Control and analysis of oriented thin films of lipid inverse bicontinuous cubic phases using grazing incidence small-angle X‑ray scattering

Lipid cubic phases are complex nanostructures that form naturally in a variety of biological systems, with applications including drug delivery and nanotemplating. Most X-ray scattering studies on lipid cubic phases have used unoriented polydomain samples as either bulk gels or suspensions of micrometer-sized cubosomes. We present a method of investigating cubic phases in a new form, as supported thin films that can be analyzed using grazing incidence small-angle X-ray scattering (GISAXS). We present GISAXS data on three lipid systems: phytantriol and two grades of monoolein (research and industrial). The use of thin films brings a number of advantages. First, the samples exhibit a high degree of uniaxial orientation about the substrate normal. Second, the new morphology allows precise control of the substrate mesophase geometry and lattice parameter using a controlled temperature and humidity environment, and we demonstrate the controllable formation of oriented diamond and gyroid inverse bicontinuous cubic along with lamellar phases. Finally, the thin film morphology allows the induction of reversible phase transitions between these mesophase structures by changes in humidity on subminute time scales, and we present timeresolved GISAXS data monitoring these transformations.

Coalescence of particles by differential sedimentation

We consider a three dimensional system consisting of a large number of small spherical particles, distributed in a range of sizes and heights (with uniform distribution in the horizontal direction). Particles move vertically at a size-dependent terminal velocity. They are either allowed to merge whenever they cross or there is a size ratio criterion enforced to account for collision efficiency. Such a system may be described, in mean field approximation, by the Smoluchowski kinetic equation with a differential sedimentation kernel. We obtain self-similar steady-state and time-dependent solutions to the kinetic equation, using methods borrowed from weak turbulence theory. Analytical results are compared with direct numerical simulations (DNS) of moving and merging particles, and a good agreement is found.

The physics of orographic gravity wave drag

The drag and momentum fluxes produced by gravity waves generated in flow over orography are reviewed, focusing on adiabatic conditions without phase transitions or radiation effects, and steady mean incoming flow. The orographic gravity wave drag is first introduced in its simplest possible form, for inviscid, linearized, non-rotating flow with the Boussinesq and hydrostatic approximations, and constant wind and static stability. Subsequently, the contributions made by previous authors (primarily using theory and numerical simulations) to elucidate how the drag is affected by additional physical processes are surveyed. These include the effect of orography anisotropy, vertical wind shear, total and partial critical levels, vertical wave reflection and resonance, non-hydrostatic effects and trapped lee waves, rotation and nonlinearity. Frictional and boundary layer effects are also briefly mentioned. A better understanding of all of these aspects is important for guiding the improvement of drag parametrization schemes.

A new data set of soil mineralogy for dust-cycle modeling

The mineralogy of airborne dust affects the impact of dust particles on direct and indirect radiative forcing, on atmospheric chemistry and on biogeochemical cycling. It is determined partly by the mineralogy of the dust-source regions and partly by size-dependent fractionation during erosion and transport. Here we present a data set that characterizes the clay and silt-sized fractions of global soil units in terms of the abundance of 12 minerals that are important for dust–climate interactions: quartz, feldspars, illite, smectite, kaolinite, chlorite, vermiculite, mica, calcite, gypsum, hematite and goethite. The basic mineralogical information is derived from the literature, and is then expanded following explicit rules, in order to characterize as many soil units as possible. We present three alternative realizations of the mineralogical maps, taking the uncertainties in the mineralogical data into account. We examine the implications of the new database for calculations of the single scattering albedo of airborne dust and thus for dust radiative forcing.

Glycerol prevents dehydration in lipid cubic phases

Lipid cubic phase samples dry out and undergo phase transitions when exposed to air. We demonstrate experimentally and theoretically that adding glycerol controllably lowers the humidity at which cubic phases form. These results broaden the potential applications of cubic phases and open up the potential of a new humidityresponsive nanomaterial.

Mechanisms of the negative shortwave cloud feedback in mid to high latitudes

Increases in cloud optical depth and liquid water path (LWP) are robust features of global warming model simulations in high latitudes, yielding a negative shortwave cloud feedback, but the mechanisms are still uncertain. We assess the importance of microphysical processes for the negative optical depth feedback by perturbing temperature in the microphysics schemes of two aquaplanet models, both of which have separate prognostic equations for liquid water and ice. We find that most of the LWP increase with warming is caused by a suppression of ice microphysical processes in mixed-phase clouds, resulting in reduced conversion efficiencies of liquid water to ice and precipitation. Perturbing the temperature-dependent phase partitioning of convective condensate also yields a small LWP increase. Together, the perturbations in large-scale microphysics and convective condensate partitioning explain more than two-thirds of the LWP response relative to a reference case with increased SSTs, and capture all of the vertical structure of the liquid water response. In support of these findings, we show the existence of a very robust positive relationship between monthly-mean LWP and temperature in CMIP5 models and observations in mixed-phase cloud regions only. In models, the historical LWP sensitivity to temperature is a good predictor of the forced global warming response poleward of about 45°, although models appear to overestimate the LWP response to warming compared to observations. We conclude that in climate models, the suppression of ice-phase microphysical processes that deplete cloud liquid water is a key driver of the LWP increase with warming and of the associated negative shortwave cloud feedback.

Control of nanomaterial self-assembly in ultrasonically levitated droplets

We demonstrate that acoustic trapping can be used to levitate and manipulate droplets of soft matter, in particular, lyotropic mesophases formed from selfassembly of different surfactants and lipids, which can be analyzed in a contact-less manner by X-ray scattering in a controlled gas-phase environment. On the macroscopic length scale, the dimensions and the orientation of the particle are shaped by the ultrasonic field, while on the microscopic length scale the nanostructure can be controlled by varying the humidity of the atmosphere around the droplet. We demonstrate levitation and in situ phase transitions of micellar, hexagonal, bicontinuous cubic, and lamellar phases. The technique opens up a wide range of new experimental approaches of fundamental importance for environmental, biological, and chemical research.

Film forming solutions based on gelatin and poly(vinyl alcohol) blends: Thermal and rheological characterizations

The objective of this work was to study the theological and thermal properties of film forming solutions (FFS) based on blends of gelatin and poly(vinyl alcohol) (PVA). The effect of the PVA concentration and plasticizer presence on the flow behavior, and viscoelastic and thermal properties of FFS was studied by steady-shear flow and oscillatory experiments, and also, by microcalorimetry. The FB presented Newtonian behavior at 30 degrees C, and the viscosity was not affected neither by the PVA concentration nor by the plasticizer. All FFS presented a phase transition during tests applying temperature scanning. It was verified that the PVA affected the viscoelastic properties of FFS by dilution of gelatin. This behavior was confirmed by microcalorimetric analysis. The behaviors of the storage (G`) and loss (G ``) moduli as a function of frequency of FFS obtained at 5 degrees C were typical of physical gels; with the G` higher than the G ``. The strength of the gels was affected by the PVA concentration. (C) 2009 Elsevier Ltd. All rights reserved.

Development of films based on blends of gelatin and poly(vinyl alcohol) cross linked with glutaraldehyde

Both gelatin and poly(vinyl alcohol) (PVA) can be cross linked with glutaraldehyde (GLU). In the case of gelatin, the GLU reacts with each e-NH2 functional group of adjacent lysine residues, while for PVA, the GLU reacts with two adjacent hydroxyl groups, forming acetal bridges. Thus it can be considered possible to cross link adjacent macromolecules of gelatin and PVA using GLU. In this context, the aims of this work were the development of biodegradable films based on blends of gelatin and poly(vinyl alcohol) cross linked with GLU, and the characterization of some of their main physical and functional properties. All the films were produced from film-forming solutions (FFS) containing 2 g macromolecules (PVA + gelatin)/100 g FFS, 25 g glycerol/100 g macromolecules, and 4 g GLU (25% solution)/100 g FFS. The FFS were prepared with two concentrations of PVA (20 or 50 g PVA/100 g macromolecules) and two reaction temperatures: 90 or 55 degrees C, applied for 30 min. The films were obtained after drying (30 degrees C/24 h) and conditioning at 25 degrees C and 58% of relative humidity for 7 days, and were then characterized. The results for the color parameters, mechanical properties, phase transitions and infrared spectra showed that some chemical modifications occurred, principally for the gelatin. However, in general, all the characteristics of the films were either typical of films based on blends of these macromolecules without cross linking, or slightly higher. A greater improvement in the properties of this material was probably not observed due to the crystallinity of the PVA, which has a melting point above 90 degrees C. The presence of microcrystals in the polymer chain probably reduced macromolecular mobility, hindering the reaction. Thus more research is necessary to produce biodegradable films with improved properties. (C) 2011 Elsevier Ltd. All rights reserved.

Aging and stationary properties of non-equilibrium symmetrical three-state models

We consider a non-equilibrium three-state model whose dynamics is Markovian and displays the same symmetry as the three-state Potts model, i.e. the transition rates are invariant under the cyclic permutation of the states. Unlike the Potts model, detailed balance is, in general, not satisfied. The aging and the stationary properties of the model defined on a square lattice are obtained by means of large-scale Monte Carlo simulations. We show that the phase diagram presents a critical line, belonging to the three-state Potts universality class, that ends at a point whose universality class is that of the Voter model. Aging is considered on the critical line, at the Voter point and in the ferromagnetic phase.

An asymmetric sandpile model with height restriction

We analyze by numerical simulations and mean-field approximations an asymmetric version of the stochastic sandpile model with height restriction in one dimension. Each site can have at most two particles. Single particles are inactive and do not move. Two particles occupying the same site are active and may hop to neighboring sites following an asymmetric rule. Jumps to the right or to the left occur with distinct probabilities. In the active state, there will be a net current of particles to the right or to the left. We have found that the critical behavior related to the transition from the active to the absorbing state is distinct from the symmetrical case, making the asymmetry a relevant field.

Emergence and loss of assortative mating in sympatric speciation

We have studied an agent model which presents the emergence of sexual barriers through the onset of assortative mating, a condition that might lead to sympatric speciation. In the model, individuals are characterized by two traits, each determined by a single locus A or B. Heterozygotes on A are penalized by introducing an adaptive difference from homozygotes. Two niches are available. Each A homozygote is adapted to one of the niches. The second trait, called the marker trait has no bearing on the fitness. The model includes mating preferences, which are inherited from the mother and subject to random variations. A parameter controlling recombination probabilities of the two loci is also introduced. We study the phase diagram by means of simulations, in the space of parameters (adaptive difference, carrying capacity, recombination probability). Three phases are found, characterized by (i) assortative mating, (ii) extinction of one of the A alleles and (iii) Hardy-Weinberg like equilibrium. We also make perturbations of these phases to see how robust they are. Assortative mating can be gained or lost with changes that present hysteresis loops, showing the resulting equilibrium to have partial memory of the initial state and that the process of going from a polymorphic panmictic phase to a phase where assortative mating acts as sexual barrier can be described as a first-order transition. (C) 2009 Published by Elsevier Ltd.

Soluble one-dimensional particle conservation models with infinitely many absorbing states

Particle conservation lattice-gas models with infinitely many absorbing states are studied on a one-dimensional lattice. As one increases the particle density, they exhibit a phase transition from an absorbing to an active phase. The models are solved exactly by the use of the transfer matrix technique from which the critical behavior was obtained. We have found that the exponent related to the order parameter, the density of active sites, is 1 for all studied models except one of them with exponent 2.

Antiferromagnetic spherical spin-glass model

We study the thermodynamic properties and the phase diagrams of a multi-spin antiferromagnetic spherical spin-glass model using the replica method. It is a two-sublattice version of the ferromagnetic spherical p-spin glass model. We consider both the replica-symmetric and the one-step replica-symmetry-breaking solutions, the latter being the most general solution for this model. We find paramagnetic, spin-glass, antiferromagnetic and mixed or glassy antiferromagnetic phases. The phase transitions are always of second order in the thermodynamic sense, but the spin-glass order parameter may undergo a discontinuous change.

Conservative ensembles for nonequilibrium lattice-gas systems

We show how to set up a constant particle ensemble for the steady state of nonequilibrium lattice-gas systems which originally are defined on a constant rate ensemble. We focus on nonequilibrium systems in which particles are created and annihilated on the sites of a lattice and described by a master equation. We consider also the case in which a quantity other than the number of particle is conserved. The conservative ensembles can be useful in the study of phase transitions and critical phenomena particularly discontinuous phase transitions.