Bending elasticity of a curved amphiphilic film decorated anchored copolymers: a small angle neutron scattering study

Microemulsion droplets (oil in water stabilized by a surfactant film) are progressively decorated with increasing amounts of poly ethylene- oxide (PEO) chains anchored in the film by the short aliphatic chain grafted at one end of the PEO chain . The evolution of the bending elasticity of the surfactant film with increasing decoration is deduced from the evolution in size and polydispersity of the droplets as reflected by small angle neutron scattering. The optimum curvature radius decreases while the bending rigidity modulus remains practically constant. The experimental results compare well with the predictions of a model developed for the bending properties of a curved film decorated by non-adsorbing polymer chains, which takes into account, the finite curvature of the film and the free diffusion of the chains on the film.Comment: 30 June 200

Robust Phase Behavior of Model Transient networks

In order to study the viscoelastic properties of certain complex fluids which are described in terms of a multiconnected transient network we have developed a convenient model system composed of microemulsion droplets linked by telechelic polymers. The phase behavior of such systems has two characteristic features: a large monophasic region which consists of two sub-regions (a fluid sol phase and a viscoelastic gel phase) separated by a percolation line and a two phase region at low volume fraction with separation into a dilute sol phase and a concentrated gel phase. From the plausible origin of these features we expect them to be very similar in different systems. We describe here the phase behavior of four different systems we prepared in order to vary the time scale of the dynamical response of the transient network; they consist of the combination of two oil(decane) in water microemulsions differing by the stabilizing surfactant monolayer (Cetyl pyridinium chloride/octanol or TX100/TX35) and of two telechelic polymers which are end-grafted poly (ethylene oxide) chains, differing by the end-grafted hydrophobic aliphatic chains (C12H25 or C18H37).Comment: April 9 200

Rheology of Lamellar Liquid Crystals in Two and Three Dimensions: A Simulation Study

We present large scale computer simulations of the nonlinear bulk rheology of lamellar phases (smectic liquid crystals) at moderate to large values of the shear rate (Peclet numbers 10-100), in both two and three dimensions. In two dimensions we find that modest shear rates align the system and stabilise an almost regular lamellar phase, but high shear rates induce the nucleation and proliferation of defects, which in steady state is balanced by the annihilation of defects of opposite sign. The critical shear rate at onset of this second regime is controlled by thermodynamic and kinetic parameters; we offer a scaling analysis that relates the critical shear rate to a critical "capillary number" involving those variables. Within the defect proliferation regime, the defects may be partially annealed by slowly decreasing the applied shear rate; this causes marked memory effects, and history-dependent rheology. Simulations in three dimensions show instead shear-induced ordering even at the highest shear rates studied here. This suggests that the critical shear rate shifts markedly upward on increasing dimensionality. This may in part reflect the reduced constraints on defect motion, allowing them to find and annihilate each other more easily. Residual edge defects in the 3D aligned state mostly point along the flow velocity, an orientation impossible in two dimensions.Comment: 18 pages, 12 figure

Calcium Triggered Lα-H2 Phase Transition Monitored by Combined Rapid Mixing and Time-Resolved Synchrotron SAXS

BACKGROUND: Awad et al. reported on the Ca(2+)-induced transitions of dioleoyl-phosphatidylglycerol (DOPG)/monoolein (MO) vesicles to bicontinuous cubic phases at equilibrium conditions. In the present study, the combination of rapid mixing and time-resolved synchrotron small-angle X-ray scattering (SAXS) was applied for the in-situ investigations of fast structural transitions of diluted DOPG/MO vesicles into well-ordered nanostructures by the addition of low concentrated Ca(2+) solutions. METHODOLOGY/PRINCIPAL FINDINGS: Under static conditions and the in absence of the divalent cations, the DOPG/MO system forms large vesicles composed of weakly correlated bilayers with a d-spacing of approximately 140 A (L(alpha)-phase). The utilization of a stopped-flow apparatus allowed mixing these DOPG/MO vesicles with a solution of Ca(2+) ions within 10 milliseconds (ms). In such a way the dynamics of negatively charged PG to divalent cation interactions, and the kinetics of the induced structural transitions were studied. Ca(2+) ions have a very strong impact on the lipidic nanostructures. Intriguingly, already at low salt concentrations (DOPG/Ca(2+)>2), Ca(2+) ions trigger the transformation from bilayers to monolayer nanotubes (inverted hexagonal phase, H(2)). Our results reveal that a binding ratio of 1 Ca(2+) per 8 DOPG is sufficient for the formation of the H(2) phase. At 50 degrees C a direct transition from the vesicles to the H(2) phase was observed, whereas at ambient temperature (20 degrees C) a short lived intermediate phase (possibly the cubic Pn3m phase) coexisting with the H(2) phase was detected. CONCLUSIONS/SIGNIFICANCE: The strong binding of the divalent cations to the negatively charged DOPG molecules enhances the negative spontaneous curvature of the monolayers and causes a rapid collapsing of the vesicles. The rapid loss of the bilayer stability and the reorganization of the lipid molecules within ms support the argument that the transition mechanism is based on a leaky fusion of the vesicles

Quantitative description of temperature induced self-aggregation thermograms determined by differential scanning calorimetry

A novel thermodynamic approach for the description of differential scanning calorimetry (DSC) experiments on self-aggregating systems is derived and presented. The method is based on a mass action model where temperature dependence of aggregation numbers is considered. The validity of the model was confirmed by describing the aggregation behavior of poly(ethylene oxide)-poly(propylene oxide) block copolymers, which are well-known to exhibit a strong temperature dependence. The quantitative description of the thermograms could be performed without any discrepancy between calorimetric and van 't Hoff enthalpies, and moreover, the aggregation numbers obtained from the best fit of the DSC experiments are in good agreement with those obtained by light scattering experiments corroborating the assumptions done in the derivation of the new model