Vasomodulatory effect of novel peroxovanadate compounds on rat aorta: Role of rho kinase and nitric oxide/cGMP pathway

The present study was undertaken to assess the role of reactive oxygen species (ROS) in rat aortic ring vasoreactivity and integrity by using various peroxovanadate (pV) compounds. All the pV compounds (1 nM-300 mu M) used in the present study exerted concentration-dependent contractions on endothelium intact rat aortic rings. All compounds with an exception of DPV-asparagine (DPV-asn) significantly altered vascular integrity as shown by diminished KCl responses. Phenylephrine (PE)-mediated contractions (3 nM-300 mu M) were unaltered in the presence of these compounds. Acetylcholine (Ach)-mediated relaxation in PE (1 mu M) pre-contracted rings was significantly reduced in presence of diperoxovanadate (DPV), poly (sodium styrene sulfonate-co-maleate)-pV (PSS-CoM-pV) and poly (sodium styrene 4-sulfonate)-pV (PSS-pV). However, no significant change in Ach-mediated responses was observed in the presence of poly (acrylate)-pV (PM-pV) and DPV-asn. DPV-asn was thus chosen to further elucidate mechanism involved in peroxide mediated modulation of vasoreactivity. DPV-asn (30 nM-300 mu M) exerted significantly more stable contractions, that was found to be catalase (100 U/ml) resistant in comparison with H(2)O(2) (30 nM-300 mu M) in endothelium intact aortic rings. These contractile responses were found to be dependent on extracellular Ca(2+) and were significantly inhibited in presence of ROS scavenger N-acetylcysteine (100 mu M). Intracellular calcium chelation by BAPTA-AM (10 mu M) had no significant effect on DPV-asn (30 nM-300 mu M) mediated contraction. Pretreatment of aortic rings by rho-kinase inhibitor Y-27632 (10 mu M) significantly inhibited DPV-asn-mediated vasoconstriction indicating role of voltage-dependent Ca(2+) influx and downstream activation of rho-kinase. The small initial relaxant effect obtained on addition of DPV-asn (30 nM-1 mu M) in PE (1 mu M) pre-contracted endothelium intact rings, was prevented in the presence of guanylate cyclase inhibitor, methylene blue (10 mu M) and/or nitric oxide synthase (NOS) inhibitor, L-NAME (100 mu M) suggesting involvement of nitric oxide and cGMP. DPV-asn, like H(2)O(2), exerted a response of vasoconstriction in normal arteries and vasodilation at low concentrations (30 nM-1 mu M) in PE-pre contracted rings with overlapping mechanisms. These findings suggest usefulness of DPV-asn having low toxicity, in exploring the peroxide-mediated effects on various vascular beds. The present study also convincingly demonstrates role of H(2)O(2) in the modulation of vasoreactivity by using stable peroxide DPV-asn and warrants future studies on peroxide mediated signaling from a newer perspective. (C) 2011 Published by Elsevier Ltd.

Dynamics of water at the interface of a small protein, enterotoxin

Fully atomistic molecular dynamics simulations have been carried out to investigate the correlation of biological activity with dynamics of water molecules in an aqueous protein solution of the toxic domain of enterotoxin (PDB ID: 1ETN). This is a small protein of 13 amino acid residues. Our study of this water soluble protein clearly reveals that water dynamics slows down in the hydration layer. Despite this general slowing down, water molecules in the vicinity of the second beta turn of this protein exhibit faster dynamics than those near other regions of the protein. Since this beta turn is believed to play a critical role in the receptor binding of this protein, the faster dynamics of water near the beta turn m ay have biological significance. The collective orientational dynamics of the water molecules in the protein solution exhibits a characteristic long time component of 27 ps, which agrees well with dielectric relaxation experiments.

A Convex Optimization Framework for Almost Budget Balanced Allocation of a Divisible Good

We address the problem of allocating a single divisible good to a number of agents. The agents have concave valuation functions parameterized by a scalar type. The agents report only the type. The goal is to find allocatively efficient, strategy proof, nearly budget balanced mechanisms within the Groves class. Near budget balance is attained by returning as much of the received payments as rebates to agents. Two performance criteria are of interest: the maximum ratio of budget surplus to efficient surplus, and the expected budget surplus, within the class of linear rebate functions. The goal is to minimize them. Assuming that the valuation functions are known, we show that both problems reduce to convex optimization problems, where the convex constraint sets are characterized by a continuum of half-plane constraints parameterized by the vector of reported types. We then propose a randomized relaxation of these problems by sampling constraints. The relaxed problem is a linear programming problem (LP). We then identify the number of samples needed for ``near-feasibility'' of the relaxed constraint set. Under some conditions on the valuation function, we show that value of the approximate LP is close to the optimal value. Simulation results show significant improvements of our proposed method over the Vickrey-Clarke-Groves (VCG) mechanism without rebates. In the special case of indivisible goods, the mechanisms in this paper fall back to those proposed by Moulin, by Guo and Conitzer, and by Gujar and Narahari, without any need for randomization. Extension of the proposed mechanisms to situations when the valuation functions are not known to the central planner are also discussed. Note to Practitioners-Our results will be useful in all resource allocation problems that involve gathering of information privately held by strategic users, where the utilities are any concave function of the allocations, and where the resource planner is not interested in maximizing revenue, but in efficient sharing of the resource. Such situations arise quite often in fair sharing of internet resources, fair sharing of funds across departments within the same parent organization, auctioning of public goods, etc. We study methods to achieve near budget balance by first collecting payments according to the celebrated VCG mechanism, and then returning as much of the collected money as rebates. Our focus on linear rebate functions allows for easy implementation. The resulting convex optimization problem is solved via relaxation to a randomized linear programming problem, for which several efficient solvers exist. This relaxation is enabled by constraint sampling. Keeping practitioners in mind, we identify the number of samples that assures a desired level of ``near-feasibility'' with the desired confidence level. Our methodology will occasionally require subsidy from outside the system. We however demonstrate via simulation that, if the mechanism is repeated several times over independent instances, then past surplus can support the subsidy requirements. We also extend our results to situations where the strategic users' utility functions are not known to the allocating entity, a common situation in the context of internet users and other problems.

Magnetic properties and specific heat of LaMn1-xTixO3+delta (0 < x <= 0.2)

We present a magnetic study of the insulating perovskite LaMn1-xTixO3+delta (0relaxation. The Curie temperature was found to decrease with increasing content of Ti. Two distinct magnetic transitions, irreversibility, non-exponential relaxation and aging effects confirm a reentrant spin-glass state for x = 0.2. The time decay of the magnetization has an algebraic functional form for times up to 2 h. The specific heat also displays characteristic features of a spin-glass system by a linear low-temperature dependence and a broadened peak near the temperature of the reentrant transition. (C) 2002 Elsevier Science B.V. All rights reserved.

Thermal cycling of Mg-MMCs

Creep resistant Mg alloy QE22 reinforced with maftec(R), saffil(R) or supertec(R) short fibres is cycled between room temperature and 308degreesC at different ramp rates in the longitudinal and transverse directions. From the careful analysis of the strain vs. temperature thermal cycling curves true material behaviour and artifacts from the dilatometer are deciphered. From this analysis true coefficient of thermal expansion and relaxation processes are deduced. Hysteresis at higher temperatures is attributed to the relaxation process, whereas hysteresis at low temperatures giving a tilt-ground shape to the thermal cycling curves is again an artifact due to the instrument. The change in ramp rate highlights this effect. Finally, the effect of thermal cycling on microstructure is examined.

String-like propagation of the 5-coordinated defect state in supercooled water: molecular origin of dynamic and thermodynamic anomalies

We find that at low temperature water, large amplitude (similar to 60 degrees) rotational jumps propagate like a string, with the length of propagation increasing with lowering temperature. The strings are formed by mobile 5-coordinated water molecules which move like a Glarum defect (J. Chem. Phys., 1960, 33, 1371), causing water molecules on the path to change from 4-coordinated to 5-coordinated and again back to 4-coordinated water, and in the process cause the tagged water molecule to jump, by following essentially the Laage-Hynes mechanism (Science, 2006, 311, 832-835). The effects on relaxation of the propagating defect causing large amplitude jumps are manifested most dramatically in the mean square displacement (MSD) and also in the rotational time correlation function of the O-H bond of the molecule that is visited by the defect (transient transition to the 5-coordinated state). The MSD and the decay of rotational time correlation function, both remain quenched in the absence of any visit by the defect, as postulated by Glarum long time ago. We establish a direct connection between these propagating events and the known thermodynamic and dynamic anomalies in supercooled water. These strings are found largely in the regions that surround the relatively rigid domains of 4-coordinated water molecules. The propagating strings give rise to a noticeable dynamical heterogeneity, quantified here by a sharp rise in the peak of the four-point density response function, chi(4)(t). This dynamics heterogeneity is also responsible for the breakdown of the Stokes-Einstein relation.

Spin Probe Signature of Freezing in Water Slow Cooling Experiment: Our Observation is Global or Local?

First systematic spin probe ESR study of water freezing has been conducted using TEMPOL and TEMPO as the probes. The spin probe signature of the water freezing has been described in terms of the collapse of narrow triplet spectrum into a single broad line. This spin probe signature of freezing has been observed at an anomalously low temperature when a milimoler solution of TEMPOL is slowly cooled from room temperature. A systematic observation has revealed a spin probe concentration dependence of these freezing and respective melting points. These results can be explained in terms of localization of spin probe and liquid water,most probably in the interstices of ice grains, in an ice matrix. The lowering of spin probe freezing point, along with the secondary evidences, like spin probe concentration dependence of peak-to-peak width in frozen limit signal, indicates a possible size dependence of these localizations/entrapments with spin probe concentration. A weak concentration dependence of spin probe assisted freezing and melting points, which has been observed for TEMPO in comparison to TEMPOL, indicates different natures of interactions with water of these two probes. This view is also supported by the relaxation behavior of the two probes.

Surface effects on stacking fault and twin formation in fcc nanofilms: A first-principles study

The free surface effects on stacking fault and twin formation in fcc metals (Al, Cu, and Ni) were examined by first-principles calculations based on density functional theory (DFT). It is found that the generalized planar fault (GPF) energies of Ni are much larger than bulk Ni with respect to Al and Cu. The discrepancy is attributed to the localized relaxation of Ni nanofilm to accommodate the large expansion of the inter-planar separation induced at the fault plane. The localized relaxation can be coupled to the electronic structure of Ni nanofilms. (C) 2011 Elsevier B.V. All rights reserved.

An interior penalty method for a sixth-order elliptic equation

We derive and study a C(0) interior penalty method for a sixth-order elliptic equation on polygonal domains. The method uses the cubic Lagrange finite-element space, which is simple to implement and is readily available in commercial software. After introducing some notation and preliminary results, we provide a detailed derivation of the method. We then prove the well-posedness of the method as well as derive quasi-optimal error estimates in the energy norm. The proof is based on replacing Galerkin orthogonality with a posteriori analysis techniques. Using this approach, we are able to obtain a Cea-like lemma with minimal regularity assumptions on the solution. Numerical experiments are presented that support the theoretical findings.

Dynamic and thermodynamic anomalies of water at low temperatures: from bulk water to reverse micelles and DNA hydration layer

Liquid water is known to exhibit remarkable thermodynamic and dynamic anomalies, ranging from solvation properties in supercritical state to an apparent divergence of the linear response functions at a low temperature. Anomalies in various dynamic properties of water have also been observed in the hydration layer of proteins, DNA grooves and inside the nanocavity, such as reverse micelles and nanotubes. Here we report studies on the molecular origin of these anomalies in supercooled water, in the grooves of DNA double helix and reverse micelles. The anomalies have been discussed in terms of growing correlation length and intermittent population fluctuation of 4- and 5-coordinated species. We establish correlation between thermodynamic response functions and mean squared species number fluctuation. Lifetime analysis of 4- and 5-coordinated species reveals interesting differences between the role of the two species in supercooled and constrained water. The nature and manifestations of the apparent and much discussed liquid-liquid transition under confinement are found to be markedly different from that in the bulk. We find an interesting `faster than bulk' relaxation in reverse micelles which we attribute to frustration effects created by competition between the correlations imposed by surface interactions and that imposed by hydrogen bond network of water.

Alternating current conduction behavior of excimer laser ablated SrBi2Nb2O9 thin films

Bi-layered Aurivillius compounds prove to be efficient candidates of nonvolatile memories. SrBi2Nb2O9 thin films were deposited by excimer laser ablation at low substrate temperature (400 °C) followed by an ex situ annealing at 750 °C. The polarization hysteresis behavior was confirmed by variation of polarization with the external applied electric field and also verified with capacitance versus voltage characteristics. The measured values of spontaneous and remnant polarizations were, respectively, 9 and 6 μC/cm2 with a coercive field of 90 kV/cm. The measured dielectric constant and dissipation factors at 100 kHz were 220 and 0.02, respectively. The frequency analysis of dielectric and ac conduction properties showed a distribution of relaxation times due to the presence of multiple grain boundaries in the films. The values of activation energies from the dissipation factor and grain interior resistance were found to be 0.9 and 1.3 eV, respectively. The deviation in these values was attributed to the energetic conditions of the grain boundaries and bulk grains. The macroscopic relaxation phenomenon is controlled by the higher resistive component in a film, such as grain boundaries at lower temperatures, which was highlighted in the present article in close relation to interior grain relaxation and conduction properties.

Population inversions behind normal shock waves in CO2‐N2‐He mixtures seeded with solid particles: Further results

The analysis of propagation of a normal shock wave in CO2‐N2‐He or H2 or H2O system seeded with solid particles is presented. The variation of translational and vibrational temperatures of gas phase and the particle temperatures in the relaxation zone behind the shock front are given in graphical form. These results show that the peak value of population inversion and the width of the inversion zone are highest for He catalyst and lowest for H2O catalyst.

Mode-coupling glass transition in a fluid confined by a periodic potential

We show that a fluid under strong spatially periodic confinement displays a glass transition within mode-coupling theory at a much lower density than the corresponding bulk system. We use fluctuating hydrodynamics, with confinement imposed through a periodic potential whose wavelength plays an important role in our treatment. To make the calculation tractable we implement a detailed calculation in one dimension. Although we do not expect simple 1d fluids to show a glass transition, our results are indicative of the behavior expected in higher dimensions. In a certain region of parameter space we observe a three-step relaxation reported recently in computer simulations [S. H. Krishnan, Ph.D. thesis, Indian Institute of Science (2005); Kim et al., Eur. Phys. J. Special Topics 189, 135 (2010)] and a glass-glass transition. We compare our results to those of Krakoviack [Phys. Rev. E 75, 031503 (2007)] and Lang et al. [Phys. Rev. Lett. 105, 125701 (2010)].

Low loss and frequency (1 kHz–1 MHz) independent dielectric characteristics of 3BaO–3TiO2–B2O3 glasses

X-ray powder diffraction along with differential thermal analysis carried out on the as-quenched samples in the 3BaO–3TiO2–B2O3 system confirmed their amorphous and glassy nature, respectively. The dielectric constants in the 1 kHz–1 MHz frequency range were measured as a function of temperature (323–748 K). The dielectric constant and loss were found to be frequency independent in the 323–473 K temperature range. The temperature coefficient of dielectric constant was estimated using Havinga’s formula and found to be 16 ppm K−1. The electrical relaxation was rationalized using the electric modulus formalism. The dielectric constant and loss were 17±0.5 and 0.005±0.001, respectively at 323 K in the 1 kHz–1 MHz frequency range which may be of considerable interest to capacitor industry.

Relaxor behavior of K0.5La0.5Bi2Nb2O9 ceramics

K0.5La0.5Bi2Nb2O9, a relaxor, was synthesized and the structural studies confirmed it to be an n = 2 member of the Aurivillius oxides. The ½{h00} and ½{hk0} types of superlattice reflections in the electron diffraction patterns reflected the presence of ordered polar regions. A broad dielectric peak with frequency dependent dielectric maximum temperature was observed. The dielectric relaxation obeyed the Vogel-Fulcher relation wherein Ea = 0.04 eV, Tf = 428 K,and ωo = 1010 Hz. The diffuseness parameter γ = 2.003 established the relaxor nature and it was attributed to the A-site cationic disorder. The piezoelectric d31 coefficient was 0.5 pC/N at 300 K and 2 pC/N at 480 K.