conducted an experiment in highly oriented, solid supported lipid bilayers to prove the feasibility of performing incoherent NSE on biological samples. Lateral lipid diffusion was measured in a fluid phase model membrane system at a length scale of 12 Å. Using the high-energy resolution of the NSE technique, we find evidence for two dynamic processes.</jats:p

Heated gas bubbles enrich, crystallize, dry, phosphorylate and encapsulate prebiotic molecules

Non-equilibrium conditions must have been crucial for the assembly of the first informational polymers of early life, by supporting their formation and continuous enrichment in a long-lasting environment. Here, we explore how gas bubbles in water subjected to a thermal gradient, a likely scenario within crustal mafic rocks on the early Earth, drive a complex, continuous enrichment of prebiotic molecules. RNA precursors, monomers, active ribozymes, oligonucleotides and lipids are shown to (1) cycle between dry and wet states, enabling the central step of RNA phosphorylation, (2) accumulate at the gas–water interface to drastically increase ribozymatic activity, (3) condense into hydrogels, (4) form pure crystals and (5) encapsulate into protecting vesicle aggregates that subsequently undergo fission. These effects occur within less than 30 min. The findings unite, in one location, the physical conditions that were crucial for the chemical emergence of biopolymers. They suggest that heated microbubbles could have hosted the first cycles of molecular evolution

Crossovers in supercooled solvation water: Effects of hydrophilic and hydrophobic interactions

Systematic 8 ns ab initio molecular dynamics (AIMD) were performed to study the structure and dynamics of water in bulk and close to hydrophobic (CH3) and hydrophilic (carbonyl) groups of tetramethylurea (TMU). Dynamical behaviour showed two crossovers: The first around the hydrophobic group at , and the second at related to the relative strengths of water-water and water-carbonyl hydrogen bonds (HBs). For bulk water, relaxation times appear to diverge at , rendering support to the liquid-liquid critical point hypothesis. To identify the effects due to the hydrophilic carbonyl group, systems of water with one methane molecule were used as references. Our findings are related to the structural and thermodynamic transitions reported for proteins in solution and may play a role in cold denaturation

Hydration Water Freezing in Single Supported Lipid Bilayers

We present a high-temperature and high-energy resolution neutron scattering investigation of hydration water freezing in single supported lipid bilayers. Single supported lipid bilayers provide a well-defined biological interface to study hydration water dynamics and coupling to membrane degrees of freedom. Nanosecond molecular motions of membrane and hydration water were studied in the temperature range 240 K &lt; T &lt; 290 K in slow heating and cooling cycles using coherent and incoherent elastic neutron scattering on a backscattering spectrometer. Several freezing and melting transitions were observed. From the length scale dependence of the elastic scattering, these transitions could be assigned to freezing and melting of hydration water dynamics, diffusive lipid, and lipid acyl-tail dynamics. Coupling was investigated by comparing the different freezing and melting temperatures. While it is often speculated that membrane and hydration water dynamics are strongly coupled, we find that membrane and hydration water dynamics are at least partially decoupled in single bilayers.</jats:p

Diffusion in membranes: Toward a two-dimensional diffusion map

For decades, quasi-elastic neutron scattering has been the prime tool for studying molecular diffusion in membranes over relevant nanometer distances. These experiments are essential to our current understanding of molecular dynamics of lipids, proteins and membrane-active molecules. Recently, we presented experimental evidence from X-ray diffraction and quasi-elastic neutron scattering demonstrating that ethanol enhances the permeability of membranes. At the QENS 2014/WINS 2014 conference we presented a novel technique to measure diffusion across membranes employing 2-dimensional quasi-elastic neutron scattering. We present results from our preliminary analysis of an experiment on the cold neutron multi-chopper spectrometer LET at ISIS, where we studied the self-diffusion of water molecules along lipid membranes and have the possibility of studying the diffusion in membranes. By preparing highly oriented membrane stacks and aligning them horizontally in the spectrometer, our aim is to distinguish between lateral and transmembrane diffusion. Diffusion may also be measured at different locations in the membranes, such as the water layer and the hydrocarbon membrane core. With a complete analysis of the data, 2-dimensional mapping will enable us to determine diffusion channels of water and ethanol molecules to quantitatively determine nanoscale membrane permeability

Cholesterol expels ibuprofen from the hydrophobic membrane core and stabilizes lamellar phases in lipid membranes containing ibuprofen

The presence of cholesterol in lipid membranes with ibuprofen suppresses partitioning of ibuprofen in the lipid tail groups and stabilizes lamellar membrane phases.</p

Partitioning of ethanol into lipid membranes and its effect on fluidity and permeability as seen by X-ray and neutron scattering

We present a combined neutron and X-ray scattering investigation to study the effect of ethanol on the molecular structure and dynamics of lipid membranes. 1,2-Dimyristoyl-sn-glycero-3-phoshatidylcholine (DMPC) powder hydrated with a 5 wt% ethanol solution (corresponding to 2 mol% of ethanol) was used in this study. From high-resolution X-ray experiments the position and partitioning of the ethanol molecules in the phospholipid bilayers was determined in their gel and fluid phases. We find that the ethanol molecules reside in the head group region of the bilayers, with 1.6 ethanol molecules per lipid molecule in the gel phase and 1.2 ethanol molecules per lipid molecule in the fluid phase. We find evidence for enhanced permeability in both fluid and gel phases of the phospholipid bilayers in the presence of ethanol molecules. Elastic and quasi-elastic neutron scattering data, obtained using a neutron backscattering spectrometer, was used to study slow, nanosecond molecular dynamics on length scales corresponding to lipid diffusion, acyl chain dynamics and solvent dynamics. While the presence of ethanol molecules had no observable effect on these types of dynamics in the fluid (L a ) phase, the membranes appeared to have a higher degree of order in gel (L b ) and ripple (P b 0 ) phases. In particular, lipid diffusion was found to be slower by a factor of two in the more rigid gel phase when ethanol was present