Synthesis, characterization and antioxidant activity of angiotensin converting enzyme inhibitors

Angiotensin converting enzyme (ACE) catalyzes the conversion of angiotensin I (Ang I) to angiotensin II (Ang II). ACE also cleaves the terminal dipeptide of vasodilating hormone bradykinin (a nonapeptide) to inactivate this hormone. Therefore, inhibition of ACE is generally used as one of the methods for the treatment of hypertension. `Oxidative stress' is another disease state caused by an imbalance in the production of oxidants and antioxidants. A number of studies suggest that hypertension and oxidative stress are interdependent. Therefore, ACE inhibitors having antioxidant property are considered beneficial for the treatment of hypertension. As selenium compounds are known to exhibit better antioxidant behavior than their sulfur analogues, we have synthesized a number of selenium analogues of captopril, an ACE inhibitor used as an antihypertensive drug. The selenium analogues of captopril not only inhibit ACE activity but also effectively scavenge peroxynitrite, a strong oxidant found in vivo.

Growing pseudo-eigenmodes and positive logarithmic norms in rotating shear flows

Rotating shear flows, when angular momentum increases and angular velocity decreases as functions of radiation coordinate, are hydrodynamically stable under linear perturbation. The Keplerian flow is an example of such a system, which appears in an astrophysical context. Although decaying eigenmodes exhibit large transient energy growth of perturbation which could govern nonlinearity in the system, the feedback of inherent instability to generate turbulence seems questionable. We show that such systems exhibiting growing pseudo-eigenmodes easily reach an upper bound of growth rate in terms of the logarithmic norm of the involved non-normal operators, thus exhibiting feedback of inherent instability. This supports the existence of turbulence of hydrodynamic origin in the Keplerian accretion disc in astrophysics. Hence, this answers the question of the mismatch between the linear theory and experimental/observed data and helps in resolving the outstanding question of the origin of turbulence therein.

Liquid-Liquid Interphase (Biphasic) as the Reaction Medium in the Assembly of a Hierarchy of Structures of 4,4 `-Azodibenzoic Acid with Zinc and Cadmium

The compounds Zn(C12H8N2)](2)C12N2H8(COO)(2)](2)center dot(C6H12O)center dot(H2O), I, Zn(C12H8N2)]C12N2H8(COO)(2)], II, Cd(C12H8N2)(H2O)]C12N2H8(COO)(2)]center dot(H2O), III, Zn(C10N2H8)]C12N2H8(COO)(2)]center dot 0.5(C10N2H8), IV, Cd(C12N2H8(COO)(2)center dot H2O], V, and Zn-3(mu(2)-O)(mu(3)-O)(3)]C12N2H8(COO)(2)], VI, have been synthesized by using a biphasic approach (I, III, V, VI) or regular hydrothermal method (II, IV). The compounds exhibit one (I and II), two (In), and three dimensionally (IV, V, VI) extended structures. The flexible azodibenzoate ligand gives rise to a 3-fold interpenetration (IV) when the synthesis was carried out using normal hydrothermal methods. The biphasic approach forms structures without any interpenetrations, especially in the three-dimensional structures of V and VI. Formation of Cd2O2 dimers in V and extended M-O(H)-M two-dimensional layers in VI suggests the subtle structural control achieved by the biphasic method. Transformation studies indicate that it is possible to transform I to II. Lewis acid catalytic studies have been performed to evaluate the role of the coordination environment in such reactions. All the compounds have been characterized by a variety of techniques that includes powder X-ray diffraction, infrared, thermogravitric analysis, UV-vis, photoluminescence studies.

Creep in TiO2 doped Zirconia: Implications for high strain rate superplasticity

In ceramics, dopants offer the possibility of higher creep rates by enhancing diffusion. The present study examines the potential for high strain rate superplasticity in a TiO2 doped zirconia, by conducting creep experiments together with microstructural characterization. It is shown that both pure and doped zirconia exhibit transitions in creep behaviour from Coble diffusion creep with n similar to 1 to an interface controlled process with n similar to 2. Doping with TiO2 enhances the creep rate by over an order of magnitude. There is evidence of substantial grain boundary sliding, consistent with diffusion creep.

Copper( 11) Complexes of Novel Tripodal Ligands containing Phenolate and Benzimidazole/Pyridine Pendants: Synthesis, Structure, Spectra and Electrochemical Behaviour

Mononuclear copper(II) complexes of tri- and tetra-dentate tripodal ligands containing phenolic hydroxyl and benzimidazole or pyridine groups have been isolated. They are of the type (CuL(X)].nH2O, [CuL(H2O)]X.nH2O or [CuL].nH2O where X = Cl-, ClO4-, N3- or NCS- and n = 0-4. The electronic spectra of all the complexes exhibit a broad absorption band around 14000 cm-1 and the polycrystalline as well as the frozen-solution EPR spectra are axial, indicating square-based geometries. The crystal structure of [CuL(Cl)] [HL = (2-hydroxy-5-nitrobenzyl)bis(2-pyridyl-methyl)amine] revealed a square-pyramidal geometry around Cu(II). The mononuclear complex crystallises in the triclinic space group P1BAR with a = 6.938(1), b = 11.782(6), c = 12.678(3) angstrom and alpha = 114.56(3), beta = 92.70(2), gamma = 95.36(2)-degrees. The co-ordination plane is comprised of one tertiary amine and two pyridine nitrogens and a chloride ion. The phenolate ion unusually occupies the axial site, possibly due to the electron-withdrawing p-nitro group. The enhanced pi delocalisation involving the p-nitrophenolate donor elevates the E1/2 values. The spectral and electrochemical results suggest the order of donor strength as nitrophenolate < pyridine < benzimidazole in the tridentate and nitrophenolate < benzimidazole < pyridine in the tetradentate ligand complexes.

Nanoscale ZnO/CdS heterostructures with engineered interfaces for high photocatalytic activity under solar radiation

Semiconductor based nanoscale heterostructures are promising candidates for photocatalytic and photovoltaic applications with the sensitization of a wide bandgap semiconductor with a narrow bandgap material being the most viable strategy to maximize the utilization of the solar spectrum. Here, we present a simple wet chemical route to obtain nanoscale heterostructures of ZnO/CdS without using any molecular linker. Our method involves the nucleation of a Cd-precursor on ZnO nanorods with a subsequent sulfidation step leading to the formation of the ZnO/CdS nanoscale heterostructures. Excellent control over the loading of CdS and the microstructure is realized by merely changing the initial concentration of the sulfiding agent. We show that the heterostructures with the lowest CdS loading exhibit an exceptionally high activity for the degradation of methylene blue (MB) under solar irradiation conditions; microstructural and surface analysis reveals that the higher activity in this case is related to the dispersion of the CdS nanoparticles on the ZnO nanorod surface and to the higher concentration of surface hydroxyl species. Detailed analysis of the mechanism of formation of the nanoscale heterostructures reveals that it is possible to obtain deterministic control over the nature of the interfaces. Our synthesis method is general and applicable for other heterostructures where the interfaces need to be engineered for optimal properties. In particular, the absence of any molecular linker at the interface makes our method appealing for photovoltaic applications where faster rates of electron transfer at the heterojunctions are highly desirable.

Hydrodynamics of R-charged D1-branes

We study the hydrodynamic properties of strongly coupled SU(N) Yang-Mills theory of the D1-brane at finite temperature and at a non-zero density of R-charge in the framework of gauge/gravity duality. The gravity dual description involves a charged black hole solution of an Einstein-Maxwell-dilaton system in 3 dimensions which is obtained by a consistent truncation of the spinning D1-brane in 10 dimensions. We evaluate thermal and electrical conductivity as well as the bulk viscosity as a function of the chemical potential conjugate to the R-charges of the D1-brane. We show that the ratio of bulk viscosity to entropy density is independent of the chemical potential and is equal to 1/4 pi. The thermal conductivity and bulk viscosity obey a relationship similar to the Wiedemann-Franz law. We show that at the boundary of thermodynamic stability, the charge diffusion mode becomes unstable and the transport coefficients exhibit critical behaviour. Our method for evaluating the transport coefficients relies on expressing the second order differential equations in terms of a first order equation which dictates the radial evolution of the transport coefficient. The radial evolution equations can be solved exactly for the transport coefficients of our interest. We observe that transport coefficients of the D1-brane theory are related to that of the M2-brane by an overall proportionality constant which sets the dimensions.

MOSAICS: Multiplexed Optimal Signal Acquisition Involving Compressed Sensing

It is possible to sample signals at sub-Nyquist rate and still be able to reconstruct them with reasonable accuracy provided they exhibit local Fourier sparsity. Underdetermined systems of equations, which arise out of undersampling, have been solved to yield sparse solutions using compressed sensing algorithms. In this paper, we propose a framework for real time sampling of multiple analog channels with a single A/D converter achieving higher effective sampling rate. Signal reconstruction from noisy measurements on two different synthetic signals has been presented. A scheme of implementing the algorithm in hardware has also been suggested.

Diffusion of sorbates in zeolites Y and A novel dependence on sorbate size and strength of sor ba t e-Zeoli t e interaction

A systematic investigation of monatomic spherical sorbates in the supercages of zeolites Y and A by molecular dynamics technique is presented. Rates of intercage diffusion, rates of cage visits, and the diffusion coefficients have been calculated as a function of the sorbate-zeolite interaction strength. These properties exhibit markedly different dependences on interaction strength for the two zeolites. The observed behavior is shown to be a consequence of the two principal mechanisms of intercage diffusion and the energetic barrier associated with them. The diffusion coefficient and other properties associated with intercage diffusion are found to be directly proportional to the reciprocal of the square of the sorbate diameter when the sorbate diameter is significantly smaller than the window diameter. As the sorbate diameter increases, a peak is observed in all the transport properties investigated including the diffusion coefficient. We call this surprising effect as the ring or levitation effect and it explains several anomalous results reported in the literature and suggests a breakdown of the geometrical criterion for diffusion of sorbates. It shows that under certain conditions nongeometrical factors play a major role and geometrical factors become secondary in the determination of the molecular sieve property. A generalized parameter has been proposed which suggests conditions under which one can expect the ring or levitation effect in any porous medium. Inverse size selectivity becomes operative under these conditions.

Dynamics of zeolite cage and its effect on the diffusion properties of sorbate: persistence of diffusion anomaly in NaA zeolite

Recent computer simulations on zeolites Y and A have found that the diffusion coefficient and the rate of intercage diffusion exhibit, apart from a linear dependence on the reciprocal of the square of the sorbate diameter, an anomalous peak as sorbate diameter approaches the window diameter. Here we report molecular dynamics simulations of zeolite NaA incorporating framework flexibility as a function of sorbate diameter in order to verify the existence of anomalous diffusion. Results suggest persistence of anomalous diffusion or ring effect. This suggests that the anomalous behavior is a general effect characteristic of zeolites Y and A. The barrier for diffusion across the eight-ring window is seen to be negative and is found to decrease with sorbate size. The effect of sorbate on the cage motion has also been investigated. Results suggest that the window expands during intercage migration only if the sorbate size is comparable to the window diameter. Flexible cage simulations yield a higher value for the diffusion coefficient and also the rate of intercage diffusion. This increase has been shown to be due to an increase in the intercage diffusions via the centralized diffusion mode rather than the surface-mediated mode. It is shown that this increase arises from an increase in the single particle density distribution in the region near the cage center.

Electrooxidation of methanol in sulfuric-acid electrolyte on platized-carbon electrodes with several functional-group characteristics

The effect of acid/base functional-groups associated with platinized-carbon electrodes on their catalytic activity toward electro-oxidation of methanol in sulfuric acid electrolyte at 60-degrees-C is studied. Platinized-carbon electrodes with sm amounts of functional groups exhibit higher catalytic activity compared to those with large concentrations of acidic/basic surface functionalities. The overpotential for methanol oxidation is minimum on electrodes of platinized carbons with pHzpc values between 6 and 7. An x-ray photoelectron spectroscopic study of various platinized carbons suggests that the acid/base surface functional-groups produce ample amounts of surface Pt-oxides and a consequent decrease in activity toward methanol oxidation.

Miscibility of Poly(aromatic acrylate)s and Methacrylates with Styrene/Acrylonitrile copolymers

Miscibilities of some poly[aromatic (meth)acrylatels namely, poly(pheny1 acrylate) (PPA), poly(pheny1 methacrylate) (PPMA), poly(benzy1 acrylate) (PBA), and poly(benzy1 methacrylate) (PBMAY polystyrene blends, have been studied through the so-called copolymer effect by incorporating acrylonitrile units in PS chains. In these systems, miscibility occurs on account of the strong repulsion between the acrylonitrile and styrene units in the copolymer. PBA and PBMA were blended with different styreneacrylonitrile (SAN) copolymers. A miscibility window has been identified for the latter system, and from these limits, the binary interaction energy density parameters (B,j.’sw) ere calculated. Using these values, the miscibilities in other homopolymer-copolymer and copolymer-copolymer systems containing benzyl methacrylate, acrylonitrile, and styrene monomer units have been predicted and subsequently verified experimentally. The miscibility window limits in poly[aromatic (meth)acrylate]s/SAN copolymer blends have been compared. PBA does not exhibit a miscibility window with SAN copolymers, which has been explained by the weak intramolecular hydrogen bonding in PBA. The miscibility window in the PBW SAN copolymer system, as observed by DSC, shows a considerable narrowing in nonradiative energy transfer (NRET) measurements, as this technique is more sensitive.

Gradient solid electrolytes for thermodynamic measurements: System Na2CO3-Na2SO4

The thermodynamic properties of Na2CO3-Na2SO4 solid solution with hexagonal structure have been measured in the temperature range of 873 to 1073 K, using a composite-gradient solid electrolyte. The cell used can be represented as The composite-gradient solid electrolyte consisted of pure Na2CO3 at one extremity and the solid solution under study at the other, with variation in composition across the electrolyte. A CO2 + O2 + Ar gas mixture was used to fix the chemical potential of sodium at each electrode. The Nernstian response of the cell to changes in partial pressures of CO2 and O2 at the electrodes has been demonstrated. The activity of Na2CO3 in the solid solution was measured by two techniques. In the first method, the electromotive force (emf) of the cell was measured with the same CO2 + O2 + Ar mixture at both electrodes. The resultant emf is directly related to the activity of Na2CO3 at the solid solution electrode. By the second approach, the activity was calculated from the difference in compositions Of CO2 + O2 + Ar mixtures at the two electrodes required to produce a null emf. Both methods gave identical results. The second method is more suitable for gradient solid electrolytes that exhibit significant electronic conduction. The activity of Na2CO3 exhibits positive deviation from Raoult's law. The excess Gibbs' energy of mixing of the solid solution can be represented using a subregular solution model such as the following: DELTAG(E) = X(1 - X)[6500(+/-200)X + 3320(+/-80)(1 - X)J mol-1 where X is the mole fraction of Na2CO3. By combining this information with the phase diagram, mixing properties of the liquid phase are obtained.

Molecular Dynamics Simulations of Orientational Relaxation in Dipolar Lattice: Lack of Diffusive Decay for Second and Higher Rank Correlation Functions

Extensive molecular dynamics simulations have been carried out to calculate the orientational correlation functions Cl(t), G(t) = [4n/(21 + l)]Ci=-l (Y*lm(sZ(0)) Ylm(Q(t))) (where Y,,(Q) are the spherical harmonics) of point dipoles in a cubic lattice. The decay of Cl(t) is found to be strikingly different from higher l-correlation functions-the latter do not exhibit diffusive dynamics even in the long time. Both the cumulant expansion expression of Lynden-Bell and the conventional memory function equation provide very good description of the Cl(t) in the short time but fail to reproduce the observed slow, long time decay of c1 (t) .

Hot deformation characteristics of INCONEL alloy MA 754 and development of a processing map

The characteristics of hot deformation of INCONEL alloy MA 754 have been studied processing maps obtained on the basis of flow stress data generated in compression in the temperature range 700-degrees-C to 1150-degrees-C and strain rate range 0.001 to 100 s-1. The map exhibited three domains. (1) A domain of dynamic recovery occurs in the temperature range 800-degrees-C to 1075-degrees-C and strain rate range 0.02 to 2 s-1, with a peak efficiency of 18 pct occurring at 950-degrees-C and 0.1 s-1. Transmission electron microscope (TEM) micrographs revealed stable subgrain structure in this domain with the subgrain size increasing exponentially with an increase in temperature. (2) A domain exhibiting grain boundary cracking occurs at temperatures lower than 800-degrees-C and strain rates lower than 0.01 s-1. (3) A domain exhibiting intense grain boundary cavitation occurs at temperatures higher than 1075-degrees-C. The material did not exhibit a dynamic recrystallization (DRX) domain, unlike other superalloys. At strain rates higher than about 1 s-1, the material exhibits flow instabilities manifesting as kinking of the elongated grains and adiabatic shear bands. The material may be safely worked in the domain of dynamic recovery but can only be statically recrystallized.