Sol-gel derived, magnesium based ionically conducting composites

Composite ionic conductors based on magnesium salts and sol-gel derived silicate-tetraethylene glycol hybrids have been synthesized. The structure of these materials has been studied by FT-IR, FT-Raman, Si-29 and C-13 NMR and XRD techniques. The composite systems can be best described as diphasic with silicate as filters in the organic phase that provides solubility of the ionic dispersants. The ionic interactions in the matrix are clearly observed in the FT-Raman spectra. The ionic conductivity is determined to be of the order of 10(-7) to 10(-5) S cm(-1) at room temperature for MgCl2 and Mg(ClO4)(2) salts respectively. The conductivity reaches 10(-4) and 10(-3) S cm(-1) at 80degreesC respectively.

Synthesis and Self-Assembly of Donor-Acceptor-Donor Based Oligothiophenes and Their Optoelectronic Properties

In this work, the synthesis of an oligothiophene having a donor acceptor donor (D-A-D) chromophore with hydrogen bonding groups is described. The D-A-D molecule was demonstrated to self-organize via intermolecular H-bonding between barbituric acid units. Interactions between the oligothiophene subunits were also found to be important, affording nanoribbons that could be observed by atomic force and transmission electron microscopy. The applicability of the oligothiophene for organic electronic applications was investigated by fabricating organic field-effect transistors (OFETs) and organic photovoltaic devices. The OFET measurements yielded p-type mobility of 7 x 10(-7) cm(2)/(Vs), and when blended with C(60)-PCBM, the photovoltaic efficiency was observed to be 0.18%.

Pruned Universal Symbol Sequences for LZW based Language identification

We present a improved language modeling technique for Lempel-Ziv-Welch (LZW) based LID scheme. The previous approach to LID using LZW algorithm prepares the language pattern table using LZW algorithm. Because of the sequential nature of the LZW algorithm, several language specific patterns of the language were missing in the pattern table. To overcome this, we build a universal pattern table, which contains all patterns of different length. For each language it's corresponding language specific pattern table is constructed by retaining the patterns of the universal table whose frequency of appearance in the training data is above the threshold.This approach reduces the classification score (Compression Ratio [LZW-CR] or the weighted discriminant score[LZW-WDS]) for non native languages and increases the LID performance considerably.

Lamb wave based identification and parameter estimation of corrosion in metallic plate structure using a circular PWAS array

A circular array of Piezoelectric Wafer Active Sensor (PWAS) has been employed to detect surface damages like corrosion using lamb waves. The array consists of a number of small PWASs of 10 mm diameter and 1 mm thickness. The advantage of a circular array is its compact arrangement and large area of coverage for monitoring with small area of physical access. Growth of corrosion is monitored in a laboratory-scale set-up using the PWAS array and the nature of reflected and transmitted Lamb wave patterns due to corrosion is investigated. The wavelet time-frequency maps of the sensor signals are employed and a damage index is plotted against the damage parameters and varying frequency of the actuation signal (a windowed sine signal). The variation of wavelet coefficient for different growth of corrosion is studied. Wavelet coefficient as function of time gives an insight into the effect of corrosion in time-frequency scale. We present here a method to eliminate the time scale effect which helps in identifying easily the signature of damage in the measured signals. The proposed method becomes useful in determining the approximate location of the corrosion with respect to the location of three neighboring sensors in the circular array. A cumulative damage index is computed for varying damage sizes and the results appear promising.

Ferrocene-Conjugated L-Tryptophan Copper(II) Complexes of Phenanthroline Bases Showing DNA Photocleavage Activity and Cytotoxicity

Ferrocene-conjugated L-tryptophan (L-Trp) reduced Schiff base (Fc-TrpH) copper(II) complexes [Cu(Fc-Trp)(L)](ClO(4)) of phenanthroline bases (L), viz. 2,2'-bipyridine (bpy in 1), 1,10-phenanthroline (phen in 2), dipyrido[3,2-d:2',3'-f]quinoxaline (dpq in 3), and dipyrido[3,2-a:2',3'-c]phenazine (dppz in 4), were prepared and characterized and their photocytotoxicity studied. Cationic reduced Schiff base (Ph-TrpH) complexes [Cu(Ph-Trp)(L)(H(2)O)] (ClO(4)) (L = phen in 5; dppz in 6) having the ferrocenyl moiety replaced by a phenyl group and the Zn(II) analogue (7) of complex 4 were prepared and used as control species. The crystal structures of 1 and 5 with respective square-planar CuN(3)O and square-pyramidal CuN(3)O(2) coordination geometry show significantly different core structures. Complexes 1-4 exhibit a Cu(II)-Cu(I) redox couple near -0.1 V and the Fc(+)-Fc couple at similar to 0.5 V vs SCE in DMF-0.1 M [Bu(4)(n)N] (ClO(4)) (Fc = ferrocenyl moiety). The complexes display a copper(II)-based d-d band near 600 nm and a Fc-centered band at similar to 450 nm in DMF-Tris-HCl buffer. The complexes are efficient binders to calf thymus DNA. They are synthetic chemical nucleases in the presence of thiol or H(2)O(2), forming hydroxyl radicals. The photoactive complexes are cleavers of pUC19 DNA in visible light, forming hydroxyl radicals. Complexes 2-6 show photocytotoxicity in HeLa cancer cells, giving IC(50) values of 4.7, 10.2, 1.3, 4.8, and 4.3 mu M, respectively, in visible light with the appearance of apoptotic bodies. The complexes also show photocytotoxicity in MCF-7 cancer cells. Nuclear chromatin cleavage has been observed with acridine orange/ethidium bromide (AO/EB) dual staining with complex 4 in visible light. The complexes induce caspase-independent apoptosis in the HeLa cells.

Correction for Bias in Downscaling GCM Simulations for Hydrologic Impact Assessment

In a statistical downscaling model, it is important to remove the bias of General Circulations Model (GCM) outputs resulting from various assumptions about the geophysical processes. One conventional method for correcting such bias is standardisation, which is used prior to statistical downscaling to reduce systematic bias in the mean and variances of GCM predictors relative to the observations or National Centre for Environmental Prediction/ National Centre for Atmospheric Research (NCEP/NCAR) reanalysis data. A major drawback of standardisation is that it may reduce the bias in the mean and variance of the predictor variable but it is much harder to accommodate the bias in large-scale patterns of atmospheric circulation in GCMs (e.g. shifts in the dominant storm track relative to observed data) or unrealistic inter-variable relationships. While predicting hydrologic scenarios, such uncorrected bias should be taken care of; otherwise it will propagate in the computations for subsequent years. A statistical method based on equi-probability transformation is applied in this study after downscaling, to remove the bias from the predicted hydrologic variable relative to the observed hydrologic variable for a baseline period. The model is applied in prediction of monsoon stream flow of Mahanadi River in India, from GCM generated large scale climatological data.

Groundwater Management in India:Physical, Institutional and Policy Alternatives

Groundwater constitutes a vital natural resource for sustaining India’s agricultural economy and meeting the country’s social, ecological and environmental goals. It is a unique resource, widely available, providing security against droughts and yet it is closely linked to surface-water resources and the hydrological cycle. Its availability depends on geo-hydrological conditions and characteristics of aquifers, from deep to alluvium, sediment crystalline rocks to basalt formations; and agro-climate from humid to subhumid and semi-arid to arid. Its reliable supply, uniform quality and temperature, relative turbidity, pollution-safe, minimal evaporation losses, and low cost of development are attributes making groundwater more attractive compared to other resources. It plays a key role in the provision of safe drinking water to rural populations. For example, already almost 80% of domestic water use in rural areas in India is groundwater-supplied, and much of it is being supplied to farms, villages and small towns. Inadequate control of the use of groundwater, indiscriminate application of agrochemicals and unrestrained pollution of the rural environment by other human activities make groundwater usage unsustainable, necessitating proper management in the face of the twin demand for water of good quality for domestic supply and adequate supply for irrigation, ensuring equity, efficiency and sustainability of the resource. Groundwater irrigation has overtaken surface irrigation in the early 1980s, supported by well energization. It is estimated that there are about 24 million energised wells and tube wells now and it is driven by demand rather than availability, evident through the greater occurrence of wells in districts with high population densities. Apart from aquifer characteristics, land fragmentation and landholding size are the factors that decide the density of wells. The ‘rise and fall’ of local economies dependent on groundwater can be summarized as: the green revolution of 1980s, groundwaterbased agrarian boom, early symptoms of groundwater overdraft, and decline of the groundwater socio-ecology. The social characteristics and policy interventions typical of each stage provide a fascinating insight into the human-resource dynamics. This book is a compilation of nine research papers discussing various aspects of groundwater management. It attempts to integrate knowledge about the physical system, the socio-economic system, the institutional set-up and the policy environment to come out with a more realistic analysis of the situation with regard to the nature, characteristics and intensity of resource use, the size of the economy the use generates, and the negative socioeconomic consequences. Complex variables addressed in this regard focusing on northern Gujarat are the stock of groundwater available in the region, its hydrodynamics, its net outflows against inflows, the economics of its intensive use (particularly irrigation in semi-arid and arid regions), its criticality in the regional hydroecological regime, ethical aspects and social aspects of its use. The first chapter by Dinesh Kumar and Singh, dwells on complex groundwater socio-ecology of India, while emphasizing the need for policy measures to address indiscriminate over-exploitation of dwindling resources. The chapter also explores the nature of groundwater economy and the role of electricity prices on it. The next chapter on groundwater issue in north Gujarat provides a description of groundwater resource characteristics followed by a detailed analysis of the groundwater depletion and quality deterioration problems in the region and their undesirable consequences on the economy, ecosystem health and the society. Considering water-buyers and wellowning farmers individually, a methodology for economic valuation of groundwater in regions where its primary usage is in agriculture, and as assessment of the groundwater economy based on case studies from north Gujarat is presented in the fourth chapter. The next chapter focuses on the extent of dependency of milk production on groundwater, which includes the water embedded in green and dry fodder and animal feed. The study made a realistic estimate of irrigation water productivity in terms of the physics and economics of milk production. The sixth chapter analyses the extent of reduction in water usage, increase in yield and overall increase in physical productivity of alfalfa with the use of the drip irrigation system. The chapter also provides a detailed synthesis of the costs and benefits associated with the use of drip irrigation systems. A linear programmingbased optimization model with the objective to minimize groundwater use taking into account the interaction between two distinct components – farming and dairying under the constraints of food security and income stability for different scenarios, including shift in cropping pattern, introduction of water-efficient crops, water- saving technologies in addition to the ‘business as usual’ scenario is presented in the seventh chapter. The results show that sustaining dairy production in the region with reduced groundwater draft requires crop shifts and adoption of water-saving technologies. The eighth chapter provides evidences to prove that the presence of adequate economic incentive would encourage farmers to adopt water-saving irrigation devices, based on the findings of market research with reference to the level of awareness among farmers of technologies and the factors that decide the adoption of water-saving technologies. However, now the marginal cost of using electricity for agricultural pumping is almost zero. The economic incentives are strong and visible only when the farmers are either water-buyers or have to manage irrigation with limited water from tube-well partnerships. The ninth chapter explores the socio-economic viability of increasing the power tariff and inducing groundwater rationing as a tool for managing energy and groundwater demand, considering the current estimate of the country’s annual economic loss of Rs 320 billion towards electricity subsidy in the farm sector. The tenth chapter suggests private tradable property rights and development of water markets as the institutional tool for achieving equity, efficiency and sustainability of groundwater use. It identifies the externalities for local groundwater management and emphasizes the need for managing groundwater by local user groups, supported by a thorough analysis of groundwater socio-ecology in India. An institutional framework for managing the resource based on participatory approach that is capable of internalizing the externalities, comprising implementation of institutional and technical alternatives for resource management is also presented. Major findings of the analyses and key arguments in each chapter are summarized in the concluding chapter. Case studies of the social and economic benefits of groundwater use, where that use could be described as unsustainable, are interesting. The benefits of groundwater use are outlined and described with examples of social and economic impacts of groundwater and the negative aspects of groundwater development with the compilation of environmental problems based on up-to-date research results. This publication with a well-edited compilation of case studies is informative and constitutes a useful publication for students and professionals.

Conductance of a photochromic molecular switch with graphene leads

We report a full self-consistent ab initio calculation of the conductance of a diarylethene-based molecular switch with two graphene electrodes. Our results show the contributions of the resonant states of the molecule, of the electrode density of states, and of graphene unique features, such as edge states. The conductivities are found to be significantly different for the two photochromic isomers at zero and finite applied bias. Further we point out the possibility of causing the switching by the application of a large potential difference between the two electrodes.

Inhibition of peroxynitrite- and peroxidase-mediated protein tyrosine nitration by imidazole-based thiourea and selenourea derivatives

In the present study, the synthesis and characterization of a series of N-methylimidazole-based thiourea and selenourea derivatives are described. The new compounds were also studied for their ability to inhibit peroxynitrite (PN)- and peroxidase-mediated nitration of protein tyrosine residues. It has been observed that the selenourea derivatives are more efficient than the thiourea-based compounds in the inhibition of protein nitration. The higher activity of selenoureas as compared to that of the corresponding thioureas can be ascribed to the zwitterionic nature of the selenourea moiety. Single crystal X-ray diffraction studies on some of the thiourea and selenourea derivatives reveal that the C S bonds in thioureas possess more of double bond character than the C=Se bonds in the corresponding selenoureas. Therefore, the selenium compounds can react with PN or hydrogen peroxide much faster than their sulfur analogues. The reactions of thiourea and selenourea derivatives with PN or hydrogen peroxide produce the corresponding sulfinic or seleninic acid derivatives, which upon elimination of sulfurous/selenous acids produce the corresponding N-methylimdazole derivatives.

Dye sensitized solar cell based on platinum decorated multiwall carbon nanotubes as catalytic layer on the counter electrode

In this study we have employed multiwall carbon nanotubes (MWCNT), decorated with platinum as catalytic layer for the reduction of tri-iodide ions in dye sensitized solar cell (DSSC). MWCNTs have been prepared by a simple one step pyrolysis method using ferrocene as the catalyst and xylene as the carbon source. Platinum decorated MWCNTs have been prepared by chemical reduction method. The as prepared MWCNTs and Pt/MWCNTs have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). In combination with a dye adsorbed TiO(2) photoanode and an organic liquid electrolyte, Pt/MWCNT composite showed an enhanced short circuit current density of 16.12 mA/cm(2) leading to a cell efficiency of 6.50% which is comparable to that of Platinum. (C) 2011 Elsevier Ltd. All rights reserved.

An experimental study of boundary layer transition induced by a cylinder wake

Boundary layer transition induced by the wake of a circular cylinder in the free stream has been investigated using the particle image velocimetry technique. Some differences between simulation and experimental studies have been reported in the literature, and these have motivated the present study. The appearance of spanwise vortices in the early stage is further confirmed here. Lambda spanwise vortex appears to evolve into a Lambda/hairpin vortex; the flow statistics also confirm such vortices. With increasing Reynolds number, based on the cylinder diameter, and with decreasing cylinder height from the plate, the physical size of these hairpin-like structures is found to decrease. Some mean flow characteristics, including the streamwise growth of the disturbance energy, in a wake-induced transition resemble those in bypass transition induced by free stream turbulence. Streamwise velocity streaks that are eventually generated in the late stage often undergo sinuous-type oscillations. Similar to other transitional flows, an inclined shear layer in the wall-normal plane is often seen to oscillate and shed vortices. The normalized shedding frequency of these vortices, estimated from the spatial spacing and the convection velocity of these vortices, is found to be independent of the Reynolds number, similar to that in ribbon-induced transition. Although the nature of free stream disturbance in a wake-induced transition and that in a bypass transition are different, the late-stage features including the flow breakdown characteristics of these two transitions appear to be similar.

Extending the Supramolecular Synthon Based Fragment Approach (SBFA) for Transferability of Multipole Charge Density Parameters to Monofluorobenzoic Acids and their Cocrystals with Isonicotinamide: Importance of C-H center dot center dot center dot O, C-H center dot center dot center dot F, and F center dot center dot center dot F Intermolecular Regions

An extension of the supramolecular synthon-based fragment approach (SBFA) method for transferability of multipole charge density parameters to include weak supramolecular synthons is proposed. In particular, the SBFA method is applied to C-H center dot center dot center dot O, C-H center dot center dot center dot F, and F center dot center dot center dot F containing synthons. A high resolution charge density study has been performed on 4-fluorobenzoic acid to build a synthon library for C-H center dot center dot center dot F infinite chain interactions. Libraries for C-H center dot center dot center dot O and F center dot center dot center dot F synthons were taken from earlier work. The SBFA methodology was applied successfully to 2- and 3-fluorobenzoic acids, data sets for which were collected in a routine manner at 100 K, and the modularity of the synthons was demonstrated. Cocrystals of isonicotinamide with all three fluorobenzoic acids were also studied with the SBFA method. The topological analysis of inter- and intramolecular interaction regions was performed using Bader's AIM approach. This study shows that the SBFA method is generally applicable to generate charge density maps using information from multiple intermolecular regions.

An eight-connected metal organic framework based on Cu(5) clusters: Synthesis, structure, magnetic and catalytic properties

A reaction of copper acetate, 5-nitroisophthalic acid in a water-methanol mixture under solvothermal condition results in a new metal-organic framework compound, [Cu(5)(mu(3)-OH)(2)(H(2)O)(6){(NO(2))-C(6)H(3)-(COO)(2)}(4)]center dot 5H(2)O, (1). The compound contains Cu5 pentameric cluster units connected by 5-nitro isophthalate (NIPA) moieties forming a CdCl(2)-like layer, which are further connected by another NIPA moiety forming the three-dimensional structure. The water molecules in (1) can be reversibly adsorbed. The removal of water accompanies a change in the colour as well as a structural re-organization. Magnetic studies suggest strong antiferromagnetie correlations between the Cu5 cluster units. The compound (1) exhibits heterogeneous Lewis acid catalysis for the cyanosilylation of imines with more than 95 % selectivity. Compound (1) has been characterized by IR, UV-vis, TGA, powder XRD studies.

Some adsorption-nucleation-based models for electrochemical phase formation

A new class of models which are based on adsorption, nucleation growth and their coupling is discussed. In particular, the potentiostatic response of a model that involves nucleative phase growth via direct incorporation and adsorptive discharge of metal ions on the free area is analysed for both instantaneous and progressive nucleation. This model is able to predict certain experimental features in the potentiostatic transient, like the initial fall, shoulder or maximum (as well as minimum) which have not been predicted by models analysed hitherto.Limiting behaviour for short and long times as well as a description of the above-mentioned features in terms of model parameters are given.A special case of the above model, viz. a reversible adsorption–nucleation model, wherein the adsorption is very fast, is shown to give rise to transients which can be distinguished from the pure nucleation-growth transients only by its parametric dependence, but not by the form.