Bruno Demé

Self-assembly of regular hollow icosahedra in salt-free catanionic solutions

Self-assembled structures having a regular hollow icosahedral form (such as those observed for proteins of virus capsids) can occur as a result of biomineralization processes, but are extremely rare in mineral crystallites. Compact icosahedra made from a boron oxide have been reported, but equivalent structures made of synthetic organic components such as surfactants have not hitherto been observed. It is, however, well known that lipids, as well as mixtures of anionic and cationic single chain surfactants, can readily form bilayers that can adopt a variety of distinct geometric forms: they can fold into soft vesicles or random bilayers (the so-called sponge phase) or form ordered stacks of flat or undulating membranes. Here we show that in salt-free mixtures of anionic and cationic surfactants, such bilayers can self-assemble into hollow aggregates with a regular icosahedral shape. These aggregates are stabilized by the presence of pores located at the vertices of the icosahedra. The resulting structures have a size of about one micrometre and mass of about 1010 daltons, making them larger than any known icosahedral protein assembly or virus capsid. We expect the combination of wall rigidity and holes at vertices of these icosahedral aggregates to be of practical value for controlled drug or DNA release.

Contribution of galactoglycerolipids to the 3-dimensional architecture of thylakoids

Thylakoid membranes, the universal structure where photosynthesis takes place in all oxygenic photosynthetic organisms from cyanobacteria to higher plants, have a unique lipid composition. They contain a high fraction of 2 uncharged glycolipids, the galactoglycerolipids mono‐ and digalactosyldiacylglycerol (MGDG and DGDG, respectively), and an anionic sulfolipid, sulfoquinovosediacylglycerol (SQDG). A remarkable feature of the evolution from cyanobacteria to higher plants is the conservation of MGDG, DGDG, SQDG, and phosphatidylglycerol (PG), the major phospholipid of thylakoids. Using neutron diffraction on reconstituted thylakoid lipid extracts, we observed that the thylakoid lipid mixture self‐organizes as a regular stack of bilayers. This natural lipid mixture was shown to switch from hexagonal II toward lamellar phase on hydration. This transition and the observed phase coexistence are modulated by the fine‐tuning of the lipid profile, in particular the MGDG/DGDG ratio, and by the hydration. Our analysis highlights the critical role of DGDG as a contributing component to the membrane stacking via hydrogen bonds between polar heads of adjacent bilayers. DGDG interactions balance the repulsive electrostatic contribution of the charged lipids PG and SQDG and allow the persistence of regularly stacked membranes at high hydration. In developmental contexts or in response to environmental variations, these properties can contribute to the highly dynamic flexibility of plastid structure.—Demé, B., Cataye, C., Block, M. A., Maréchal, E., Jouhet, J. Contribution of galactoglycerolipids to the 3‐dimensional architecture of thylakoids. FASEB J. 28, 3373–3383 (2014). www.fasebj.org

Hydration dependent studies of highly aligned multilayer lipid membranes by neutron scattering

We investigated molecular motions on a picosecond timescale of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) model membranes as a function of hydration by using elastic and quasielastic neutron scattering. Two different hydrations corresponding to approximately nine and twelve water molecules per lipid were studied, the latter being the fully hydrated state. In our study, we focused on head group motions by using chain deuterated lipids. Information on in-plane and out-of-plane motions could be extracted by using solid supported DMPC multilayers. Our studies confirm and complete former investigations by König et al. [J. Phys. II (France) 2, 1589 (1992)] and Rheinstädter et al. [Phys. Rev. Lett. 101, 248106 (2008)] who described the dynamics of lipid membranes, but did not explore the influence of hydration on the head group dynamics as presented here. From the elastic data, a clear shift of the main phase transition from the P(β) ripple phase to the L(α) liquid phase was observed. Decreasing water content moves the transition temperature to higher temperatures. The quasielastic data permit a closer investigation of the different types of head group motion of the two samples. Two different models are needed to fit the elastic incoherent structure factor and corresponding radii were calculated. The presented data show the strong influence hydration has on the head group mobility of DMPC.

Disposition of ceramide in model lipid membranes determined by neutron diffraction.

The lipid matrix present in the uppermost layer of the skin, the stratum corneum, plays a crucial role in the skin barrier function. The lipids are organized into two lamellar phases. To gain more insight into the molecular organization of one of these lamellar phases, we performed neutron diffraction studies. In the diffraction pattern, five diffraction orders were observed attributed to a lamellar phase with a repeat distance of 5.4 nm. Using contrast variation, the scattering length density profile could be calculated showing a typical bilayer arrangement. To obtain information on the arrangement of ceramides in the unit cell, a mixture that included a partly deuterated ceramide was also examined. The scattering length density profile of the 5.4-nm phase containing this deuterated ceramide demonstrated a symmetric arrangement of the ceramides with interdigitating acyl chains in the center of the unit cell.

Swelling of a Lecithin Lamellar Phase Induced by Small Carbohydrate Solutes

In this paper, we consider the effect of adding small carbohydrate solutes (small sugars) to DMPC (1,2-dimyristoyl-sn-glycero-3-phosphocholine) L(alpha) dispersions and the consequences on the force balance at zero osmotic pressure (maximal swelling). We show the importance of long incubations required to obtain samples at thermodynamic equilibrium where molecular diffusion has been completed. The monotonic increase of maximal swelling versus sugar content occurs as a combined effect of the screening of the van der Waals contribution and fluctuations in the lamellar stacks. According to this new approach, it is shown that changes in dielectric properties result in a much less pronounced effect than entropic forces (undulations) generated by the softening of the membranes at high sugar content. However, this sugar-induced swelling cannot be explained quantitatively by adding an entropic contribution to molecular interactions. Quantitative disagreement between the proposed mechanism and our observations is due either to nonadditivity of molecular interactions with entropic forces or to the relation used to account for the entropic contribution.

Study of the Influence of the Penetration Enhancer Isopropyl Myristate on the Nanostructure of Stratum Corneum Lipid Model Membranes Using Neutron Diffraction and Deuterium Labelling

In order to elucidate the mode of action of the lipophilic penetration enhancer isopropyl myristate (IPM) on a molecular scale, we investigated oriented quaternary stratum corneum (SC) lipid model membranes based on ceramide AP, cholesterol, palmitic acid and cholesterol sulfate containing 10 wt% IPM by means of neutron diffraction. Our results indicate that IPM affects the lamellar lipid assembly in terms of bilayer perturbation and disordering. Phase segregation occurred, indicating that IPM is not likely to mix properly with the other SC lipids due to its branched structure. We used selective deuterium labelling to localize the penetration enhancer, and could successfully prove the presence of IPM in the two coexisting lamellar phases. We conclude that IPM’s mode of action as penetration promoter is presumably based on incorporation into the SC lipid matrix, extraction of certain SC lipids into a separate phase and perturbation of the multilamellar lipid assembly.

In-plane distribution in mixtures of cationic and anionic surfactants

Mixtures of cationic and anionic surfactants, also called “catanionic” mixtures, self-assemble into aggregates which show a rich variety of morphologies in the nanometre to micron range controlled by the molar ratio between surfactants. At the molecular scale, little is known about the local distribution of surfactants in the bilayer. Here, we determine the in-plane distribution of the cationic and anionic surfactants in catanionic bilayers using neutron scattering and the contrast matching technique. The coexistence of two different in-plane orders is experimentally demonstrated: both surfactants share a common two-dimensional hexagonal lattice with a long-range order, but the distribution of alternate (+) and (−) charged head groups shows only a two-dimensional liquid-like local order. Comparing experiments and Monte-Carlo simulations, we establish that this lateral liquid order is attenuated by the counterions of the bilayers, but is less than expected in a mean-field approach. This demonstrates that electrostatic interactions participate in, but do not completely determine, the local distribution of surfactants of opposite charge in the bilayer.

Conformation, defects, and dynamics of a discotic liquid crystal and their influence on charge transport.

Future applications of discotic liquid crystals (DLCs) in electronic devices depend on a marked improvement of their conductivity properties. We present a study of 2,3,6,7,10,11-hexakishexyloxytriphenylene (HAT6) and show how local conformation, structural defects, and thermal motions on the picosecond time scale strongly affect the efficient charge transport in DLCs. A direct and successful comparison of classical molecular dynamics (MD) simulations with both neutron powder diffraction and quasielastic neutron scattering (QENS) give a full insight into the structural and dynamical properties of HAT6. The local conformation of HAT6 molecules is characterized by a mutual rotation (twist) angle of about 37° and typically a mutual aromatic-core distance of 3.4 Å instead of the average distance of 3.65 Å usually quoted. We show that a considerable number of structural traps is present in HAT6, which persist at the picosecond time scale. We find that the high disorder in the mutual positions of the aromatic cores is an important factor contributing to the limited conductivity of HAT6 compared to larger DLCs.

Inner structure of adsorbed ionic microgel particles.

Microgel particles of cross-linked poly(NIPAM-co-acrylic acid) with different acrylic acid contents are investigated in solution and in the adsorbed state. As a substrate, silicon with a poly(allylamine hydrochloride) (PAH) coating is used. The temperature dependence of the deswelling of the microgel particles was probed with atomic force microscopy (AFM). The inner structure of the adsorbed microgel particles was detected with grazing incidence small angle neutron scattering (GISANS). Small angle neutron scattering (SANS) on corresponding microgel suspensions was performed for comparison. Whereas the correlation length of the polymer network shows a divergence in the bulk samples, in the adsorbed microgel particles it remains unchanged over the entire temperature range. In addition, GISANS indicates changes in the particles along the surface normal. This suggests that the presence of a solid surface suppresses the divergence of internal fluctuations in the adsorbed microgels close to the volume phase transition.

Polysaccharides at interfaces 1. Adsorption of cholesteryl-pullulan derivatives at the solution-air interface. Kinetic study by surface tension measurements

The surface properties of a series of cholesteryl-pullulan (CHP) derivatives have been assessed by surface tension measurements at the solution-air interface. The results reveal that these properties are related to the nature of the hydrophobic cholesteryl group substituted in pullulan, and that the unsubstituted polysaccharide does not display any surface activity. The adsorption kinetics of such an amphiphilic macromolecule has been shown to be diffusion controlled, obeying the Ward and Tordai¨diffusional model only at low solution concentrations. In the 2 × 10−7–5 × 10−6 mol l−1 concentration range for which this model is verified, the calculated diffusion coefficients are concentration dependent. The non-ideality of the system at higher concentrations may be explained both by the presence of solute/solute interactions in solution and in adsorbed monolayers, and by the existence of an adsorbed layer, even at time t0, which prevents the process of adsorption from being governed only by diffusion.