Dynamic Monte Carlo algorithm for out-of-equilibrium processes in colloidal dispersions.

Colloids have a striking relevance in a wide spectrum of industrial formulations, spanning from personal care products to protective paints. Their behaviour can be easily influenced by extremely weak forces, which disturb their thermodynamic equilibrium and dramatically determine their performance. Motivated by the impact of colloidal dispersions in fundamental science and formulation engineering, we have designed an efficient Dynamic Monte Carlo (DMC) approach to mimic their out-of-equilibrium dynamics. Our recent theory, which provided a rigorous method to reproduce the Brownian motion of colloids by MC simulations, is here generalised to reproduce the Brownian motion of colloidal particles during transitory unsteady states, when their thermodynamic equilibrium is significantly modified. To this end, we investigate monodisperse and bidisperse rod-like particles in the isotropic phase and apply an external field that forces their reorientation along a common direction and induces an isotropic-to-nematic phase transition. We also study the behaviour of the system once the external field is removed. Our simulations are in excellent quantitative agreement with Brownian Dynamics simulations when the DMC results are rescaled with a time-dependent acceptance ratio, which depends on the strength of the applied field.

Phase behaviour of hard board-like particles.

We examine the phase behaviour of colloidal suspensions of hard board-like particles (HBPs) as a function of their shape anisotropy, and observe a fascinating spectrum of nematic, smectic, and columnar liquid-crystalline phases, whose formation is entirely driven by excluded volume effects. We map out the phase diagram of short and long HBPs by gradually modifying their shape from prolate to oblate and investigate the long-range order of the resulting morphologies along the phase directors and perpendicularly to them. The intrinsic biaxial nature of these particles promotes the formation of translationally ordered biaxial phases, but does not show solid evidence that it would, per se, promote the formation of the biaxial nematic phase. Our simulations shed light on the controversial existence of the discotic smectic phase, whose layers are as thick as the minor particle dimension, which is stable in a relatively large portion of our phase diagrams. Additionally, we modify the Onsager theory to describe the isotropic-nematic phase transition of freely rotating biaxial particles as a function of the particle width, and find a relatively strong first-order signature, in excellent agreement with our simulations. In an attempt to shed light on the elusive formation of the biaxial nematic phase, we apply this theory to predict the uniaxial-biaxial nematic phase transition and confirm, again in agreement with simulations, the prevailing stability of the translationally ordered smectic phase over the orientationally ordered biaxial nematic phase.

Diffusion in systems crowded by active force-dipole molecules.

Experimental studies of systems containing active proteins that undergo conformational changes driven by catalytic chemical reactions have shown that the diffusion coefficients of passive tracer particles and active molecules are larger than the corresponding values when chemical activity is absent. Various mechanisms have been proposed for such behavior, including, among others, force dipole interactions of molecular motors moving on filaments and collective hydrodynamic effects arising from active proteins. Simulations of a multi-component system containing active dumbbell molecules that cycle between open and closed states, a passive tracer particle and solvent molecules are carried out. Consistent with experiments, it is shown that the diffusion coefficients of both passive particles and the dumbbells themselves are enhanced when the dumbbells are active. The dependence of the diffusion enhancement on the volume fraction of dumbbells is determined, and the effects of crowding by active dumbbell molecules are shown to differ from those due to inactive molecules.

Ultra-responsive soft matter from strain-stiffening hydrogels.

The stiffness of hydrogels is crucial for their application. Nature's hydrogels become stiffer as they are strained. This stiffness is not constant but increases when the gel is strained. This stiffening is used, for instance, by cells that actively strain their environment to modulate their function. When optimized, such strain-stiffening materials become extremely sensitive and very responsive to stress. Strain stiffening, however, is unexplored in synthetic gels since the structural design parameters are unknown. Here we uncover how readily tuneable parameters such as concentration, temperature and polymer length impact the stiffening behaviour. Our work also reveals the marginal point, a well-described but never observed, critical point in the gelation process. Around this point, we observe a transition from a low-viscous liquid to an elastic gel upon applying minute stresses. Our experimental work in combination with network theory yields universal design principles for future strain-stiffening materials.

Frustration of the isotropic-columnar phase transition of colloidal hard platelets by a transient cubatic phase.

Using simulations and theory, we show that the cubatic phase is metastable for three model hard platelets. The locally favored structures of perpendicular particle stacks in the fluid prevent the formation of the columnar phase through geometric frustration resulting in vitrification. Also, we find a direct link between structure and dynamic heterogeneities in the cooperative rotation of particle stacks, which is crucial for the devitrification process. Finally, we show that the lifetime of the glassy cubatic phase can be tuned by surprisingly small differences in particle shape.

Orientational order of carbon nanotube guests in a nematic host suspension of colloidal viral rods.

In order to investigate the coupling between the degrees of alignment of elongated particles in binary nematic dispersions, surfactant stabilized single-wall carbon nanotubes (CNTs) have been added to nematic suspensions of colloidal rodlike viruses in aqueous solution. We have independently measured the orientational order parameter of both components of the guest-host system by means of polarized Raman spectroscopy and by optical birefringence, respectively. Our system allows us therefore to probe the regime where the guest particles (CNTs) are shorter and thinner than the fd virus host particles. We show that the degree of order of the CNTs is systematically smaller than that of the fd virus particles for the whole nematic range. These measurements are in good agreement with predictions of an Onsager-type second-viral theory, which explicitly includes the flexibility of the virus particles, and the polydispersity of the CNTs.

Phase diagram of hard snowman-shaped particles.

We present the phase diagram of hard snowman-shaped particles calculated using Monte Carlo simulations and free energy calculations. The snowman particles consist of two hard spheres rigidly attached at their surfaces. We find a rich phase behavior with isotropic, plastic crystal, and aperiodic crystal phases. The crystalline phases found to be stable for a given sphere diameter ratio correspond mostly to the close packed structures predicted for equimolar binary hard-sphere mixtures of the same diameter ratio. However, our results also show several crystal-crystal phase transitions, with structures with a higher degree of degeneracy found to be stable at lower densities, while those with the best packing are found to be stable at higher densities.

High-level virial theory of hard spheroids.

We present a method for calculating high-order virial expansions of the isotropic-nematic phase transition which we apply here to hard spheroids. Studying a range of aspect ratios, for both oblate and prolate particles, we obtain equations of state, coexistence densities, and nematic order parameters, using expansions truncated at up to eighth virial level. For particles of large aspect ratios our results show rapid convergence, with truncation at sixth order sufficient to give excellent agreement with simulation data. For more spherical particles the convergence is less rapid, with results for up to eighth-order theory approaching but still not reaching simulation data. Our results indicate that high-order viral expansions are better suited to predicting equations of state than coexistence densities. We also test the validity of using the Onsager trial function to approximate the orientational distribution function, finding only small errors when making this approximation.

Caesarean Sections at Juba Teaching Hospital 2008-2009

A summary and analysis of all recorded emergency and elective caesarean sections (CS) performed at Juba Teaching Hospital (JTH); Juba; Southern Sudan from October 2008 to September 2009 was made. During this period 430 CS were performed giving a mean of 1.2 each day; the main reason being cited as obstructed labour. Thirty of the babies delivered by CS died giving a neonatal morality rate of 7. Due to various /non-comprehensive reporting methods it is difficult to measure the maternal mortality rate associated with CS. Overall 11.2of all deliveries were CS; in accordance with WHO targets1. The majority of caesarean sections were performed using a general anaesthetic or ketamine (79for emergency and 62for elective surgery). These rates are much higher than those in the published guidance of best practice in the UK (Royal College of Anaesthetists Guideline 2006)

Theory and computer simulation for the cubatic phase of cut spheres.

The phase behavior of a system of hard-cut spheres has been studied using a high-order virial theory and by Monte Carlo simulation. The cut-sphere particles are disks of thickness L formed by symmetrically truncating the end caps of a sphere of diameter D . The virial theory predicts a stable nematic phase for aspect ratio LD=0.1 and a stable cubatic phase for LD=0.15-0.3 . The virial series converges rapidly on the equation of state of the isotropic and nematic phases, while for the cubatic phase the convergence is slower, but still gives good agreement with the simulation at high order. It is found that a high-order expansion (up to B8 ) is required to predict a stable cubatic phase for LD> or =0.15 , indicating the importance of many-body interactions in stabilizing this phase. Previous simulation work on this system has focused on aspect ratios LD=0.1 , 0.2, and 0.3. We expand this to include also LD=0.15 and 0.25, and we introduce a fourth-rank tensor to measure cubatic ordering. We have applied a multiparticle move which dramatically speeds the attainment of equilibrium in the nematic phase and therefore is of great benefit in the study of the isotropic-nematic phase transition. In agreement with the theory, our simulations confirm the stability of the nematic phase for LD=0.1 and the stability of the cubatic phase over the nematic for LD=0.15-0.3 . There is, however, some doubt about the stability of the cubatic phase with respect to the columnar. We have shown that the cubatic phase found on compression at LD=0.1 is definitely metastable, but the results for LD=0.2 were less conclusive.

Computer simulation and high level virial theory of Saturn-ring or UFO colloids.

Monte Carlo simulations are used to map out the complete phase diagram of hard body UFO systems, in which the particles are composed of a concentric sphere and thin disk. The equation of state and phase behavior are determined for a range of relative sizes of the sphere and disk. We show that for relatively large disks, nematic and solid phases are observed in addition to the isotropic fluid. For small disks, two different solid phases exist. For intermediate sizes, only a disordered fluid phase is observed. The positional and orientational structure of the various phases are examined. We also compare the equations of state and the nematic-isotropic coexistence densities with those predicted by an extended Onsager theory using virial coefficients up to B(8).

Elastic constants of hard thin platelets by Monte Carlo simulation and virial expansion.

In this paper we present an investigation into the calculation of the Frank elastic constants of hard platelets via molecular simulation and virial expansion beyond second order. Monte Carlo simulations were carried out and director fluctuations measured as a function of wave vector k, giving the elastic constants through a fit in the low-k limit. Additionally, the virial expansion coefficients of the elastic constants up to sixth order were calculated, and the validity of the theory determined by comparison with the simulation results. The simulation results are also compared with experimental measurements on colloidal suspensions of platelike particles.