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Glycolipids in biological membranes are ubiquitous and believed to be involved in the formation of ordered functional domains. However, our current knowledge about such ...glycolipid-enriched domains is limited because they are inherently difficult to characterize.
We use grazing-incidence X-ray diffraction, isotherm measurements, and Brewster angle microscopy to investigate the phase behavior and miscibility in Langmuir lipid monolayers containing glycolipids.
Glycolipid-enriched domains give rise to distinct diffraction patterns that allow for a systematic structural investigation and reveal a rich phenomenology, ranging from near-complete demixing to the formation of mixed domains with unique features. The phase behavior is governed by the headgroup chemistry and by the length and saturation of the tails.
All surfaces in water experience at short separations hydration repulsion or hydrophobic attraction, depending on the surface polarity. These interactions dominate the more long-ranged electrostatic ...and van der Waals interactions and are ubiquitous in biological and colloidal systems. Despite their importance in all scenarios where the surface separation is in the nanometer range, the origin of these hydration interactions is still unclear. Using atomistic solvent-explicit molecular dynamics simulations, we analyze the interaction free energies of charge-neutral model surfaces with different elastic and water-binding properties. The surface polarity is shown to be the most important parameter that not only determines the hydration properties and thereby the water contact angle of a single surface but also the surface–surface interaction and whether two surfaces attract or repel. Elastic properties of the surfaces are less important. On the basis of surface contact angles and surface–surface binding affinities, we construct a universal interaction diagram featuring three different interaction regimeshydration repulsion, cavitation-induced attractionand for intermediate surface polaritiesdry adhesion. On the basis of scaling arguments and perturbation theory, we establish simple combination rules that predict the interaction behavior for combinations of dissimilar surfaces.
Hydration repulsion dominates the interaction between polar surfaces in water at nanometer separations and ultimately prevents the sticking together of biological matter. Although confirmed by a ...multitude of experimental methods for various systems, its mechanism remained unclear. A simulation technique is introduced that yields accurate pressures between solvated surfaces at prescribed water chemical potential and is applied to a stack of phospholipid bilayers. Experimental pressure data are quantitatively reproduced and the simulations unveil a rich microscopic picture: Direct membrane–membrane interactions are attractive but overwhelmed by repulsive indirect water contributions. Below about 17 water molecules per lipid, this indirect repulsion is of an energetic nature and due to desorption of hydration water; for larger hydration it is entropic and suggested to involve water depolarization. This antagonistic nature and the presence of various compensating contributions indicate that the hydration repulsion is less universal than previously assumed and rather involves finely tuned surface-water interactions.
We established a bacterial membrane model with monolayers of bacterial lipopolysaccharides (LPS Re and LPS Ra) and quantified their viscoelastic properties by using an interfacial stress rheometer ...coupled to a Langmuir film balance. LPS Re monolayers exhibited purely viscous behaviour in the absence of calcium ions, while the same monolayers underwent a viscous-to-elastic transition upon compression in the presence of Ca(2+). Our results demonstrated for the first time that LPSs in bacterial outer membranes can form two-dimensional elastic networks in the presence of Ca(2+). Different from LPS Re monolayers, the LPS Ra monolayers showed a very similar rheological transition both in the presence and absence of Ca(2+), suggesting that longer saccharide chains can form 2D physical gels even in the absence of Ca(2+). By exposure of the monolayers to the antimicrobial peptide protamine, we could directly monitor the differences in resistance of bacterial membranes according to the presence of calcium.
Carbohydrates such as the trisaccharide motif LeX are key constituents of cell surfaces. Despite intense research, the interactions between carbohydrates of apposing cells or membranes are not well ...understood. In this article, we investigate carbohydrate-carbohydrate interactions in membrane adhesion as well as in solution with extensive atomistic molecular dynamics simulations that exceed the simulation times of previous studies by orders of magnitude. For LeX, we obtain association constants of soluble carbohydrates, adhesion energies of lipid-anchored carbohydrates, and maximally sustained forces of carbohydrate complexes in membrane adhesion that are in good agreement with experimental results in the literature. Our simulations thus appear to provide a realistic, detailed picture of LeX-LeX interactions in solution and during membrane adhesion. In this picture, the LeX-LeX interactions are fuzzy, i.e. LeX pairs interact in a large variety of short-lived, bound conformations. For the synthetic tetrasaccharide Lac 2, which is composed of two lactose units, we observe similarly fuzzy interactions and obtain association constants of both soluble and lipid-anchored variants that are comparable to the corresponding association constants of LeX. The fuzzy, weak carbohydrate-carbohydrate interactions quantified in our simulations thus appear to be a generic feature of small, neutral carbohydrates such as LeX and Lac 2.
Many organisms rely on mineral nutrients taken directly from the soil or aquatic environment, and therefore, developed mechanisms to cope with the limitation of a given essential nutrient. For ...example, photosynthetic cells have well-defined responses to phosphate limitation, including the replacement of cellular membrane phospholipids with non-phosphorous lipids. Under phosphate starvation, phospholipids in extraplastidial membranes are replaced by betaine lipids in microalgae. In higher plants, the synthesis of betaine lipid is lost, driving plants to other strategies to cope with phosphate starvation where they replace their phospholipids by glycolipids.
The aim of this work was to evaluate to what extent betaine lipids and PC lipids share physicochemical properties and could substitute for each other. By neutron diffraction experiments and dynamic molecular simulation of two synthetic lipids, the dipalmitoylphosphatidylcholine (DPPC) and the dipalmitoyl-diacylglyceryl-N,N,N-trimethylhomoserine (DP-DGTS), we found that DP-DGTS bilayers are thicker than DPPC bilayers and therefore are more rigid. Furthermore, DP-DGTS bilayers are more repulsive, especially at long range, maybe due to unexpected unscreened electrostatic contribution. Finally, DP-DGTS bilayers could coexist in the gel and fluid phases.
The different properties and hydration responses of PC and DGTS provide an explanation for the diversity of betaine lipids observed in marine organisms and for their disappearance in seed plants.
Membrane systems that naturally occur as densely packed membrane stacks contain high amounts of glycolipids whose saccharide headgroups display multiple small electric dipoles in the form of hydroxyl ...groups. Experimentally, the hydration repulsion between glycolipid membranes is of much shorter range than that between zwitterionic phospholipids whose headgroups are dominated by a single large dipole. Using solvent-explicit molecular dynamics simulations, here we reproduce the experimentally observed, different pressure-versus-distance curves of phospholipid and glycolipid membrane stacks and show that the water uptake into the latter is solely driven by the hydrogen bond balance involved in non-ideal water/sugar mixing. Water structuring effects and lipid configurational perturbations, responsible for the longer-range repulsion between phospholipid membranes, are inoperative for the glycolipids. Our results explain the tight cohesion between glycolipid membranes at their swelling limit, which we here determine by neutron diffraction, and their unique interaction characteristics, which are essential for the biogenesis of photosynthetic membranes.
Specific local arrangements of molecules are the structural fingerprints of important biological processes in cells and tissues but difficult to access experimentally. In the recent work by Bernhardt ...et al (2017 New J. Phys. 19 013012) such order on the nanometer scale has been investigated by in situ correlation of fluorescence-based cell visualization and nano-focused x-ray diffraction. This approach enables selective diffraction analysis guided by fluorescence imaging and opens new perspectives for the investigation of ordered nanostructures in living matter such as fiber bundles, membrane architectures, and newly-formed biominerals.
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