Phase Separation in Binary Fluid Mixtures with Continuously Ramped Temperature

We consider the demixing of a binary fluid mixture, under gravity, which is steadily driven into a two phase region by slowly ramping the temperature. We assume, as a first approximation, that the system remains spatially isothermal, and examine the interplay of two competing nonlinearities. One of these arises because the supersaturation is greatest far from the meniscus, creating inversion of the density which can lead to fluid motion; although isothermal, this is somewhat like the Benard problem (a single-phase fluid heated from below). The other is the intrinsic diffusive instability which results either in nucleation or in spinodal decomposition at large supersaturations. Experimental results on a simple binary mixture show interesting oscillations in heat capacity and optical properties for a wide range of ramp parameters. We argue that these oscillations arise under conditions where both nonlinearities are important

Unfolding dynamics of proteins under applied force

Understanding the mechanisms of protein folding is a major challenge that is being addressed effectively by collaboration between researchers in the physical and life sciences. Recently, it has become possible to mechanically unfold proteins by pulling on their two termini using local force probes such as the atomic force microscope. Here, we present data from experiments in which synthetic protein polymers designed to mimic naturally occurring polyproteins have been mechanically unfolded. For many years protein folding dynamics have been studied using chemical denaturation, and we therefore firstly discuss our mechanical unfolding data in the context of such experiments and show that the two unfolding mechanisms are not the same, at least for the proteins studied here. We also report unexpected observations that indicate a history effect in the observed unfolding forces of polymeric proteins and explain this in terms of the changing number of domains remaining to unfold and the increasing compliance of the lengthening unstructured polypeptide chain produced each time a domain unfolds

The Johnson-Segalman model with a diffusion term in Couette flow

We study the Johnson-Segalman (JS) model as a paradigm for some complex fluids which are observed to phase separate, or ``shear-band'' in flow. We analyze the behavior of this model in cylindrical Couette flow and demonstrate the history dependence inherent in the local JS model. We add a simple gradient term to the stress dynamics and demonstrate how this term breaks the degeneracy of the local model and prescribes a much smaller (discrete, rather than continuous) set of banded steady state solutions. We investigate some of the effects of the curvature of Couette flow on the observable steady state behavior and kinetics, and discuss some of the implications for metastability.Comment: 14 pp, to be published in Journal of Rheolog

Molecular observation of contour-length fluctuations limiting topological confinement in polymer melts

In order to study the mechanisms limiting the topological chain confinement in polymer melts, we have performed neutron-spin-echo investigations of the single-chain dynamic-structure factor from polyethylene melts over a large range of chain lengths. While at high molecular weight the reptation model is corroborated, a systematic loosening of the confinement with decreasing chain length is found. The dynamic-structure factors are quantitatively described by the effect of contour-length fluctuations on the confining tube, establishing this mechanism on a molecular level in space and time

Ten Years After: An ‘Austerity Audit’ of Services and Living Conditions for People Living with HIV in the UK, a Decade after the Financial Crisis

Cite as: HIV Psychosocial Network (2018). Ten Years After: An ‘Austerity Audit’ of Services and Living Conditions for People Living with HIV in the UK, a Decade after the Financial Crisis

Coexistence and Phase Separation in Sheared Complex Fluids

We demonstrate how to construct dynamic phase diagrams for complex fluids that undergo transitions under flow, in which the conserved composition variable and the broken-symmetry order parameter (nematic, smectic, crystalline, etc.) are coupled to shear rate. Our construction relies on a selection criterion, the existence of a steady interface connecting two stable homogeneous states. We use the (generalized) Doi model of lyotropic nematic liquid crystals as a model system, but the method can be easily applied to other systems, provided non-local effects are included.Comment: 4 pages REVTEX, 5 figures using epsf macros. To appear in Physical Review E (Rapid Communications

Spinodal-assisted crystallization in polymer melts

Recent experiments in some polymer melts quenched below the melting temperature have reported spinodal kinetics in small-angle x-ray scattering before the emergence of a crystalline structure. To explain these observations we propose that the coupling between density and chain conformation induces a liquid-liquid binodal within the equilibrium liquid-crystalline solid coexistence region. A simple phenomenological theory is developed to illustrate this idea, and several experimentally testable consequences are discussed. Shear is shown to enhance the kinetic role of the hidden binodal

Parallel Excluded Volume Tempering for Polymer Melts

We have developed a technique to accelerate the acquisition of effectively uncorrelated configurations for off-lattice models of dense polymer melts which makes use of both parallel tempering and large scale Monte Carlo moves. The method is based upon simulating a set of systems in parallel, each of which has a slightly different repulsive core potential, such that a thermodynamic path from full excluded volume to an ideal gas of random walks is generated. While each system is run with standard stochastic dynamics, resulting in an NVT ensemble, we implement the parallel tempering through stochastic swaps between the configurations of adjacent potentials, and the large scale Monte Carlo moves through attempted pivot and translation moves which reach a realistic acceptance probability as the limit of the ideal gas of random walks is approached. Compared to pure stochastic dynamics, this results in an increased efficiency even for a system of chains as short as $N = 60$ monomers, however at this chain length the large scale Monte Carlo moves were ineffective. For even longer chains the speedup becomes substantial, as observed from preliminary data for $N = 200$

Combining steady state and temperature jump IR spectroscopy to investigate the allosteric effects of ligand binding to dsDNA

Changes in the structural dynamics of double stranded (ds)DNA upon ligand binding have been linked to the mechanism of allostery without conformational change, but direct experimental evidence remains elusive. To address this, a combination of steady state infrared (IR) absorption spectroscopy and ultrafast temperature jump IR absorption measurements has been used to quantify the extent of fast (∼100 ns) fluctuations in (ds)DNA·Hoechst 33258 complexes at a range of temperatures. Exploiting the direct link between vibrational band intensities and base stacking shows that the absolute magnitude of the change in absorbance caused by fast structural fluctuations following the temperature jump is only weakly dependent on the starting temperature of the sample. The observed fast dynamics are some two orders of magnitude faster than strand separation and associated with all points along the 10-base pair duplex d(GCATATATCC). Binding the Hoechst 33258 ligand causes a small but consistent reduction in the extent of these fast fluctuations of base pairs located outside of the ligand binding region. These observations point to a ligand-induced reduction in the flexibility of the dsDNA near the binding site, consistent with an estimated allosteric propagation length of 15 Å, about 5 base pairs, which agrees well with both molecular simulation and coarse-grained statistical mechanics models of allostery leading to cooperative ligand binding

Phase Separation of Rigid-Rod Suspensions in Shear Flow

We analyze the behavior of a suspension of rigid rod-like particles in shear flow using a modified version of the Doi model, and construct diagrams for phase coexistence under conditions of constant imposed stress and constant imposed strain rate, among paranematic, flow-aligning nematic, and log-rolling nematic states. We calculate the effective constitutive relations that would be measured through the regime of phase separation into shear bands. We calculate phase coexistence by examining the stability of interfacial steady states and find a wide range of possible ``phase'' behaviors.Comment: 23 pages 19 figures, revised version to be published in Physical Review