Revealing crystalline domains in a mollusc shell single-crystalline prism.

Biomineralization integrates complex processes leading to an extraordinary diversity of calcareous biomineral crystalline architectures, in intriguing contrast with the consistent presence of a sub-micrometric granular structure. Hence, gaining access to the crystalline architecture at the mesoscale, that is, over a few granules, is key to building realistic biomineralization scenarios. Here we provide the nanoscale spatial arrangement of the crystalline structure within the 'single-crystalline' prisms of the prismatic layer of a Pinctada margaritifera shell, exploiting three-dimensional X-ray Bragg ptychography microscopy. We reveal the details of the mesocrystalline organization, evidencing a crystalline coherence extending over a few granules. We additionally prove the existence of larger iso-oriented crystalline domains, slightly misoriented with respect to each other, around one unique rotation axis, and whose shapes are correlated with iso-strain domains. The highlighted mesocrystalline properties support recent biomineralization models involving partial fusion of oriented nanoparticle assembly and/or liquid droplet precursors.

Neutron reflectivity measurements at the oil/water interface for the study of stimuli-responsive emulsions⋆.

Stable stimuli-responsive emulsions between oil and water are formed with an amphiphilic block copolymer bearing polystyrene (PS) and poly(dimethylaminoethyl methacrylate) (PDMAEMA) moieties. Different kinds of emulsions like direct, multiple or inverse ones are reproducibly formed as a function of chemical parameters such as p H and salt concentration. To test the correlation between the different nature of the emulsion and the conformation of the polymer chain at the interface, neutron reflectometry at the oil/water interface was carried out. An original sample cell was built and the procedure to get reliable results with it on the FIGARO reflectometer at the Institut Laue-Langevin is described. Results show that for direct emulsions, the copolymer is much more extended on the water side than on the oil side. In the case where multiple emulsions are stabilized, the conformation is strongly modified and is compatible with a more equilibrated extension of the chain on both sides. The inverse case shows that the extension in oil is stronger than in water. These results are discussed in term of polymer brushes (charged or neutral) extension with respect to salt addition and hydrophobic interactions.

Correction: Breaking of the Bancroft rule for multiple emulsions stabilized by a single stimulable polymer.

Correction for 'Breaking of the Bancroft rule for multiple emulsions stabilized by a single stimulable polymer' by L. Besnard et al., Soft Matter, 2014, 10, 7073-7087.

Breaking of the Bancroft rule for multiple emulsions stabilized by a single stimulable polymer.

We investigated emulsions of water and toluene stabilized by (co)polymers consisting of styrene (S) and 2-(dimethylamino)ethyl methacrylate (DMAEMA) monomer units with different compositions and structures such as a PDMAEMA homopolymer, a P(S-co-DMAEMA) random copolymer and various PS-b-PDMAEMA and PS-b-(S-co-DMAEMA) block copolymers. The model system is used to study the fundamental conditions under which the different kinds of polymer-stabilized emulsions (direct oil in water, inverse water in oil and multiple emulsions) are stabilized or destabilized by pH change (at constant temperature). Polymer properties like chain conformation at the toluene-water interface as probed by SANS and neutron reflectivity at the liquid-liquid interface, the oil-water partitioning of the polymer chains (Bancroft's rule of thumb) as determined by UV spectroscopy and interfacial tensions measured by the rising and spinning drop techniques are determined. Overall, results evidence that the curvature sign, as defined by positive and negative values as the chain segments occupy preferentially the water and toluene sides of the interface respectively, reliably predicts the emulsion kind. In contrast, the Bancroft rule failed at foreseeing the emulsion type. In the region of near zero curvature the crossover from direct to inverse emulsions occurs through the formation of either unstable coexisting direct and inverse emulsions (i) or multiple emulsions (ii). The high compact adsorption of the chains at the interface as shown by low interfacial tension values does not allow to discriminate between both cases. However, the toluene-water partitioning of the polymeric emulsifier is still a key factor driving the formation of (i) or (ii) emulsions. Interestingly, the stabilization of the multiple emulsions can be tuned to a large extent as the toluene-water polymer partitioning can be adjusted using quite a large number of physico-chemical parameters linked to polymer architecture like diblock length ratio or polymer total molar mass, for example. Moreover, we show that monitoring the oil-water partitioning aspect of the emulsion system can also be used to lower the interfacial tension at low pH to values slightly higher than 0.01 mN m(-1), irrespective of the curvature sign.

The European strategy for accelerator-based photon science.

The League of European Accelerator-based Photon Sources (LEAPS), comprising 19 large-scale user facilities in 10 member and associated states, has put forward for the first time a European strategy for a transformative way of cooperation, thereby mobilizing the members' substantial expertise in photon science and technology, in infrastructure management and service to users and stakeholders. This European Strategy for Accelerator-based Photon Sources-ESAPS 2022-is a coherent pan-European plan addressing the future challenges and needs of the new era in research and innovation, designed to put Europe in a global leadership position in important future key technologies. In ESAPS2022, ambitious facility upgrades and technology development plans as well as a new strategic challenge-driven use of these facilities are discussed.

Supported bilayers: combined specular and diffuse X-ray scattering.

A method is proposed for the analysis of specular and off-specular reflectivity from supported lipid bilayers. Both thermal fluctuations and the "static" roughness induced by the substrate are carefully taken into account. Examples from supported bilayers and more complex systems comprising a bilayer adsorbed or grafted on the substrate and another "floating" bilayer are given. The combined analysis of specular and off-specular reflectivity allows the precise determination of the structure of adsorbed and floating bilayers, their tension, bending rigidity and interaction potentials. We show that this new method gives a unique opportunity to investigate phenomena like protrusion modes of adsorbed bilayers and opens the way to the investigation of more complex systems including different kinds of lipids, cholesterol or peptides.

Reduction in the surface energy of liquid interfaces at short length scales

Liquid-vapour interfaces, particularly those involving water, are common in both natural and artificial environments. They were first described as regions of continuous variation of density, caused by density fluctuations within the bulk phases. In contrast, the more recent capillary-wave models assumes a step-like local density profile across the liquid-vapour interface, whose width is the result of the propagation of thermally excited capillary waves. The model has been validated for length scales of tenths of micrometres and larger, but the structure of liquid surfaces on submicrometre length scales--where the capillary theory is expected to break down--remains poorly understood. Here we report grazing-incidence X-ray scattering experiments that allow for a complete determination of the free surface structure and surface energy for water and a range of organic liquids. We observe a large decrease of up to 75% in the surface energy of submicrometre waves that cannot be explained by capillary theory, but is in accord with the effects arising from the non-locality of attractive intermolecule interactions as predicted by a recent density functional theory. Our data, and the results of comparable measurements on liquid solutions, metallic alloys, surfactants, lipids and wetting films should thus provide a stringent test for any new theories that attempt to describe the structure of liquid interfaces with nanometre-scale resolution.

Hydrated cholesterol: phospholipid domains probed by synchrotron radiation.

X-ray scattering experiments on mixed films of cholesterol and phospholipids at air-water and Si solid-water interfaces were undertaken to glean information on pathological crystallization of cholesterol bilayers. Grazing-incidence X-ray diffraction patterns at the air-water interface of various cholesterol:dipalmitoyl-phosphatidylcholine (Ch:DPPC) monolayer mixtures compressed beyond monolayer collapse yielded the established 10 x 7.5 Ų Ch bilayer motif, for Ch:DPPC molar ratios higher than 2.5:1. Attempts to obtain a diffraction signal from various Ch:phospholipid film mixtures at the Si solid-water interface, indicative of the presence of the Ch bilayer motif, were unsuccessful. Only after removal of sufficient water from the cell was a weak diffraction signal obtained suggestive of a cholesterol film two bilayers thick. Off-specular X-ray reflectivity measurements made on a 1.75:1 mixture of Ch and bovine cardiac phosphatidylcholine (BCPC) deposited as a bilayer on a Si wafer and placed in a cell filled with water yielded positive results. The derived electron density profile showed the presence of a bilayer mixture consistent with a phase separation of cholesterol and BCPC, and possible formation of a crystalline cholesterol bilayer within the hydrated mixed bilayer, but not a proof thereof.

Grazing Incidence X-ray diffraction on Langmuir films: toward atomic resolution.

We have analyzed grazing incidence diffration (GIXD) data from condensed phases of Langmuir films of long-chain fatty acids at the air-water interface by using a new method consisting of a careful extraction of the structure factors followed by fitting of molecular parameters. We show that, contrary to the general belief, the information contained in GIXD spectra is enough to obtain near-atomic structural information. In particular, we directly determine for the first time the orientation of the chain backbone planes and of the carboxylic headgroups and we evaluate chain conformation defects. This new method allowed us to evidence a new phase of symmetry p2gm at high pressure, corresponding to a minimum in lattice energy, but never observed.

Growth of bimolecular films of three-tailed amphiphiles.

The three-tailed amphiphile ferric stearate molecule, which forms a bimolecular layer on water surface with molecules in the lower and upper layers in different conformations, has been studied to understand transfer and growth of bimolecular films on the surface of hydrophilic silicon substrates. This bimolecular film forms a two-dimensional lattice on water with a slightly distorted hexagonal lattice where both the in-plane and out-of-plane domain sizes are small. The film also showed larger microscopic rigidity compared to its macroscopic mechanical response. This asymmetric bimolecular layer was found to be preserved when the film is transferred on the substrates at different values of surface pressures ranging from 1 mN/m to near-collapse (55 mN/m). Both the upper and lower layers become denser and interfaces between these layers become sharper with increase in deposition pressure but the growths have different natures. The lower layer of transferred film is dense from 1 mN/m and, except for a steplike increase between 20 and 30 mN/m, changes slowly in density. The density of the upper molecular layer grows continuously with surface pressure.

Dramatic enhancement of capillary wave fluctuations of a decorated water surface.

We have demonstrated by x-ray diffuse scattering that a bimolecular layer of a preformed three-tailed amphiphile, ferric stearate, drastically enhances capillary wave fluctuations on water surface due to a reduction in surface tension to 1 mN/m . The bimolecular layer is composed of molecules in symmetric configuration, on top of molecules in asymmetric configuration with ferric ions in contact with water. Unlike the usual Langmuir monolayers, this layer of molecules does not rupture under compression, but becomes thicker. This behavior mimics folding of a membrane on a liquid surface and is closely related to the cohesive interaction brought by the ferric ions. The low effective tension of this artificial membrane depends on the available area and reduces as the microscopic excess area increases.

pH-dependent kinetics of MgCl2 adsorption under a fatty-acid Langmuir film.

The effect of subphase pH (5.5 and 10.5) on the structure of behenic-acid monolayers was investigated during Mg(2+) adsorption by means of Grazing Incidence X-ray Diffraction (GIXD) and Brewster Angle Microscopy (BAM). The final phase corresponding to an ion superlattice commensurate to the behenic-acid cell is pH-independent. In contrast, the sequence of phases evidenced from the initial L(2)-phase to this final state presents at pH 10.5 an additional stage associated to a film condensation toward the L' (2)-phase. The structures of the intermediate states preceding the superstructure nucleation are slightly different, both with a short-range fatty-acid order. Finally, a laser light effect that could result from visible light absorption by the inorganic complexes is evidenced in the final state as well as in the intermediate phases.

Oil-in-water microemulsions stabilized by charged diblock copolymers.

We present here oil-in-water microemulsions stabilized by charged diblock copolymers alone, along with their structural characterization by small-angle neutron scattering measurements. They consist of swollen spherical micelles containing small amounts of oil in their core, which is surrounded by a corona of stretched polyelectrolyte chains. Structural changes, including core size variations, are evidenced when using a cosurfactant, or upon addition of salt, through a contraction of the charged corona. Attempts to relate the micellar structure to the individual copolymer characteristics are also presented, and show that the size of the hydrophobic block mainly determines that of the micelles.

Structure and fluctuations of a single floating lipid bilayer.

A single lipid molecular bilayer of 17 or 18 carbon chain phosphocholines, floating in water near a flat wall, is prepared in the bilayer gel phase and then heated to the fluid phase. Its structure (electron density profile) and height fluctuations are determined by using x-ray reflectivity and non-specular scattering. By fitting the off-specular signal to that calculated for a two-dimensional membrane using a Helfrich Hamiltonian, we determine the three main physical quantities that govern the bilayer height fluctuations: The wall attraction potential is unexpectedly low; the surface tension, roughly independent on chain length and temperature, is moderate (approximately 5 x 10(-4) J.m(-2)) but large enough to dominate the intermediate range of the fluctuation spectrum; and the bending modulus abruptly decreases by an order-of-magnitude from 10(-18) J to 10(-19) J at the bilayer gel-to-fluid transition.

Thickness and density profiles of polyelectrolyte brushes: dependence on grafting density and salt concentration.

We have performed neutron reflectivity measurements on a monolayer of charged diblock copolymers in a Langmuir trough, and determined precise density profiles of the polyelectrolyte brush at different densities. We obtain profiles in good agreement with existing self-consistent field computations, both for the osmotic and the salted brush regime. We show that the osmotic brush's thickness increases with density.

X-ray synchrotron study of liquid-vapor interfaces at short length scales: effect of long-range forces and bending energies.

We have investigated the small-scale structure of the liquid-vapor interface using synchrotron x-ray scattering for liquids with different molecular structures and interactions. The effective momentum-dependent surface energy first decreases from its macroscopic value due to the effect of long-range forces, and then increases with increasing wave vector. The results are analyzed using a recent density functional theory. The large wave-vector increase is attributed to a bending energy for which local and nonlocal contributions are equally important.

Organization of cyanobiphenyl liquid crystal molecules in prewetting films spreading on silicon wafers.

We observe prewetting films of 8CB (4'-n-octyl-4-cyanobiphenyl) spreading at room temperature on silicon wafers by ellipsometry and x-ray reflectivity. Ellipsometry indicates the formation of a nondense monolayer spreading in front of a 45-A-thick film. X-ray reflectivity, performed using a ribbon geometry for the liquid crystal (LC) reservoir, allows us to determine the organization of the 8CB molecules in the homogenous film. It consists of a trilayer stacking with a smecticlike bilayer standing above a polar monolayer with tilted molecules. We show that the thickness of the bilayer is equal to the smectic periodicity in the bulk material and that the tilt angle of the molecules in contact with the solid surface is close to 60 degrees, in good agreement with second-harmonic generation studies reported by other groups. Such organization can be precisely determined using x-ray reflectivity because it induces a modulation of the electron density along the normal to the surface. Furthermore, a study of the ellispometric profile of a drop heated in the nematic phase, where we observe a complete spreading of the LC, shows the complex structuration of the LC close to the solid interface. In particular, the spreading behavior of the trilayer compared to the subsequent smecticlike bilayers indicates the existence of specific interaction between the trilayer and silicon wafer.