Poly(triazolyl methacrylate) glycopolymers as potential targeted unimolecular nanocarriers.

Synthetic glycopolymers are increasingly investigated as multivalent ligands for a range of biological and biomedical applications. This study indicates that glycopolymers with a fine-tuned balance between hydrophilic sugar pendant units and relatively hydrophobic polymer backbones can act as single-chain targeted nanocarriers for low molecular weight hydrophobic molecules. Non-covalent complexes formed from poly(triazolyl methacrylate) glycopolymers and low molecular weight hydrophobic guest molecules were characterised through a range of analytical techniques - DLS, SLS, TDA, fluorescence spectroscopy, surface tension analysis - and molecular dynamics (MD) modelling simulations provided further information on the macromolecular characteristics of these single chain complexes. Finally, we show that these nanocarriers can be utilised to deliver a hydrophobic guest molecule, Nile red, to both soluble and surface-immobilised concanavalin A (Con A) and peanut agglutinin (PNA) model lectins with high specificity, showing the potential of non-covalent complexation with specific glycopolymers in targeted guest-molecule delivery.

Dynamical splayed ferromagnetic ground state in the quantum spin ice Yb(2)Sn(2)O(7).

From magnetic, specific heat, (170)Yb Mössbauer effect, neutron diffraction, and muon spin relaxation measurements on polycrystalline Yb(2)Sn(2)O(7), we show that below the first order transition at 0.15 K all of the Yb(3+) ions are long-range magnetically ordered and each has a moment of 1.1 µ(B) which lies at ≃ 10° to a common fourfold cubic axis. The four sublattice moments have four different directions away from this axis and are therefore noncoplanar. We term this arrangement splayed ferromagnetism. This ground state has a dynamical component with a fluctuation rate in the megahertz range. The net ferromagnetic exchange interaction has an anisotropy that favors the local threefold axis. We discuss our results in terms of the phase diagram proposed by Savary and Balents [Phys. Rev. Lett. 108, 037202 (2012)] for a pyrochlore lattice of Kramers 1/2 effective spins.

Design and commissioning of a high magnetic field muon spin relaxation spectrometer at the ISIS pulsed neutron and muon source.

The high magnetic field (HiFi) muon instrument at the ISIS pulsed neutron and muon source is a state-of-the-art spectrometer designed to provide applied magnetic fields up to 5 T for muon studies of condensed matter and molecular systems. The spectrometer is optimised for time-differential muon spin relaxation studies at a pulsed muon source. We describe the challenges involved in its design and construction, detailing, in particular, the magnet and detector performance. Commissioning experiments have been conducted and the results are presented to demonstrate the scientific capabilities of the new instrument.

Magnetic frustration in the disordered pyrochlore Yb(2)GaSbO(7).

In the pyrochlore Yb(2)GaSbO(7), the Yb(3+) sublattice forms a network of corner sharing tetrahedra and the second sublattice is made up of disordered, non-magnetic Ga(3+) and Sb(5+) ions. We have examined this compound using magnetic susceptibility, (170)Yb Mössbauer spectroscopy (down to 0.03 K) and muon spin relaxation (µSR) (down to 0.02 K) measurements. We establish the size of the Yb(3+) magnetic moments and that of the Yb(3+)-Yb(3+) coupling. At low temperatures, the correlated moments fluctuate between directions that are well tilted relative to the local [111] axis. The lattice disorder does not quench the frustration induced low temperature spin fluctuations but it does remove the first order dynamic transition that is present in the crystallographically ordered counterpart Yb(2)Ti(2)O(7). Below 1.0 K, the fluctuation rate of the correlated moments decreases progressively as the temperature is reduced and the moments remain dynamic down to 0.02 K where the rate is 7 × 10(7) s(-1). Magnetic frustration is operative in Yb(2)GaSbO(7) where the Yb(3+)-Yb(3+) interaction is antiferromagnetic as it is in Yb(2)Ti(2)O(7) where the interaction is ferromagnetic.

Partition instability in water-immersed granular systems.

It is well known that a system of grains, vibrated vertically in a cell divided into linked columns, may spontaneously move into just one of the columns due to the inelastic nature of their collisions. Here we study the behavior of a water-immersed system of spherical barium titanate particles in a rectangular cell which is divided into two columns, linked by two connecting holes, one at the top and one at the bottom of the cell. Under vibration the grains spontaneously move into just one of the columns via a gradual transfer of grains through the connecting hole at the base of the cell. We have developed numerical simulations that are able to reproduce this behavior and provide detailed information on the instability mechanism. We use this knowledge to propose a simple analytical model for this fluid-driven partition instability based on two coupled granular beds vibrated within an incompressible fluid.

Chain formation of spheres in oscillatory fluid flows.

A collection of spherical particles subjected to horizontal oscillatory fluid flow is known to form chains perpendicular to the direction of the oscillation. We have developed computer simulations to model such a system and have validated them against experiments carried out in a small fluid-filled cell. In both experiment and simulation we find that the particles go through the same stages of evolution from a dispersed initial configuration to an ordered chain structure. We then use our computer simulations to investigate in detail the interactions responsible for chain formation and the interaction between fully formed chains.

The donor nature of muonium in undoped, heavily n-type and p-type InAs.

The charge state of muonium has been investigated in p-type doped, nominally undoped (low n-type) and heavily n-type doped InAs. The donor Mu(+) state is shown to be the dominant defect in all cases. Consequently, muonium does not simply counteract the prevailing conductivity in this material. This is consistent with the charge neutrality level lying above the conduction band minimum in InAs.

Influence of magnetic cohesion on the stability of granular slopes.

We use a molecular dynamics model to simulate the formation and evolution of a granular pile in two dimensions in order to gain a better understanding of the role of magnetic interactions in avalanche dynamics. We find that the angle of repose increases only slowly with magnetic field; the increase in angle is small even for intergrain cohesive forces many times stronger than gravity. The magnetic forces within the bulk of the pile partially cancel as a result of the anisotropic nature of the dipole-dipole interaction between grains. However, we show that this cancellation effect is not sufficiently strong to explain the discrepancy between the angle of repose in wet systems and magnetically cohesive systems. In our simulations we observe shearing deep within the pile, and we argue that it is this motion that prevents the angle of repose from increasing dramatically. We also investigate different implementations of friction with the front and back walls of the container, and conclude that the nature of the friction dramatically affects the influence of magnetic cohesion on the angle of repose.

Migration of an asymmetric dimer in oscillatory fluid flow.

We describe the motion of an asymmetric dimer across a horizontal surface when exposed to an oscillatory fluid flow. The dimer consists of two spheres of distinct sizes, rigidly attached to each other. The dimer is found to move in a direction perpendicular to the fluid flow, with the smaller sphere foremost. We have determined how the speed depends upon the vibratory conditions, on the fluid viscosity, and on the dimer size and aspect ratio. Computer simulations are used to give an insight into the mechanism responsible for the motion. We use a scaling argument based on the asymmetry of the streaming flow to predict the approximate dependence of the migration speed on the system parameters.

The majority of adrenocorticotropin receptor (melanocortin 2 receptor) mutations found in familial glucocorticoid deficiency type 1 lead to defective trafficking of the receptor to the cell surface.

CONTEXT: There are at least 24 missense, nonconservative mutations found in the ACTH receptor [melanocortin 2 receptor (MC2R)] that have been associated with the autosomal recessive disease familial glucocorticoid deficiency (FGD) type 1. The characterization of these mutations has been hindered by difficulties in establishing a functional heterologous cell transfection system for MC2R. Recently, the melanocortin 2 receptor accessory protein (MRAP) was identified as essential for the trafficking of MC2R to the cell surface; therefore, a functional characterization of MC2R mutations is now possible. OBJECTIVE: Our objective was to elucidate the molecular mechanisms responsible for defective MC2R function in FGD. METHODS: Stable cell lines expressing human MRAPalpha were established and transiently transfected with wild-type or mutant MC2R. Functional characterization of mutant MC2R was performed using a cell surface expression assay, a cAMP reporter assay, confocal microscopy, and coimmunoprecipitation of MRAPalpha. RESULTS: Two thirds of all MC2R mutations had a significant reduction in cell surface trafficking, even though MRAPalpha interacted with all mutants. Analysis of those mutant receptors that reached the cell surface indicated that four of six failed to signal, after stimulation with ACTH. CONCLUSION: The majority of MC2R mutations found in FGD fail to function because they fail to traffic to the cell surface.

Dynamics and reactivity of positively charged muonium in heavily doped Si:B and comparisons with hydrogen.

The detailed dynamics of the positively charged muonium (Mu+) in heavily doped p-type Si:B is reported. Below 200 K, Mu+ is static and isolated, and is located in a stretched Si-Si bond. Above approximately 200 K, Mu+ diffuses incoherently. At temperatures higher than 300 K, the Mu+-B- complex is formed while above 520 K, it starts to dissociate. There is significant enhancement of the diffusion of Mu+ in Si compared to H+ and D+-this is attributed to its smaller mass.

Interaction between intruders in vibrated granular beds.

Two neutrally buoyant intruder particles in a granular bed fluidized by vertical, sinusoidal vibration are known to interact with each other over a range of about five intruder diameters. Using molecular dynamics simulations, we investigate in detail the spatial and temporal nature of this interaction. We show that the force of attraction between intruders can be calculated from the local density and kinetic energy using a simple equation of state. Moreover, the interaction can be changed from attractive to repulsive by reducing the coefficient of restitution between the intruders and host particles, one of the key results of this work.

Magneto-vibratory separation of glass and bronze granular mixtures immersed in a paramagnetic liquid.

A fluid-immersed granular mixture may spontaneously separate when subjected to vertical vibration, separation occurring when the ratio of particle inertia to fluid drag is sufficiently different between the component species of the mixture. Here, we describe how fluid-driven separation is influenced by magneto-Archimedes buoyancy, the additional buoyancy force experienced by a body immersed in a paramagnetic fluid when a strong inhomogeneous magnetic field is applied. In our experiments glass and bronze mixtures immersed in paramagnetic aqueous solutions of MnCl2 have been subjected to sinusoidal vertical vibration. In the absence of a magnetic field the separation is similar to that observed when the interstitial fluid is water. However, at modest applied magnetic fields, magneto-Archimedes buoyancy may balance the inertia/fluid-drag separation mechanism, or it may dominate the separation process. We identify the vibratory and magnetic conditions for four granular configurations, each having distinctive granular convection. Abrupt transitions between these states occur at well-defined values of the magnetic and vibrational parameters. In order to gain insight into the dynamics of the separation process we use computer simulations based on solutions of the Navier-Stokes' equations. The simulations reproduce the experimental results revealing the important role of convection and gap formation in the stability of the different states.

Intruder clustering in three-dimensional granular beds.

We present results of computer simulations for neutrally buoyant intruders in a vertically vibrated three-dimensional granular bed of smaller host particles. Under sinusoidal excitation, pairs of intruders interact over a distance of several intruder diameters; a group of intruders forms a cluster. The strength of the interaction grows as the number of intruders is increased. We show that the tendency to cluster may be manipulated through the use of nonsinusoidal excitation, which allows partial mixing. Finally, we investigate the effects of walls on the clustering of intruders.

Velocity statistics in dissipative, dense granular media.

We use a two-dimensional random-force model to investigate the velocity distributions in driven granular media. In general, the shape of the distribution is found to depend on the degree of dissipation and the packing fraction but, in highly dissipative systems, the velocity distributions have tails close to exponential. We show that these arise from the dynamics of single particles traveling in dilute regions and influenced predominantly by the random force. A self-consistent kinetic theory is developed to describe this behavior.

Instabilities in vertically vibrated fluid-grain systems.

When a bed of fluid-immersed fine grains is exposed to vertical vibration a wealth of phenomena may be observed. At low frequencies a horizontal bed geometry is generally unstable and the bed breaks spatial symmetry, acquiring a tilt. At the same time it undergoes asymmetric granular convection. Fine binary mixtures may separate completely into layers or patterns of stripes. The separated regions may exhibit instabilities in which they undergo wave-like motion or exhibit quasi-periodic oscillations. We briefly review these and a number of related behaviours, identifying the physical mechanisms behind each. Finally, we discuss the magneto-vibratory separation of binary mixtures which results from exposing each component to a different effective gravity and describe the influence of a background fluid on this process.

Interaction of spheres in oscillatory fluid flows.

Rigid spherical particles in oscillating fluid flows form interesting structures as a result of fluid mediated interactions. Here we show that spheres under horizontal vibration align themselves at right angles to the oscillation and sit with a gap between them. The details of this behavior have been investigated through experiments and simulations. We have carried out experiments in which a pair of stainless steel spheres is shaken horizontally in a cell filled with glycerol-water fluid mixtures of three different viscosities, at various frequencies and amplitudes of oscillation. There is an equilibrium gap between the particles resulting from a long-range attraction and a short-range repulsion. The size of the gap was found to depend on the fluid viscosity and the vibratory parameters, and we have identified two distinct scaling regimes for the dependence of the gap on the system parameters. Using a Navier-Stokes solver the same system was simulated. The interaction force between the spheres was measured and the streaming flows induced by the motion were determined.

Spin dynamics and magnetic order in magnetically frustrated Tb2Sn2O7.

We report a study of the geometrically frustrated magnetic material Tb2Sn2O7 by the positive muon-spin relaxation technique. No signature of a static magnetically ordered state is detected while neutron magnetic reflections are observed in agreement with a published report. This is explained by the dynamical nature of the ground state of Tb2Sn2O7: the Tb3+ magnetic moment characteristic fluctuation time is approximately 10(-10) s. The strong effect of the magnetic field on the muon-spin-lattice relaxation rate at low fields indicates a large field-induced increase of the magnetic density of states of the collective excitations at low energy.

Stochastic dynamics of a rod bouncing upon a vibrating surface.

We describe the behavior of a rod bouncing upon a horizontal surface which is undergoing sinusoidal vertical vibration. The predictions of computer simulations are compared with experiments in which a stainless-steel rod bounces upon a metal-coated glass surface. We find that, as the dimensionless acceleration parameter Gamma is increased appreciably above unity, the motion of a long rod passes from periodic or near-periodic motion into stochastic dynamics. Within this stochastic regime the statistics of the times between impacts follow distributions with tails of approximately Gaussian form while the probability distributions of the angles at impact have tails that are close to exponential. We determine the dependence of each distribution upon the length of the rod, upon frequency, and on Gamma. The statistics of the total energy and of the translational and rotational components each approximately follow a Boltzmann distribution in their tails, the translational and rotational energy components being strongly correlated. The time-averaged mean vertical translational energy is significantly larger than the mean rotational energy, and both are considerably larger than the energy associated with horizontal motion.

Traveling waves in a water-immersed binary granular system vibrated within an annular cell.

It has been known since the time of Faraday that vertically vibrated fine grains may spontaneously form piles through their interaction with a fluid. More recently, it has been observed that a fine binary mixture may separate under vertical vibration through the differential influence of the fluid on the two granular components. Here, we report a detailed study of a system of water-immersed bronze and glass grains held between two coaxial cylinders. Under vertical vibration, the bronze separates to form a layer above the glass, which itself breaks symmetry to form a pile. Symmetry is broken a second time by the bronze forming layers of different thicknesses upon the two slopes of the glass pile. The pile then travels as a wave with the thicker bronze layer upon its leading surface. We examine the conditions for these traveling waves and determine how their speed varies with particle size, frequency, and amplitude of vibration. A model is developed which provides a semiquantitative account of the wave motion.