Synthesis, antimicrobial, DNA-binding and photonuclease studies of Cobalt(III) and Nickel(II) Schiff base complexes

New metal complexes of the type M(nih)(L)](PF6)(n)center dot xAH(2)O and M(nih)(2)](PF6)center dot xH(2)O (where M = Co(III) or Ni(II), L = 1,10-phenanthroline (phen)/or 2,2' bipyridine (bpy), nih = 2-hydroxy-1-naphthaldehyde isonicotinoyl hydrazone, n = 2 or 1 and x = 3 or 2) have been synthesized and characterized by elemental analysis, magnetic, IR and H-1 NMR spectral data. The electronic and magnetic moment 2.97-3.07 B.M. data infers octahedral geometry for all the complexes. The IR data reveals that Schiff base (nih) form coordination bond with the metal ion through azomethine-nitrogen, phenolic-oxygen and carbonyl-oxygen in a tridentate fashion. In addition, DNA-binding properties of these six metal complexes were investigated using absorption spectroscopy, viscosity measurements and thermal denaturation methods. The results indicated that the nickel(II) complex strongly bind with calf-thymus DNA with intrinsic DNA binding constant K-b value of 4.9 x 10(4) M-1 for (3), 4.2 x 10(4) M-1 for (4), presumably via an intercalation mechanism compared to cobalt(III) complex with K-b value of 4.6 x 10(4) M-1 (1) and 4.1 x 10(4) M-1 (2). The DNA Photoclevage experiment shows that, the complexes act as effective DNA cleavage agent. (C) 2012 Elsevier B.V. All rights reserved.

A GIS (geographical information system)-based spatial data mining approach for optimal location and capacity planning of distributed biomass power generation facilities: A case study of Tumkur district, India

This paper primarily intends to develop a GIS (geographical information system)-based data mining approach for optimally selecting the locations and determining installed capacities for setting up distributed biomass power generation systems in the context of decentralized energy planning for rural regions. The optimal locations within a cluster of villages are obtained by matching the installed capacity needed with the demand for power, minimizing the cost of transportation of biomass from dispersed sources to power generation system, and cost of distribution of electricity from the power generation system to demand centers or villages. The methodology was validated by using it for developing an optimal plan for implementing distributed biomass-based power systems for meeting the rural electricity needs of Tumkur district in India consisting of 2700 villages. The approach uses a k-medoid clustering algorithm to divide the total region into clusters of villages and locate biomass power generation systems at the medoids. The optimal value of k is determined iteratively by running the algorithm for the entire search space for different values of k along with demand-supply matching constraints. The optimal value of the k is chosen such that it minimizes the total cost of system installation, costs of transportation of biomass, and transmission and distribution. A smaller region, consisting of 293 villages was selected to study the sensitivity of the results to varying demand and supply parameters. The results of clustering are represented on a GIS map for the region.

Robust formulations for clustering-based large-scale classification

Chebyshev-inequality-based convex relaxations of Chance-Constrained Programs (CCPs) are shown to be useful for learning classifiers on massive datasets. In particular, an algorithm that integrates efficient clustering procedures and CCP approaches for computing classifiers on large datasets is proposed. The key idea is to identify high density regions or clusters from individual class conditional densities and then use a CCP formulation to learn a classifier on the clusters. The CCP formulation ensures that most of the data points in a cluster are correctly classified by employing a Chebyshev-inequality-based convex relaxation. This relaxation is heavily dependent on the second-order statistics. However, this formulation and in general such relaxations that depend on the second-order moments are susceptible to moment estimation errors. One of the contributions of the paper is to propose several formulations that are robust to such errors. In particular a generic way of making such formulations robust to moment estimation errors is illustrated using two novel confidence sets. An important contribution is to show that when either of the confidence sets is employed, for the special case of a spherical normal distribution of clusters, the robust variant of the formulation can be posed as a second-order cone program. Empirical results show that the robust formulations achieve accuracies comparable to that with true moments, even when moment estimates are erroneous. Results also illustrate the benefits of employing the proposed methodology for robust classification of large-scale datasets.

Effect of hydrogen charging on tensile properties of B-modified Ti-6Al-4V alloy

Trace addition of B to Ti and its alloys leads to a marked microstructural refinement, which in turn enhances the tensile and fatigue properties of the as-cast alloys. This can be particularly advantageous in applications wherein Ti alloys are used in the as-cast form. In some of these, the environment containing H and Ti alloy components is susceptible to embrittlement due to H uptake. Whether the addition of B to Ti-6Al-4V improves the relative mechanical performance of such cast components used in H environments is examined in this work. Cast Ti-6Al-4V-xB (0 <= x <= 0.55 wt%) alloys were H charged at 500 and 700 degrees C for up to 4 h. Microstructures and room temperature tensile properties of the resulting alloys have been evaluated. Experimental results show that charging at 700 degrees C for 2 h leads to the formation of titanium hydride in the microstructure, which in turn causes severe embrittlement. For shorter durations of charging, a marginal increase in strength was noted, which is attributed to the solid solution strengthening by H. The mechanical performance of the B modified alloys was found to be relatively higher, implying that B addition not only refines the as-cast microstructure but also is beneficial in applications that involve H environment A direct correlation between the volume fraction of TiB particles in the microstructure and the relative reduction in the strength of H-embrittled alloys suggests that the addition of B to Ti alloys, in optimum quantities, can be utilized as a strategy to design alloys that are more resistant to H embrittlement.

Engineering Gold Nanoparticle Interaction by PAMAM Dendrimer

Bare faceted gold nanoparticles (AuNPs) have a tendency to aggregate through a preferred attachment of the 111] surfaces. We have used fully atomistic classical molecular dynamics simulations to obtain a quantitative estimate of this surface interaction using umbrella sampling (US) at various temperatures. To tune this surface interaction, we use polyamidoamine (PAMAM) dendrimer to coat the gold surface under various conditions. We observe a spontaneous adsorption of the protonated as well as nonprotonated PAMAM dendrimer on the AuNP surface. The adsorbed dendrimer on the nanoparticle surface strongly alters the interaction between the nanoparticles. We calculate the interaction between dendrimercoated AuNPs using US and show how the interaction between two bare faceted AuNPs can be tuned as a function of dendrimer concentration and charge (pH dependent) With appropriate choice of the dendrimer concentration and charge, two strongly interacting AuNPs can be made effectively noninteracting. Our simulation results demonstrate a strategy to tune the nanoparticle interaction, which can help in engineering self-assembly of such nanoparticles.

Non-polio enteroviruses and their association with acute diarrhea in children in India

A causative agent in approximately 40% of diarrhea] cases. still remains unidentified. Though many enteroviruses (EVs) are transmitted through fecal-oral route and replicate in the intestinal cells, their association with acute diarrhea has not so far been recognized due to lack of detailed epidemiological investigations. This long-term, detailed molecular epidemiological study aims to conclusively determine the association of non-polio enteroviruses (NPEVs) with acute diarrhea in comaparison with rotavirus (RV) in children. Diarrheal stool specimens from 2161 children aged 0-2 years and 169 children between 2 and 9 years, and 1800 normal stool samples from age-matched healthy children between 0 and 9 years were examined during 2008-2012 for enterovirus (oral polio vaccine strains (OPVs) and NPEVs). Enterovirus serotypes were identified by complete VP1 gene sequence analysis. Enterovirus and rotavirus were detected in 19.01% (380/2330) and 13.82% (322/2330) diarrheal stools. During the study period, annual prevalence of EV- and RV-associated diarrhea ranged between 8% and 22%, but with contrasting seasonal prevalence with RV predominating during winter months and NPEV prevailing in other seasons. NPEVs are associated with epidemics-like outbreaks during which they are detected in up to 50% of diarrheic children, and in non-epidemic seasons in 0-10% of the patients. After subtraction of OPV-positive diarrheal cases (1.81%), while NPEVs are associated with about 17% of acute diarrhea, about 6% of healthy children showed asymptomatic NPEV excretion. Of 37 NPEV serotypes detected in diarrheal children, seven echovirus types 1, 7, 11, 13, 14, 30 and 33 are frequently observed, with Ell being more prevalent followed by E30. In conclusion, NPEVs are significantly associated with acute diarrhea, and NPEVs and rotavirus exhibit contrasting seasonal predominance. This study signifies the need for a new direction of research on enteroviruses involving systematic analysis of their contribution to diarrheal burden. (C) 2013 Elsevier B.V. All rights reserved.

Transmission electron microscopy study of Ni-rich, Ag-Ni nanowires

Present work provides an electrodeposition based methodology for synthesizing Ni-rich, Ag-Ni nanowires using an alumina template. Ag-Ni system shows negligible solid solubility in the bulk. Detailed structural and compositional characterization of as-synthesized nanowires using transmission electron microscopy technique revealed a two phase microstructure. Regions along and near the nanowire axis contained crystalline Ag-Ni solid solution phase with Ag-rich composition. Whereas, regions away from the axis and near the nanowire boundary predominantly contained nanocrystalline Ni-rich, Ni-Ag solid solution phase. (C) 2013 Elsevier B. V. All rights reserved.

Improved LSB stegananalysis based on analysis of adjacent pixel pairs

We propose a simple, reliable method based on probability of transitions and distribution of adjacent pixel pairs for steganalysis on digital images in spatial domain subjected to Least Significant Bit replacement steganography. Our method is sensitive to the statistics of underlying cover image and is a variant of Sample Pair Method. We use the new method to estimate length of hidden message reliably. The novelty of our method is that it detects from the statistics of the underlying image, which is invariant with embedding, whether the results it calculate are reliable or not. To our knowledge, no steganalytic method so far predicts from the properties of the stego image, whether its results are accurate or not.

Evolution of microstructure and texture in Ni49.4Ti38.6Hf12 shape memory alloy during hot rolling

This paper deals with the evolution of microstructure and texture during hot rolling of hafnium containing NiTi based shape memory alloy Ni49.4Ti38.6Hf12. The formation of the R-phase has been associated with the precipitation of (Ti,Hf)(2)Ni phase. The crystallographic texture of the parent phase B2 as well as the product phases R and B19' have been determined. It has been found that the variant selection during the B2 -> R phase transformation is quite strong compared to the case of the B2 -> B19' transformation. During deformation, the texture of the austenite phase evolves with strong Goss and Bs components. After transformation to martensitic structure, it gives rise to a 011]parallel to RD fiber. Microstructure and texture studies reveal the occurrence of partial dynamic recrystallization during hot rolling. Large strain heterogeneities that occur surrounding (Ti,Hf)(2)Ni precipitates are relieved through extended dynamic recovery instead of particle stimulated nucleation.

Gibbs free energy of formation of rhodium sulfides

Using a solid-state electrochemical technique, thermodynamic properties of three sulfide phases (RhS0.882, Rh3S4, Rh2S3) in the binary system (Rh + S) are measured as a function of temperature over the range from (925 to 1275) K. Single crystal CaF2 is used as the electrolyte. The auxiliary electrode consisting of (CaS + CaF2) is designed in such a way that the sulfur chemical potential converts into an equivalent fluorine potential at each electrode. The sulfur potentials at the measuring electrodes are established by the mixtures of (Rh + RhS0.882), (RhS0.882 + Rh3S4) and (Rh3S4 + Rh2S3) respectively. A gas mixture (H-2 + H2S + Ar) of known composition fixes the sulfur potential at the reference electrode. A novel cell design with physical separation of rhodium sulfides in the measuring electrode from CaS in the auxiliary electrode is used to prevent interaction between the two sulfide phases. They equilibrate only via the gas phase in a hermetically sealed reference enclosure. Standard Gibbs energy changes for the following reactions are calculated from the electromotive force of three cells: 2.2667Rh (s) + S-2 (g) -> 2.2667RhS(0.882) (s), Delta(r)G degrees +/- 2330/(J . mol(-1)) = -288690 + 146.18 (T/K), 4.44RhS(0.882) (s) + S-2 (g) -> 1.48Rh(3)S(4) (s), Delta(r)G degrees +/- 2245/(J . mol(-1)) = -245596 + 164.31 (T/K), 4Rh(3)S(4) (s) + S-2 (g) -> 6Rh(2)S(3) (s), Delta(r)G degrees +/- 2490/(J . mol(-1)) = -230957 + 160: 03 (T/K). Standard entropy and enthalpy of formation of rhodium sulfides from elements in their normal standard states at T = 298.15 K are evaluated. (C) 2013 Elsevier Ltd. All rights reserved.

Response of vertically loaded pile in clay: a probabilistic study

This study presents the response of a vertically loaded pile in undrained clay considering spatially distributed undrained shear strength. The probabilistic study is performed considering undrained shear strength as random variable and the analysis is conducted using random field theory. The inherent soil variability is considered as source of variability and the field is modeled as two dimensional non-Gaussian homogeneous random field. Random field is simulated using Cholesky decomposition technique within the finite difference program and Monte Carlo simulation approach is considered for the probabilistic analysis. The influence of variance and spatial correlation of undrained shear strength on the ultimate capacity as summation of ultimate skin friction and end bearing resistance of pile are examined. It is observed that the coefficient of variation and spatial correlation distance are the most important parameters that affect the pile ultimate capacity.

Experiments and analysis of propagation front under gasification regimes in a packed bed

The paper analyses the results of experiments on the propagation rate in a fuel bed under gasification conditions in a co-current reactor configuration. Experiments using wood chips with different values of moisture content have been conducted under gasification conditions. The influence of air mass flux on the propagation rate, peak temperature and gas quality is investigated. It is observed from the experiments that the flame front propagation rate initially increases as the air mass flux increased, reaching a peak propagation rate, and further increase in the air mass flux results in a decrease in the propagation rate. However, the bed movement increases with the increase in air mass flux. The experimental results provide an understanding on influence of the fuel properties on propagation front. The surface area per unit volume of the particles in the packed bed plays an important role in the propagation rate. It has been argued that the flaming pyrolysis contributes towards the flame propagation as opposed to the overall combustion process in a packed bed. The calorific value of the producer gas generated is nearly the same over the entire range of air mass flux for bone-dry and 10% moist wood. (C) 2014 Elsevier B.V. All rights reserved.

Rapid determination of main constituents of packed juices by reverse phase-high performance liquid chromatography: an insight in to commercial fruit drinks

The present work reports the compositional analysis of thirteen different packed fruit juices using high performance liquid chromatography (HPLC). Vitamin C, organic acids (citric and malic) and sugars (fructose, glucose and sucrose) were separated, analyzed and quantified using different reverse phase methods. A new rapid reverse phase HPLC method was developed for routine analysis of vitamin C in fruit juices. The precision results of the methods showed that the relative standard deviations of the repeatability and reproducibility were < 0.05 and < 0.1 respectively. Correlation coefficient of the calibration models developed was found to be higher than 0.99 in each case. It has been found that the content of Vitamin C was less variable amongst different varieties involved in the study. It is also observed that in comparison to fresh juices, the packed juices contain lesser amounts of vitamin C. Citric acid was found as the major organic acids present in packed juices while maximum portion of sugars was of sucrose. Comparison of the amount of vitamin C, organic acids and sugars in same fruit juice of different commercial brands is also reported.

Transmission of elastic waves through a frictional boundary

Incident energy gets transmitted, reflected and absorbed across an interface in jointed rock mass leading to energy dissipation and alteration of waves. Wave velocities get attenuated during their propagation across joints and this behavior is studied using bender/extender element tests. The velocity attenuation and modulus reduction observed in experimental tests are modeled with three dimensional distinct element code and results are validated. Normal propagation of an incident shear wave through a jointed rock mass cause slip of the rock blocks if shear stress of wave exceeds the shear strength of the joint. As the properties of joint determine the transmission of energy across an interface, a parametric study is then conducted with the validated numerical model by varying the parameters that may determine the energy transmission across a joint using modified Miller's method. Results of the parametric study are analyzed and presented in the paper. (C) 2014 Elsevier Ltd. All rights reserved.

Spatial variation of seismicity parameters across India and adjoining areas

An attempt has been made to quantify the variability in the seismic activity rate across the whole of India and adjoining areas (0–45°N and 60–105°E) using earthquake database compiled from various sources. Both historical and instrumental data were compiled and the complete catalog of Indian earthquakes till 2010 has been prepared. Region-specific earthquake magnitude scaling relations correlating different magnitude scales were achieved to develop a homogenous earthquake catalog for the region in unified moment magnitude scale. The dependent events (75.3%) in the raw catalog have been removed and the effect of aftershocks on the variation of b value has been quantified. The study area was divided into 2,025 grid points (1°91°) and the spatial variation of the seismicity across the region have been analyzed considering all the events within 300 km radius from each grid point. A significant decrease in seismic b value was seen when declustered catalog was used which illustrates that a larger proportion of dependent events in the earthquake catalog are related to lower magnitude events. A list of 203,448 earth- quakes (including aftershocks and foreshocks) occurred in the region covering the period from 250 B.C. to 2010 A.D. with all available details is uploaded in the website http://www.civil.iisc.ernet.in/*sreevals/resource.htm.