Highly Confined Stacks of Graphene Oxide Sheets in Water

Since the discovery of graphene oxide (GO), the most accessible of the precursors of graphene, this material has been widely studied for applications in science and technology. In this work, we describe a procedure to obtain GO dispersions in water at high concentrations, these highly dehydrated dispersions being in addition fully redispersible by dilution. With the availability of such concentrated samples, it was possible to investigate the structure of hydrated GO sheets in a previously unexplored range of concentrations, and to evidence a structural phase transition. Tentatively applying models designed for describing the small-angle scattering curve in the Smectic A (or L$_{\alpha}$) phase of lyotropic systems, it was possible to extract elastic parameters characterising the system on the dilute side of the transition, thereby evidencing the relevance of both electrostatic and steric (Helfrich) interactions in stabilising aqueous lamellar stacks of GO sheetsComment: 11 pages, 10 figure

Self-Assembling Behavior of Glycerol Monoundecenoate in Water

The self-assembling properties of glycerol esters in water are well known. Still, few data on glycerol monoesters of undecylenic acid are available. The aim of this study was to highlight the behavior of glycerol monoundecenoate (GM-C11:1) in different diluted and concentrated states. Its self-assembling properties in water and upon solid inorganic surfaces were investigated in the diluted state using surface tension experiments, atomic force microscopy, and cryogenic transmission electron microscopy studies. In the concentrated state, the gelling properties in the presence of water were investigated using polarized light microscopy, differential scanning calorimetry (DSC), and small-angle X-ray scattering (SAXS) experiments. GM-C11:1 at 100 mg/L self-assembles at the liquid/air interfaces as aggregates of approximately 20 nm in diameter, organized into concentric forms. These aggregates are spherical globules composed of several molecules of GM-C11:1. At higher concentrations (1000 and 104 mg/L), GM-C11:1 is able to uniformly coat liquid/air and liquid/solid interfaces. In bulk, GM-C11:1 forms spontaneously aggregates and vesicles. In a more concentrated state, GM-C11:1 assembles into lamellar Lβ and Lα forms in water. By cross-referencing SAXS and DSC findings, we were able to distinguish between interlamellar water molecules strongly bound to GM-C11:1 and other molecules remaining unbound and considered to be “mobile” water. The percentage of water strongly bound was proportional to the percentage of GM-C11:1 in the system. In this case, GM-C11:1 appears to be an effective molecule for surface treatments for which water retention is important

The study the properties structurals and elastics of phases lamellar of lipid.

Lamellar systems composed of lipid bilayers have been widely used as model system\ud for investigating properties of biological membranes, interactions between membranes and with biomolecules. The composition of the membrane determines its\ud three dimensional shape and its properties such as rigidity and compressibility\ud which play an important role on membrane fusion, protein adhesion, interactions\ud between proteins, etc. We present a systematic study of a lamellar system composed of lecithin and a commercial co-surfactant (Simusol), which is a mixture of\ud ethoxylated fatty acids. Using X ray scattering and a new procedure to fit X-ray\ud experimental data, we determine relevant parameters characterizing the lamellar\ud structure, varying membrane composition from 100% of lecithin to 100% of Simulsol. We present experimental data illustrating the swelling behavior for the membrane of different compositions and the respective behavior of the Caillé parameter.\ud From and GISAXS experiments on oriented films under controlled humidity we investigate the compressibility of the lamellar phase and the effect of incorporating\ud co-surfactant. Combining the Caillé parameter and compressibility studies we determine the bending rigidity of membranes. The results obtained with this experimental approach and new procedure to fit X-ray experimental allows us to identify\ud structural changes in the bilayer depending both on hydration and co-surfactant\ud content, with implications on elastic properties of membranes

Enhanced Food Anticipatory Activity Associated with Enhanced Activation of Extrahypothalamic Neural Pathways in Serotonin2C Receptor Null Mutant Mice

The ability to entrain circadian rhythms to food availability is important for survival. Food-entrained circadian rhythms are characterized by increased locomotor activity in anticipation of food availability (food anticipatory activity). However, the molecular components and neural circuitry underlying the regulation of food anticipatory activity remain unclear. Here we show that serotonin2C receptor (5-HT2CR) null mutant mice subjected to a daytime restricted feeding schedule exhibit enhanced food anticipatory activity compared to wild-type littermates, without phenotypic differences in the impact of restricted feeding on food consumption, body weight loss, or blood glucose levels. Moreover, we show that the enhanced food anticipatory activity in 5-HT2CR null mutant mice develops independent of external light cues and persists during two days of total food deprivation, indicating that food anticipatory activity in 5-HT2CR null mutant mice reflects the locomotor output of a food-entrainable oscillator. Whereas restricted feeding induces c-fos expression to a similar extent in hypothalamic nuclei of wild-type and null mutant animals, it produces enhanced expression in the nucleus accumbens and other extrahypothalamic regions of null mutant mice relative to wild-type subjects. These data suggest that 5-HT2CRs gate food anticipatory activity through mechanisms involving extrahypothalamic neural pathways

Twisted smectics as the liquid crystal analogues of type II superconductors

In 1972, de Gennes pointed out the formal analogy between the Landau-Ginzburg Hamiltonians describing the phase transition from normal to superconductor on one hand and from nematic to smectic A liquid crystals on the other hand. This elegant analogy became a source of inspiration not only for theoreticians, as it revealed and emphasised the beauty and the richness of the physics of liquid crystals, but also for chemists in their constant search for novel liquid crystalline structures. The analogy with type I superconductors was first described and bore an appropriate educational value: the expulsion of twist in smectic liquid crystals can be viewed as equivalent to the well-known Meissner effect in superconductors.However, the investigation of the type II condition definitely opened new doors as it led to the discovery of fantastic new liquid crystal structures. In 1988, Renn and Lubensky 'invented' the Twist Grain Boundary (TGB) smectic phase as the direct analogue of the Abrikosov flux lattice. The twist penetrates the smectic layers of a TGB via a twisted lattice of screw dislocations analogous to magnetic vortices, just as the magnetic field penetrates the type II superconductor. We review in this paper the major steps of the experimental studies of the TGB phases and show that the observed behaviours closely follow the superconductor model, hence illustrating the depth of de Gennes' analogy

Self-Assembly of Fatty Acid-Alkylboladiamine Salts

Long-chain fatty acids are insoluble in aqueous solution and form crystal precipitates. It is then of particular importance to determine the physicochemical parameters allowing their dispersion in water to improve their bioavailability and their utilization as surfactants. Herein, we report a study on salt-free catanionic systems in aqueous solution made of mixtures between palmitic or stearic fatty acids and alkylboladiamines (Abd's) differing by their alkyl chain length. Phase contrast microscopy, solid-state NMR, Fourier transform infrared spectroscopy, and small-angle neutron scattering were used to characterize the phase behavior of these systems at molar ratio of fatty acid to Abd of 1 and 2. Whatever the Abd and the molar ratio, fatty acids were embedded at low temperature in a bilayer gel phase which crystallizes after a period of rest. At an equimolar ratio, the gel phases transited upon raising the temperature to an isotropic phase made of wormlike micelles except in the case of the ethylenediamine chain for which a lamellar fluid phase was observed. At a molar ratio of 2 and high temperature, fatty acids were embedded in a lamellar fluid phase which self-orients with its stacking axis perpendicular to the magnetic field. However, for a long alkylboladiamine such as spermine, wormlike micelles formed. The phase behavior at high temperature is discussed in terms of molecular volume

From Nucleobases to Nucleolipids: An ITC Approach on the Thermodynamics of Their Interactions in Aqueous Solutions

Hybrid constructions based on nucleosides and lipophilic components, known as nucleolipids, have become an extremely interesting class of molecules, especially for their potential biomedical applications. In this matter, it seemed important to define the nature and estimate the strength of their interaction with polynucleotides by different ways. We report in this work a systematic investigation through isothermal titration calorimetry of the thermodynamics of the association and dissociation of adenine and thymine derivatives, not previously performed...

Dense Phases of γ-Gliadins in Confined Geometries

The binary phase diagram of γ-gliadin, a wheat storage protein, in water was explored thanks to the microevaporator, an original PDMS microfluidic device. This protein, usually qualified as insoluble in aqueous environments, displayed a partial solubility in water. Two liquid phases, a very dilute and a dense phase, were identified after a few hours of accumulation time in the microevaporator. This liquid–liquid phase separation (LLPS) was further characterized through in situ micro-Raman spectroscopy of the dilute and dense protein phases. Micro-Raman spectroscopy showed a specific orientation of phenylalanine residues perpendicular to the PDMS surfaces only for the diluted phase. This orientation was ascribed to the protein adsorption at interfaces, which would act as nuclei for the growth of dense phase in bulk. This study, thanks to the use of both aqueous solvent and a microevaporator, would provide some evidence for a possible physicochemical origin of the gliadin assembly in the endoplasmic reticulum of albumen cells, leading to the formation of dense phases called protein bodies. The microfluidic tool could be used also in food science to probe protein–protein interactions in order to build up phase diagrams

Dense Phases of γ-Gliadins in Confined Geometries

The binary phase diagram of γ-gliadin, a wheat storage protein, in water was explored thanks to the microevaporator, an original PDMS microfluidic device. This protein, usually qualified as insoluble in aqueous environments, displayed a partial solubility in water. Two liquid phases, a very dilute and a dense phase, were identified after a few hours of accumulation time in the microevaporator. This liquid–liquid phase separation (LLPS) was further characterized through in situ micro-Raman spectroscopy of the dilute and dense protein phases. Micro-Raman spectroscopy showed a specific orientation of phenylalanine residues perpendicular to the PDMS surfaces only for the diluted phase. This orientation was ascribed to the protein adsorption at interfaces, which would act as nuclei for the growth of dense phase in bulk. This study, thanks to the use of both aqueous solvent and a microevaporator, would provide some evidence for a possible physicochemical origin of the gliadin assembly in the endoplasmic reticulum of albumen cells, leading to the formation of dense phases called protein bodies. The microfluidic tool could be used also in food science to probe protein–protein interactions in order to build up phase diagrams

Confined diffusion of hydrophilic probes inserted in lyotropic lamellar phases

The dynamic behaviour of three hydrophilic probes (two dyes and one fluorescently-labelled protein) inserted in the water layers of lyotropic lamellar phases has been studied by confocal fluorescence recovery experiments. Two different, ionic (AOT/NaCl/H2O) and non-ionic (C12E5/hexanol/H2O) host systems were studied. The confinement effect has been carefully monitored using the swelling properties of the lamellar phases. In all cases, we measure the evolution of the probe diffusion coefficient in the layer plane D versus the separation between the membranes dw. Depending on the composition of the lamellar phase, this distance can be continuously adjusted from 500˚A to about 20˚A. For all systems, we observe a first regime, called dilute regime, where the diffusion coefficient decreases almost linearly with 1/dw. In this regime, the Fax´en theory for the friction coefficient of a spherical particle symmetrically dragged between two rigid walls can largely explain our results. More unexpectedly, when the membranes are non-ionic, and also quite flexible (C12E5/hexanol in water), we observe the existence of a second, concentrated (or confined) regime, where the diffusion coefficient is nearly constant and different from zero for membrane separations smaller than the particle size. This new regime can be heuristically explained by simple arguments taking into account the membrane fluidity