Metallo-beta-lactamase and phosphotriesterase activities of some zinc(II) complexes

Metallo-beta-lactamases (m beta l) and phosphotriesterase (PTE) are zinc(II) enzymes, which hydrolyze the beta-lactam antibiotics and toxic organophosphotriesters, respectively. In the present work, we have synthesized a few asymmetric phenolate-based ligands by sequential Mannich reaction and their corresponding zinc(II) complexes. These zinc(II) complexes were studied for their m beta l and PTE activities. It is shown that the zinc(II) complexes can hydrolyze oxacillin, the beta-lactam antibiotic, at much higher rates as compared to the hydrolysis of p-nitrophenyl diphenylphosphate (PNPDPP), the phosphotriester. Among the complexes studied, the binuclear asymmetric complex 1 having a water molecule coordinated to one of the zinc(II) ions exhibits much better mbl activity than the mononuclear complexes. However, the mononuclear zinc(II) complexes having labile chloride ions exhibit significant PTE activity, which can be ascribed to the replacement of chloride ions by hydroxide ions during hydrolysis reactions. (C) 2011 Elsevier B.V. All rights reserved.

Graphitic Carbon as Durable Cathode-Catalyst Support for PEFCs

Long-term deterioration in the performance of PEFCs is attributed largely to reduction in active area of the platinum catalyst at cathode, usually caused by carbon-support corrosion. It is found that the use of graphitic carbon as cathode-catalyst support enhances its long-term stability in relation to non-graphitic carbon. This is because graphitic-carbon-supported- Pt (Pt/GrC) cathodes exhibit higher resistance to carbon corrosion in-relation to non-graphitic-carbon-supported- Pt (Pt/Non-GrC) cathodes in PEFCs during accelerated stress test (AST) as evidenced by chronoamperometry and carbon dioxide studies. The corresponding change in electrochemical surface area (ESA), cell performance and charge-transfer resistance are monitored through cyclic voltammetry (CV), cell polarisation and impedance measurements, respectively. The degradation in performance of PEFC with Pt/GrC cathode is found to be around 10% after 70 h of AST as against 77% for Pt/Non-GrC cathode. It is noteworthy that Pt/GrC cathodes can withstand even up to 100 h of AST with nominal effect on their performance. Xray diffraction (XRD), Raman spectroscopy, transmission electron microscopy and cross-sectional field-emission scanning electron microscopy (FE-SEM) studies before and after AST suggest lesser deformation in catalyst layer and catalyst particles for Pt/GrC cathodes in relation to Pt/Non-GrC cathodes, reflecting that graphitic carbon-support resists carbon corrosion and helps mitigating aggregation of Pt-particles.

Temperature profiles of accretion discs around rapidly rotating strange stars in general relativity: A comparison with neutron stars

We compute the temperature profiles of accretion discs around rapidly rotating strange stars, using constant gravitational mass equilibrium sequences of these objects, considering the full effect of general relativity. Beyond a certain critical value of stellar angular momentum (J), we observe the radius ( $r_{\rm orb}$) of the innermost stable circular orbit (ISCO) to increase with J (a property seen neither in rotating black holes nor in rotating neutron stars). The reason for this is traced to the crucial dependence of ${\rm d}r_{\rm orb}/{\rm d}J$ on the rate of change of the radial gradient of the Keplerian angular velocity at $r_{\rm orb}$ with respect to J. The structure parameters and temperature profiles obtained are compared with those of neutron stars, as an attempt to provide signatures for distinguishing between the two. We show that when the full gamut of strange star equation of state models, with varying degrees of stiffness are considered, there exists a substantial overlap in properties of both neutron stars and strange stars. However, applying accretion disc model constraints to rule out stiff strange star equation of state models, we notice that neutron stars and strange stars exclusively occupy certain parameter spaces. This result implies the possibility of distinguishing these objects from each other by sensitive observations through future X-ray detectors.

Influences of the springtime northern Indian biomass burning over the central Himalayas

The influences of the springtime northern Indian biomass burning are shown for the first time over the central Himalayas by using three years (2007-2009) of surface and space based observations along with a radiative transfer model. Near-surface ozone, black carbon (BC), spectral aerosol optical depths (AODs) and the meteorological parameters are measured at a high altitude site Nainital (29.37 degrees N, 79.45 degrees E, 1958 m amsl) located in the central Himalayas. The satellite observations include the MODIS derived fire counts and AOD (0.55 mu m), and OMI derived tropospheric column NO(2), ultraviolet aerosol index and single scattering albedo. MODIS fire counts and BC observations are used to identify the fire-impacted periods (372 h during 2007-2009) and hence the induced enhancements in surface BC, AOD (0.5 mu m) and ozone are estimated to be 1802 ng m(-3) (similar to 145%), 0.3 (similar to 150%) and 19 ppbv (similar to 34%) respectively. Large enhancements (53-100%) are also seen in the satellite derived parameters over a 2 degrees x 2 degrees region around Nainital. The present analysis highlights the northern Indian biomass burning induced cooling at the surface (-27 W m(-2)) and top of the atmosphere (-8 W m(-2)) in the lesser polluted high altitude regions of the central Himalayas. This cooling leads to an additional atmospheric warming of 19 W m(-2) and increases the lower atmospheric heating rate by 0.8 K day(-1). These biomass burning induced changes over the central Himalayan atmosphere during spring may also lead to enhanced short-wave absorption above clouds and might have an impact on the monsoonal rainfall.

Thermodynamic properties of Pt5La, Pt5Ce, Pt5Pr, Pt5Tb and Pt5Tm intermetallics

The Gibbs’ energies of formation of Pt5La, Pt5Ce, Pt5Pr, Pt5Tb and Pt5 Tm intermetallic compounds have been determined in the temperature range 870–1100 K using the solid state cell:Ta,M + MF3 /CaF2 /Pt5 M + Pt + MF3 ,TaTaM+MF3CaF2Pt5M+Pt+MF3Ta.The reversible emf of the cell is directly related to the Gibbs’ energy of formation of the Pt5M compound. The results can be summarized by the equations:DGf° á Pt5 La ñ = - 373,150 + 6 ·60 T( ±300 )J mol - 1 DGf° á Pt5 Ce ñ = - 367,070 + 5 ·79 T( ±300 )J mol - 1 DGf° á Pt5 Pr ñ = - 370,540 + 4 ·69 T( ±300 )J mol - 1 DGf° á Pt5 Tb ñ = - 372,280 + 4 ·11 T( ±300 )J mol - 1 DGf° á Pt5 Tm ñ = - 368,230 + 4 ·89 T( ±300 )J mol - 1 Unknown control sequence '\hfill'relative to the low temperature allotropic form of the lanthanide element and solid platinum as standard states The enthalpies of formation of all the Pt5M intermetallic compounds obtained in this study are in good agreement with Miedema’s model. The experimental values are more negative than those calculated using the model. The variation of the thermodynamic properties of Pt5M compounds with atomic number of the lanthanide element is discussed in relation to valence state and molar volume.

Phase relations and Gibbs energies of spinel phases and solid solutions in the system Mg-Rh-O

Pure stoichiometric MgRh(2)O(4) could not be prepared by solid state reaction from an equimolar mixture of MgO and Rh(2)O(3) in air. The spinel phase formed always contained excess of Mg and traces of Rh or Rh(2)O(3). The spinel phase can be considered as a solid solution of Mg(2)RhO(4) in MgRh(2)O(4). The compositions of the spinel solid solution in equilibrium with different phases in the ternary system Mg-Rh-O were determined by electron probe microanalysis. The oxygen potential established by the equilibrium between Rh + MgO + Mg(1+x)Rh(2-x)O(4) was measured as a function of temperature using a solid-state cell incorporating yttria-stabilized zirconia as an electrolyte and pure oxygen at 0.1 MPa as the reference electrode. To avoid polarization of the working electrode during the measurements, an improved design of the cell with a buffer electrode was used. The standard Gibbs energies of formation of MgRh(2)O(4) and Mg(2)RhO(4) were deduced from the measured electromotive force (e.m.f.) by invoking a model for the spinel solid solution. The parameters of the model were optimized using the measured composition of the spinel solid solution in different phase fields and imposed oxygen partial pressures. The results can be summarized by the equations: MgO + beta -Rh(2)O(3) -> MgRh(2)O(4); Delta G degrees (+ 1010)/J mol(-1) = -32239 + 7.534T; 2MgO + RhO(2) -> Mg(2)RhO(4); Delta G degrees(+/- 1270)/J mol(-1) = 36427 -4.163T; Delta G(M)/J mol(-1) = 2RT(xInx + (1-x)In(1-x)) + 4650x(1-x), where Delta G degrees is the standard Gibbs free energy change for the reaction and G(M) is the free energy of mixing of the spinel solid solution Mg(1+x)Rh(2-x)O(4). (C) 2011 Elsevier B. V. All rights reserved.

Knowledge-Based Approach Using Support Vector Machine for Transmission Line Distance Relay Co-ordination

In this paper, knowledge-based approach using Support Vector Machines (SVMs) are used for estimating the coordinated zonal settings of a distance relay. The approach depends on the detailed simulation studies of apparent impedance loci as seen by distance relay during disturbance, considering various operating conditions including fault resistance. In a distance relay, the impedance loci given at the relay location is obtained from extensive transient stability studies. SVMs are used as a pattern classifier for obtaining distance relay co-ordination. The scheme utilizes the apparent impedance values observed during a fault as inputs. An improved performance with the use of SVMs, keeping the reach when faced with different fault conditions as well as system power flow changes, are illustrated with an equivalent 265 bus system of a practical Indian Western Grid.

Multi-decadal variation of the net downward shortwave radiation over south Asia: The solar dimming effect

The solar radiation flux at the earth's surface has gone through decadal changes of decreasing and increasing trends over the globe. These phenomena known as dimming and brightening, respectively, have attracted the scientific interest in relation to the changes in radiative balance and climate. Despite the interest in the solar dimming/brightening phenomenon in various parts of the world, south Asia has not attracted great scientific attention so far. The present work uses the net downward shortwave radiation (NDSWR) values derived from satellites (Modern Era Retrospective-analysis for Research and Applications, MERRA 2D) in order to examine the multi-decadal variations in the incoming solar radiation over south Asia for the period of 1979-2004. From the analysis it is seen that solar dimming continues over south Asia with a trend of -0.54 Wm(-2) yr(-1). Assuming clear skies an average decrease of -0.05 Wm(-2)yr(-1) in NDSWR was observed, which is attributed to increased aerosol emissions over the region. There is evidence that the increase in cloud optical depth plays the major role for the solar dimming over the area. The cloud optical depth (MERRA retrievals) has increased by 10.7% during the study period, with the largest increase to be detected for the high-level (atmospheric pressure P < 400 hPa) clouds (31.2%). Nevertheless, the decrease in solar radiation and the role of aerosols and clouds exhibit large monthly and seasonal variations directly affected by the local monsoon system, the anthropogenic and natural aerosol emissions. All these aspects are examined in detail aiming at shedding light into the solar dimming phenomenon over a densely populated area. (C) 2011 Elsevier Ltd. All rights reserved.

Fractional Hilbert transform extensions and associated analytic signal construction

The analytic signal (AS) was proposed by Gabor as a complex signal corresponding to a given real signal. The AS has a one-sided spectrum and gives rise to meaningful spectral averages. The Hilbert transform (HT) is a key component in Gabor's AS construction. We generalize the construction methodology by employing the fractional Hilbert transform (FrHT), without going through the standard fractional Fourier transform (FrFT) route. We discuss some properties of the fractional Hilbert operator and show how decomposition of the operator in terms of the identity and the standard Hilbert operators enables the construction of a family of analytic signals. We show that these analytic signals also satisfy Bedrosian-type properties and that their time-frequency localization properties are unaltered. We also propose a generalized-phase AS (GPAS) using a generalized-phase Hilbert transform (GPHT). We show that the GPHT shares many properties of the FrHT, in particular, selective highlighting of singularities, and a connection with Lie groups. We also investigate the duality between analyticity and causality concepts to arrive at a representation of causal signals in terms of the FrHT and GPHT. On the application front, we develop a secure multi-key single-sideband (SSB) modulation scheme and analyze its performance in noise and sensitivity to security key perturbations. (C) 2013 Elsevier B.V. All rights reserved.

Magnetic field induced delocalization in multi-wall carbon nanotube-polystyrene composite at high fields

In well dispersed multi-wall carbon nanotube-polystyrene composite of 15 wt%, with room temperature conductivity of similar to 5 S/cm and resistivity ratio R-2K/R-200K] of similar to 1.4, the temperature dependence of conductivity follows a power-law behavior. The conductivity increases with magnetic field for a wide range of temperature (2-200 K), and power-law fits to conductivity data show that localization length (xi) increases with magnetic field, resulting in a large negative magnetoresistance (MR). At 50T, the negative MR at 8 K is similar to 13% and it shows a maximum at 90K (similar to 25%). This unusually large negative MR indicates that the field is delocalizing the charge carriers even at higher temperatures, apart from the smaller weak localization contribution at T < 20 K. This field-induced delocalization mechanism of MR can provide insight into the intra and inter tube transport. (C) 2013 Elsevier Ltd. All rights reserved.

Contribution of forest fire ash and plant litter decay on stream dissolved composition in a sub-humid tropical watershed (Mule Hole, Southern India)

The current understanding of wildfire effects on water chemistry is limited by the quantification of the elemental dissolution rates from ash and element release rate from the plant litter, as well as quantification of the specific ash contribution to stream water chemistry. The main objective of the study was to provide such knowledge through combination of experimental modelling, field data and end-member mixing analysis (EMMA) of wildfire impact on a watershed scale. The study concerns watershed effects of fire in the Indian subcontinent, a region that is typically not well represented in the fire science literature. In plant litter ash, major elements are either hosted in readily-soluble phases (K, Mg) such as salts, carbonates and oxides or in less-soluble carrier-phases (Si, Ca) such as amorphous silica, quartz and calcite. Accordingly, elemental release rates, inferred from ash leaching experiments in batch reactor, indicated that the element release into solution followed the order K > Mg > Na > Si > Ca. Experiments on plant litter leaching in mixed-flow reactor indicated two dissolution regimes: rapid, over the week and slower over the month. The mean dissolution rates at steady-state (R-ss) indicated that the release of major elements from plant litter followed the order Ca > Si > Cl > Mg > K > Na. R-ss for Si and Ca for tree leaves and herbaceous species are similar to those reported for boreal and European tree species and are higher than that from the dissolution of soil clay minerals. This identifies tropical plant litters as important source of Si and Ca for tropical surface waters. In the wildfire-impacted year 2004, the EMMA indicated that the streamflow composition (Ca, K, Mg, Na, Si, Cl) was controlled by four main sources: rainwater, throughfall, ash leaching and soil solution. The influence of the ash end-member was maximal early in the rainy season (the two first storm events) and decreased later in the rainy season, when the stream was dominated by the throughfall end-member. The contribution of plant litter decay to the streamwater composition for a year not impacted by wildfire is significant with estimated solute fluxes originating from this decay greatly exceed, for most major elements, the annual elemental dissolved fluxes at the Mule Hole watershed outlet. This highlighted the importance of solute retention and vegetation back uptake processes within the soil profile. Overall, the fire increased the mobility and export of major elements from the soils to the stream. It also shifted the vegetation-related contribution to the elemental fluxes at the watershed outlet from long-term (seasonal) to short-term (daily to monthly). (C) 2014 Elsevier B.V. All rights reserved.

Do stable isotopes in carbonate cement of Mio-Pleistocene Himalayan sediments record paleoecological and paleoclimatic changes?

Non-pedogenic carbonates, such as carbonate cement and nodules in the sandstones, are quite common in the terrestrial geological record. Unlike pedogenic carbonates, their stable isotope ratios lack investigations for paleo-climatic reconstructions. The present investigation therefore, explores the possibility of use of stable isotope studies of non-pedogenic carbonates from the Mb-Pleistocene Siwalik Group of sediments exposed in the Ramnagar sub-basin of the NW Himalaya. Petrographic studies reveal the dominance of micrite fabric in carbonate nodules both of pedogenic and non-pedogenic samples irrespective of specific stratigraphic unit However, calcite as cement in the sandstones shows the dominance of micrite fabric in the younger in age sediments. Seventy-two non-pedogenic carbonate samples from the carbonate nodules and cement in the Siwalik sandstones, ranging in age between similar to 1 Ma and 12.2 Ma, were analyzed for delta C-13 and delta O-18 values. The delta C-13 values vary from -24.77 parts per thousand to -1.1 parts per thousand and delta O-18 values vary from -15.34 parts per thousand to -7.81 parts per thousand. Pedogenic and non-pedogenic carbonates ranging in age between similar to 1 Ma and 6 Ma have largely similar delta C-13 values and the range of delta C-13 values indicate the dominance of C-4 type of vegetation. However, unlike pedogenic carbonates which showed the dominance of C-3 type of vegetation pre- 7 Ma on the basis of delta C-13 -depleted isotopic values (Singh et al., 2011), delta C-13 values are largely enriched in the corresponding aged non-pedogenic carbonates revealing no information on specific type of vegetation. Likewise, paleoprecipitational reconstructions from delta O-18 values in pedogenic carbonates showed a progressive increase in aridity from similar to 12 Ma to recent excluding short term increases in rainfall/monsoon intensity at around 10 Ma, 5 Ma, and 1.8 Ma (Singh et al., 2012). On the contrary, such reconstructions are not possible from the delta O-18 values of non-pedogenic carbonates and indeed the delta O-18 values of non-pedogenic carbonates are largely depleted to as much as 6 parts per thousand from the corresponding pedogenic carbonates. Such differences in delta C-13 and delta O-18 values of non-pedogenic carbonates from pedogenic carbonates are primarily due to the dependence of the former on groundwater conditions responsible for precipitating carbonate. Further, a comparison of isotopic values between non-pedogenic and pedogenic carbonates can be interpreted that post-6 Ma and pre-6 Ma non-pedogenic carbonates were largely formed by shallow and deep groundwater conditions respectively. The result of these investigative studies therefore, suggests that the stable delta C-13 and delta O-18 values of non-pedogenic carbonates, unlike the pedogenic carbonates and irrespective of nature of calcite fabric, showed their little importance in paleoclimatic and paleoecological reconstructions. (C) 2014 Elsevier B.V. All rights reserved.

Modifications in Trypsin Digestion Protocol for Increasing the Efficiency and Coverage

Standard trypsin digestion protocol of proteins followed by MALDI-MS analysis has been realized as an important tool for the identification and characterization of proteins. In this article, we proposed the elimination of the step of `staining/de-staining of gel pieces' in in-gel digestion protocol in order to improve the efficiency of trypsin digestion. Coomassie dye is known to interfere with digestion of proteins by trypsin and the procedure of staining-de-staining could result in loss of photoaffinity probe, post translational modifications and catalytic activities of enzymes. Further, we studied parameters like hydrophobicity and isoelectric point, and attempted to quantitatively relate it to the efficiency of trypsin digestion. We suggest that properties of proteins should be considered and trypsin digestion protocol should be appropriately modified as per sequence and other information.

Experimental and numerical studies on protection of buried pipelines and underground utilities using geocells

This paper presents the results of the laboratory model tests and the numerical studies conducted on small diameter PVC pipes, buried in geocell reinforced sand beds. The aim of the study was to evaluate the suitability of the geocell reinforcement in protecting the underground utilities and buried pipelines. In addition to geocells, the efficacy of only geogrid and geocell with additional basal geogrid cases were also studied. A PVC (Poly Vinyl Chloride) pipe with external diameter 75 mm and thickness 1.4 mm was used in the experiments. The vehicle tire contact pressure was simulated by applying the pressure on the top of the bed with the help of a steel plate. Results suggest that the use of geocells with additional basal geogrid considerably reduces the deformation of the pipe as compared to other types of reinforcements. Further, the depth of placement of pipe was also varied between 1B to 2B (B is the width of loading plate) below the plate in the presence of geocell with additional basal geogrid. More than 50% reduction in the pressure and more than 40% reduction in the strain values were observed in the presence of reinforcements at different depths as compared to the unreinforced beds. Conversely, the performance of the subgrade soil was also found to be marginally influenced by the position of the pipe, even in the presence of the relatively stiff reinforcement system. Further, experimental results were validated with 3-dimensional numerical studies using FLAC(3D) (Fast Lagrangian Analysis of Continua in 3D). A good agreement in the measured pipe stain values were observed between the experimental and numerical studies. Numerical studies revealed that the geocells distribute the stresses in the lateral direction and thus reduce the pressure on the pipe. In addition, the results of the 1-g model tests were scaled up to the prototype case of the shallow buried pipeline below the pavement using the appropriate scaling laws. (C) 2015 Elsevier Ltd. All rights reserved.

Sound radiation from a perforated panel set in a baffle with a different perforation ratio

A finite flexible perforated panel set in a differently perforated rigid baffle is considered. The radiation efficiency from such a panel is derived using a 2-D wavenumber domain formulation. This generalization is later used to represent a more practical case of a perforated panel fixed in an unperforated baffle. The perforations are in the form of an array of uniformly distributed circular holes. A complex impedance model for the holes available in the literature is used. An averaged fluid particle velocity is derived using the continuity equation and the surface pressure is derived using an appropriate momentum equation. The discontinuity in the perforate impedance (due to different hole dimensions or perforation ratio) at the panel-baffle interface is carefully taken into account. It is found that there exists a `coupling' of different wavenumbers of the spatially mean fluid particle velocity field. The change in the resonance frequencies and the modeshapes of the panel due to the perforations is taken into account using the Receptance method. Analytical expressions for the radiated power and radiation efficiency are derived in an integral form and numerical results are presented. Several comparisons are made to understand the radiation efficiency curves. Since both the resistive and reactive components of the hole impedance are taken into account, the model is directly applicable to micro-perforated panels also. (C) 2016 Elsevier Ltd. All rights reserved.