Phase Coexistence of Complex Fluids in Shear Flow

We present some results of recent calculations of rigid rod-like particles in shear flow, based on the Doi model. This is an ideal model system for exhibiting the generic behavior of shear-thinning fluids (polymer solutions, wormlike micelles, surfactant solutions, liquid crystals) in shear flow. We present calculations of phase coexistence under shear among weakly-aligned (paranematic) and strongly-aligned phases, including alignment in the shear plane and in the vorticity direction (log-rolling). Phase coexistence is possible, in principle, under conditions of both common shear stress and common strain rate, corresponding to different orientations of the interface between phases. We discuss arguments for resolving this degeneracy. Calculation of phase coexistence relies on the presence of inhomogeneous terms in the dynamical equations of motion, which select the appropriate pair of coexisting states. We cast this condition in terms of an equivalent dynamical system, and explore some aspects of how this differs from equilibrium phase coexistence.Comment: 16 pages, 10 figures, submitted to Faraday Discussion

The dielectric spectrum of the polyelectrolyte solutions

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Synthesis and Cell Adhesive Properties of Linear and Cyclic RGD Functionalized Polynorbornene Thin Films

Described herein is the efficient synthesis and evaluation of bioactive arginine-glycine-aspartic acid (RGD) functionalized polynorbornene-based materials for cell adhesion and spreading. Polynorbornenes containing either linear or cyclic RGD peptides were synthesized by ring-opening metathesis polymerization (ROMP) using the well-defined ruthenium initiator [(H_(2)IMes)(pyr)_(2)(Cl)_(2)Ru═CHPh]. The random copolymerization of three separate norbornene monomers allowed for the incorporation of water-soluble polyethylene glycol (PEG) moieties, RGD cell recognition motifs, and primary amines for postpolymerization cross-linking. Following polymer synthesis, thin-film hydrogels were formed by cross-linking with bis(sulfosuccinimidyl) suberate (BS^3), and the ability of these materials to support human umbilical vein endothelial cell (HUVEC) adhesion and spreading was evaluated and quantified. When compared to control polymers containing either no peptide or a scrambled RDG peptide, polymers with linear or cyclic RGD at varying concentrations displayed excellent cell adhesive properties in both serum-supplemented and serum-free media. Polymers with cyclic RGD side chains maintained cell adhesion and exhibited comparable integrin binding at a 100-fold lower concentration than those carrying linear RGD peptides. The precise control of monomer incorporation enabled by ROMP allows for quantification of the impact of RGD structure and concentration on cell adhesion and spreading. The results presented here will serve to guide future efforts for the design of RGD functionalized materials with applications in surgery, tissue engineering, and regenerative medicine

Drug-Loaded, Bivalent-Bottle-Brush Polymers by Graft-through ROMP

Graft through ring-opening metathesis polymerization (ROMP) using ruthenium N heterocyclic carbene catalysts has enabled the synthesis of bottle-brush polymers with unprecedented ease and control Here we report the first bivalent-brush polymers, these materials were prepared by graft through ROMP of drug-loaded poly(ethylene glycol) (PEG) based macromonomers (MMs) Anticancer drugs doxorubicin (DOX) and camptothecin (CT) were attached to a norbornene alkyne-PEG MM via a photocleavable linker ROMP of either or both drug loaded MMs generated brush homo and copolymers with low polydispersities and defined molecular weights. Release of free DOX and CT from these materials was initiated by exposure to 365 nm light All of the CT and DOX polymers were at least 10 fold more toxic to human cancer cells after photoinitiated drug release while a copolymer carrying both CT and DOX displayed 30-fold increased toxicity upon irradiation Graft through ROMP of drug loaded macromonomers provides a general method for the systematic study of structure function relationships for stimuli responsive polymers in biological systems

Habituation of the C-start response in larval zebrafish exhibits several distinct phases and sensitivity to NMDA receptor blockade.

The zebrafish larva has been a valuable model system for genetic and molecular studies of development. More recently, biologists have begun to exploit the surprisingly rich behavioral repertoire of zebrafish larvae to investigate behavior. One prominent behavior exhibited by zebrafish early in development is a rapid escape reflex (the C-start). This reflex is mediated by a relatively simple neural circuit, and is therefore an attractive model behavior for neurobiological investigations of simple forms of learning and memory. Here, we describe two forms of short-lived habituation of the C-start in response to brief pulses of auditory stimuli. A rapid form, persisting for ≥1 min but <15 min, was induced by 120 pulses delivered at 0.5-2.0 Hz. A more extended form (termed "short-term habituation" here), which persisted for ≥25 min but <1 h, was induced by spaced training. The spaced training consisted of 10 blocks of auditory pulses delivered at 1 Hz (5 min interblock interval, 900 pulses per block). We found that these two temporally distinguishable forms of habituation are mediated by different cellular mechanisms. The short-term form depends on activation of N-methyl-d-aspartate receptors (NMDARs), whereas the rapid form does not

Achieving precise mechanical control in intrinsically noisy systems

How can precise control be realized in intrinsically noisy systems? Here, we develop a general theoretical framework that provides a way of achieving precise control in signal-dependent noisy environments. When the control signal has Poisson or supra-Poisson noise, precise control is not possible. If, however, the control signal has sub-Poisson noise, then precise control is possible. For this case, the precise control solution is not a function, but a rapidly varying random process that must be averaged with respect to a governing probability density functional. Our theoretical approach is applied to the control of straight-trajectory arm movement. Sub-Poisson noise in the control signal is shown to be capable of leading to precise control. Intriguingly, the control signal for this system has a natural counterpart, namely the bursting pulses of neurons-trains of Dirac-delta functions-in biological systems to achieve precise control performance

Reconstruction Control of Magnetic Properties during Epitaxial Growth of Ferromagnetic Mn_3-δGa on Wurtzite GaN(0001)

Binary ferromagnetic Mn_3-δGa (1.2<3-δ≤1.5) crystalline thin films have been epitaxially grown on wurtzite GaN(0001) surfaces using rf N-plasma molecular beam epitaxy. The film structure is face-centered tetragonal with CuAu type-I (L1_0) ordering with (111) orientation. The in-plane epitaxial relationship to GaN is nearly ideal with [11̅ 0]_MnGa∥[11̅ 00]_GaN and [112̅ ]_MnGa∥[112̅ 0]_GaN. We observe magnetic anisotropy along both the in-plane and out-of-plane directions. The magnetic moments are found to depend on the Mn/(Mn+Ga) flux ratio and can be controlled by observation of the surface reconstruction during growth, which varies from 1×1 to 2×2 with increasing Mn stoichiometry

Viscoelasticity of two-layer-vesicles in solution

The dynamic shape relaxation of the two-layer-vesicle is calculated. In additional to the undulation relaxation where the two bilayers move in the same direction, the squeezing mode appears when the gap between the two bilayers is small. At large gap, the inner vesicle relaxes much faster, whereas the slow mode is mainly due to the outer layer relaxation. We have calculated the viscoelasticity of the dilute two-layer-vesicle suspension. It is found that for small gap, the applied shear drives the undulation mode strongly while the slow squeezing mode is not much excited. In this limit the complex viscosity is dominated by the fast mode contribution. On the other hand, the slow mode is strongly driven by shear for larger gap. We have determined the crossover gap which depends on the interaction between the two bilayers. For a series of samples where the gap is changed systematically, it is possible to observe the two amplitude switchings

The effect of the antisickling compound GBT1118 on the permeability of red blood cells from patients with sickle cell anemia.

Sickle cell anemia (SCA) is one of the commonest severe inherited disorders. Nevertheless, effective treatments remain inadequate and novel ones are avidly sought. A promising advance has been the design of novel compounds which react with hemoglobin S (HbS) to increase oxygen (O2 ) affinity and reduce sickling. One of these, voxelotor (GBT440), is currently in advanced clinical trials. A structural analogue, GBT1118, was investigated in the current work. As RBC dehydration is important in pathogenesis of SCA, the effect of GBT1118 on RBC cation permeability was also studied. Activities of Psickle , the Gardos channel and the KCl cotransporter (KCC) were all reduced. Gardos channel and KCC activities were also inhibited in RBCs treated with Ca2+ ionophore or the thiol reagent N-ethylmaleimide, indicative of direct effects on these two transport systems. Consistent with its action on RBC membrane transporters, GBT1118 significantly increased RBC hydration. RBC hemolysis was reduced in a nonelectrolyte lysis assay. Further to its direct effects on O2 affinity, GBT1118 was therefore found to reduce RBC shrinkage and fragility. Findings reveal important effects of GBT1118 on protecting sickle cells and suggest that this is approach may represent a useful therapy for amelioration of the clinical complications of SCA.Sultanate of Oman His Majesty Sultan Qaboos's 1000 grants British Heart Foundatio

Deposition of La2Zr2O7 Film by Chemical Solution Deposition

La2Zr2O7 (LZO) formation of bulk powders and of films by Chemical Solution Deposition (CSD) process have been studied using propionates. The treatment involved a one step cycle in the reducing forming gas (Ar-5%H2) to be compatible with Ni-5at%W RABITS. Large amount of residual carbon was found in LZO powders formed in these conditions (10 wt %). The volume fraction of the cube texture in LZO films on Ni-5at%w RABITS was found to be a function of the speed of the gas flown above sample. This phenomenon is discussed in considering the C deposited from the carbon-containing gases emitted during the pyrolysis of the precursor. Using proper conditions (950 ^\circC and the speed of gas of 6.8\times10^{-2} m/s), LZO films with good surface crystallinity could be obtained on Ni-5at%W RABITS as demonstrated by X-ray diffraction, electron backscattered diffraction and RHEED. The existence of residual carbon in oxide films is a common question to films deposited by CSD processes under reducing condition