RESUMO
Water activity and its relationship with interactions stabilising lamellar stacks of mixed lipid bilayers in their fluid state are investigated by means of osmotic pressure measurements coupled with small-angle X-ray scattering. The (electrically neutral) bilayers are composed of a mixture in various proportions of lecithin, a zwitterionic phospholipid, and Simulsol, a non-ionic cosurfactant with an ethoxylated polar head. For highly dehydrated samples the osmotic pressure profile always exhibits the "classical" exponential decay as hydration increases but, depending on Simulsol to lecithin ratio, it becomes either of the "bound" or "unbound" types for more water-swollen systems. A simple thermodynamic model is used for interpreting the results without resorting to the celebrated but elusive "hydration forces".
Assuntos
Interações Hidrofóbicas e Hidrofílicas , Bicamadas Lipídicas/química , Termodinâmica , Pressão Osmótica , Tensoativos/química , Água/químicaRESUMO
Structure and interactions stabilising the lamellar stack of mixed lipid bilayers in their fluid state are investigated by means of small-angle X-ray scattering. The (electrically neutral) bilayers are composed of a mixtures of lecithin, a zwitterionic phospholipid, and Simulsol, a non-ionic cosurfactant with an ethoxylated polar head. The soft confinement of the bilayer hydrophilic components is varied by changing hydration and bilayer composition, as well as the length of the cosurfactant polar head. Structural transitions are observed at low hydration, in the stacking order for the longer cosurfactant, and in the mixed bilayers for the shorter one. At higher hydration, the swelling of the lamellar stacks occurs with a significant, but continuous evolution in the mixed bilayer structure. The bilayer structural changes are discussed in analogy with the so-called "brush-to-mushroom" transition induced by lateral confinement, relevant for long linear polymers grafted onto rigid surfaces, taking also into account the role of vertical confinement.
RESUMO
Simultaneous measurements of small-angle neutron scattering and dynamic light scattering have been performed on a binary mixture of partially miscible liquids, 2,6-dimethylpyridine and water. At critical composition the temperature dependence of the correlation length of fluctuations in composition is strongly affected by the addition of nanoparticles of a triblock copolymer polyethylene oxide-polypropylene oxide-polyethylene oxide. A crossover between Ising-type critical behavior and mean-field critical behavior is observed when the correlation length is equal to the size of the nanoparticles.
RESUMO
Using Fluorescence Recovery After Photobleaching, we investigate the Brownian motion of DNA rod-like fragments in two distinct anisotropic phases with a local nematic symmetry. The height of the measurement volume ensures the averaging of the anisotropy of the in-plane diffusive motion parallel or perpendicular to the local nematic director in aligned domains. Still, as shown in using a model specifically designed to handle such a situation and predicting a non-Gaussian shape for the bleached spot as fluorescence recovery proceeds, the two distinct diffusion coefficients of the DNA particles can be retrieved from data analysis. In the first system investigated (a ternary DNA-lipid lamellar complex), the magnitude and anisotropy of the diffusion coefficient of the DNA fragments confined by the lipid bilayers are obtained for the first time. In the second, binary DNA-solvent system, the magnitude of the diffusion coefficient is found to decrease markedly as DNA concentration is increased from isotropic to cholesteric phase. In addition, the diffusion coefficient anisotropy measured within cholesteric domains in the phase coexistence region increases with concentration, and eventually reaches a high value in the cholesteric phase.
Assuntos
DNA/química , Difusão , Modelos Químicos , Movimento (Física) , Anisotropia , Simulação por Computador , Fragmentação do DNA , Fluorescência , Bicamadas Lipídicas/química , FotodegradaçãoRESUMO
The structure of a complex between hydrated DNA and a non-cationic lipid is studied, including its phase diagram. The complex is spontaneously formed by adding DNA fragments (ca. 150 base pairs in length) to non-cationic lipids and water. The self-assembly process often leads to highly ordered structures. The structures were studied by combining X-ray scattering, fluorescence and polarized microscopy, as well as freeze-fracture experiments with transmission electron microscopy. We observe a significant increase of the smectic order as DNA is incorporated into the water layers of the lamellar host phase, and stabilization of single phase domains for large amounts of DNA. The effect of confinement on DNA ordering is investigated by varying the water content, following three dilution lines. A rich polymorphism is found, ranging from weakly correlated DNA-DNA in-plane organizations to highly ordered structures, where transmembrane correlations lead to the formation of columnar rectangular and columnar hexagonal superlattices of nucleotides embedded between lipid lamellae. From these observations, we suggest that addition of DNA to the lamellar phase significantly restricts membrane fluctuations above a certain concentration and helps the formation of the lipoplex. The alteration of membrane steric interactions, together with the appearance of interfacial interactions between membranes and DNA molecules may be a relevant mechanism for the emergence of highly ordered structures in the concentrated regime.
Assuntos
DNA/química , Lipídeos/química , Animais , Bovinos , DNA/metabolismo , Metabolismo dos Lipídeos , Água/químicaRESUMO
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/ H(2)O and non-ionic ( C(12)E(5) /hexanol/ H(2)O 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 ( perpendicular) versus the separation between the membranes d(w). Depending on the composition of the lamellar phase, this distance can be continuously adjusted from 500A to about 20A. For all systems, we observe a first regime, called dilute regime, where the diffusion coefficient decreases almost linearly with 1/d (w) . In this regime, the Faxén 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 ( C(12)E(5) /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.
Assuntos
Ácido Dioctil Sulfossuccínico/química , Bicamadas Lipídicas/química , Soluções/química , Tensoativos/química , Difusão , Fluorescência , Hexanóis/química , Fluidez de Membrana , Microscopia Confocal , Modelos Moleculares , Transição de Fase , Soroalbumina Bovina/química , Cloreto de Sódio/química , Propriedades de Superfície , Água/químicaRESUMO
We studied the micelle formation of a diblock copolymer of styrene and ethylene oxide in mixtures of 2,6-dimethylpyridine (2,6-lutidine) and water. Micelles are formed in a broad solvent composition range with a volume fraction of water ranging from 0.05 to 0.85, where neither polystyrene nor polyethylene oxide homopolymers are soluble. The diffusion behavior of pure solvent mixtures and in solutions of copolymer micelles is reported. In LTD/water mixtures, two diffusive processes corresponding to self-difusion and two modes belonging to mutual diffusion and diffusion of solvent clusters have been found. In copolymer solutions, the mode of copolymer micelle diffusion replaces the mode of solvent cluster diffusion. Quasielastic light scattering, small-angle neutron scattering, and pulsed-field gradient NMR have been employed in our study.
RESUMO
We report X-ray resonant scattering experiments performed on the prototype liquid-crystalline compound MHPOBC doped with a chemical probe containing a resonant atom (selenium). We determined directly for the first time the microscopic 3- and 4-layer structure of the ferrielectric subphases (SmC(FI1)* and SmC(FI2)*) present in MHPOBC. Despite the low fraction of the selenium probe, the resonant signal is strong enough to allow an unambiguous determination of the basic structure of the ferrielectric subphases. These experiments demonstrate that the resonant scattering technique can be extended to liquid crystalline materials without resonant element and may stimulate new studies. A non-resonant Bragg reflection was also found in the SmC(FI1)* phase in pure MHPOBC, consistent with the 3-layer distorted model, but never detected before.
Assuntos
Compostos Férricos/química , Cristais Líquidos/química , Manufaturas/análise , Teste de Materiais/métodos , Espalhamento de Radiação , Difração de Raios XRESUMO
We study asymmetric block copolymers with the simple diblock AB architecture, in the case where the longer block A is both hydrophobic and "soft", whereas the shorter block B is hydrophilic and "hard". Materials with such a particular combination of physico-chemical and mechanical properties have distinctive advantages, in particular for designing water-compatible adhesive materials. The phase diagram is established, combining NMR and SAXS characterisations of the materials. The swelling with water is monitored through gravimetry and "time-resolved" SAXS. Indications of maintained adhesive properties in a wet environment are given.
RESUMO
We perform traction experiments on viscous liquids highly confined between parallel plates, a geometry known as the probe-tack test in the adhesion community. Direct observation during the experiment coupled to force measurement shows the existence of several mechanisms for releasing the stress: while fingering is favored for low traction velocities, low confinement and low viscosity, nucleation of bubbles occurs in the opposite conditions. It is possible to quantitatively predict the transition between the two regimes and, in many respects, describe the shape of the force response. Using a model for purely viscous fluids, we also present a phase diagram for the different force peak regimes that remarkably accounts for the data. Our results show that conspicuous features of the traction curve commonly thought to be characteristic of soft viscoelastic solids like adhesives are already encountered in liquid materials.