Air oxygenation chemistry of 4-TBC catalyzed by chloro bridged dinuclear copper(II) complexes of pyrazole based tridentate ligands: synthesis, structure, magnetic and computational studies

Four dinuclear bis(mu-Cl) bridged copper(II) complexes, Cu-2(mu-Cl)(2)(L-X)(2)](ClO4)(2) (L-X = N,N-bis(3,5-dimethylpyrazole-1-yl)-methyl]benzylamine with X = H(1), OMe(2), Me(3) and Cl(4)), have been synthesized and characterized by the single crystal X-ray diffraction method. In these complexes, each copper(II) center is penta-coordinated with square-pyramidal geometry. In addition to the tridentate L-X ligand, a chloride ion occupies the last position of the square plane. This chloride ion is also bonded to the neighboring Cu(II) site in its axial position forming an SP-I dinuclear Cu(II) unit that exhibits small intramolecular ferromagnetic interactions and supported by DFT calculations. The complexes 1-3 exhibit methylmonooxygenase (pMMO) behaviour and oxidise 4-tert-butylcatechol (4-TBCH2) with molecular oxygen in MeOH or MeCN to 4-tert-butyl-benzoquinone (4-TBQ), 5-methoxy-4-tert-butyl-benzoquinone (5-MeO-4-TBQ) as the major products along with 6,6'-Bu-t-biphenyl-3,4,3',4'-tetraol and others as minor products. These are further confirmed by ESI- and FAB-mass analyses. A tentative catalytic cycle has been framed based on the mass spectral analysis of the products and DFT calculations on individual intermediates that are energetically feasible.

Impact of pit-toilet leachate on groundwater chemistry and role of vadose zone in removal of nitrate and E-coli pollutants in Kolar District, Karnataka, India

Assessment of chemistry of groundwater infiltrated by pit-toilet leachate and contaminant removal by vadose zone form the focus of this study. The study area is Mulbagal Town in Karnataka State, India. Groundwater level measurements and estimation of unsaturated permeability indicated that the leachate recharged the groundwater inside the town at the rate of 1 m/day. The average nitrate concentration of groundwater inside the town (148 mg/L) was three times larger than the permissible limit (45 mg/L), while the average nitrate concentration of groundwater outside the town (30 mg/L) was below the permissible limit. The groundwater inside the town exhibited E. coli contamination, while groundwater outside the town was free of pathogen contamination. Infiltration of alkalis (Na+, K+) and strong acids (Cl-, SO4 (2-)) caused the mixed Ca-Mg-Cl type (60 %) and Na-Cl type (28 %) facies to predominate groundwater inside the town, while, Ca-HCO3 (35 %), mixed Ca-Mg-Cl type (35 %) and mixed Ca-Na-HCO3 type (28 %) facies predominated groundwater outside/periphery of town. Reductions in E. coli and nitrate concentrations with vadose zone thickness indicated its participation in contaminant removal. A 4-m thickness of unsaturated sand + soft, disintegrated weathered rock deposit facilitates the removal of 1 log of E. coli pathogen. The anoxic conditions prevailing in the deeper layers of the vadose zone (> 19 m thickness) favor denitrification resulting in lower nitrate concentrations (28-96 mg/L) in deeper water tables (located at depths of -29 to -39 m).

Influence of anthropogenic contamination on groundwater chemistry in Mulbagal town, Kolar District, India

Geochemical studies are performed to examine the impact of leachate infiltration from on-site sewage disposal systems on the groundwater chemistry in Mulbagal town, Kolar District, Karnataka State, India. The leachate infiltration imposed nitrate concentrations ranging from 4 mg/L to 388 mg/L in the groundwater samples; it was observed that 79% of the samples exhibited nitrate concentrations in excess of drinking water permissible limit (45 mg/L). The average (of 43 measurements) E. coli levels in the groundwater samples corresponded to 189 MPN/100 mL and 55% of the samples tested exhibit pathogen contamination. Results also showed that the groundwater in the study area is characterized by acidic pH, large calcium + magnesium ion and Na/Cl ratios of < unity causing majority of the ground water samples to classify as Ca-Mg-Cl type and Na-Cl type. Saturation index (SI) computation using Visual MINTEQ program showed that the groundwater samples are under-saturated with respect to calcite. The theoretical SI values (of calcite) however suggested that the groundwater samples ought to be over-saturated with calcite. Under-saturation of the groundwater samples with calcite is attributed to increased dissolution of the mineral in the acidic environment of the groundwater.

Chromite-silicate chemistry of the Neoarchean Sittampundi Complex, southern India: Implications for subduction-related arc magmatism

The Neoarchean layered anorthositic complex at Sittampundi in southern India is known for its chromitite layers that are mostly associated with anorthosite (An(90-100)). The chromitites contain FeAl-rich chromites concentrated in layers between amphibole-rich layers with a dominant mineralogy of amphibole-spinel-plagiocase+/-sapphirine. The chromite-rich layers contain only amphibole and plagioclase. Mineral compositions illustrated by X-ray composition maps and profiles show subtle chemical differences. The chrome spinels are of refractory grade with Cr2O3 and Al2O3 contents varying between 34-40 wt.% and 23-28 wt.%. The chromite compositions are noticeably different from those in layered igneous intrusions of the Bushveld-Stillwater type. The existence of original highly calcic plagioclase, FeAl-rich chromite, and magmatic amphibole is consistent with derivation from a parental magma of hydrous tholeiitic composition that was most likely generated in a supra-subduction zone arc setting. In terms of mineralogy and field relations, the Sittampundi chromitites are remarkably similar to anorthosite-hosted chromitites in the Neoarchean Fiskensset anorthositic complex, Greenland. We propose that the Sittampundi chromitites formed by partial melting of unusually aluminous harzburgite in a hydrated mantle wedge above a subduction zone. This melting process produced hydrous, aluminous basalt, which fractionated at depth to give rise to a variety of high-alumina basalt compositions from which the anorthositic complex with its cumulate chromite-rich and amphibole-rich layers formed within the magma chamber of a supra-subduction zone arc. (C) 2011 Elsevier B.V. All rights reserved.

Influence of physical structure and chemistry of diesel soot suspended in hexadecane on lubrication of steel-on-steel contact

Soot generated from the combustion process in diesel engines affect engine tribology. In this paper, two diesel soot samples; from engine exhaust and oil filter are suspended in hexadecane oil and the suspension is used to lubricate a steel ball on steel flat sliding contact at a contact pressure of 1.3 GPa. The friction and wear of the steel flat are recorded. The data are compared with those recorded when the soot is generated by burning ethylene gas. The rationale for the comparatively poor tribology of diesel soot is explored by quantifying the size and shape of primary particles and agglomerates, hardness of single primary soot particles, the crystallinity and surface and near surface chemistry of soot and interparticle adhesion.

Performance evaluation of chemistry transport models over India

Using continuous and near-real time measurements of the mass concentrations of black carbon (BC) aerosols near the surface, for a period of 1 year (from January to December 2006) from a network of eight observatories spread over different environments of India, a space-time synthesis is generated. The strong seasonal variations observed, with a winter high and summer low, are attributed to the combined effects of changes in synoptic air mass types, modulated strongly by the atmospheric boundary layer dynamics. Spatial distribution shows much higher BC concentration over the Indo-Gangetic Plain (IGP) than the peninsular Indian stations. These were examined against the simulations using two chemical transport models, GOCART (Goddard Global Ozone Chemistry Aerosol Radiation and Transport) and CHIMERE for the first time over Indian region. Both the model simulations significantly deviated from the measurements at all the stations; more so during the winter and pre-monsoon seasons and over mega cities. However, the CHIMERE model simulations show better agreement compared with the measurements. Notwithstanding this, both the models captured the temporal variations; at seasonal and subseasonal timescales and the natural variabilities (intra-seasonal oscillations) fairly well, especially at the off-equatorial stations. It is hypothesized that an improvement in the atmospheric boundary layer (ABL) parameterization scheme for tropical environment might lead to better results with GOCART.

Investigation of phase separation in bulk heterojunction solar cells via supramolecular chemistry

In this work, we have prepared two donor-acceptor-donor (D-A-D) pi-conjugated oligomers to investigate the effect of phase separation on the performance of bulk heterojunction (BHJ) solar cells. These charge transfer low band gap pi-conjugated oligomers (TTB and NMeTTB) were synthesized by Knoevenagel condensation of terthiophenecarbaldehyde and barbiturate appended pyran derivative. The thin film morphology of both the oligomers and along with electron acceptor 6,6]-phenyl-C60-butyric acid methyl ester (PC61BM) was investigated by atomic force microscopy (AFM) and transmission electron microscopy (TEM). The blend of NMeTTB and PC61BM thin film yield highly ordered thin film, whereas there was clear phase separation between TTB and PC61BM in thin film. The BHJ solar cell was fabricated using a blend of NMeTTB and TTB with PC61BM acceptor in 1:1 ratio as active layer, and a power conversion efficiency of 1.8% was obtained. This device characteristic was compared with device having TTB:PC61BM as active layer, and large difference is observed in photocurrents. This poor performance of TTB in BHJ devices was attributed to the difference in the nanoscale morphology of the corresponding derivatives. We rationalize our findings based on the low charge carrier mobility in organic field-effect transistors and miscibility/phase separation parameter of binary components (oligomers and PC61BM) in the active layer of bulk heterojunction solar cells.

Phase chemistry of the system Nb-Rh-O

Phase relations in the system Nb-Rh-O at 1223 K were investigated by isothermal equilibration of eleven compositions and analysis of quenched samples using OM, XRD, SEM and EDS. The oxide phase in equilibrium with the alloy changes progressively from NbO to NbO2, NbO2.422 and Nb2O5-x with increasing Rh. Only one ternary oxide NbRhO4 with tetragonal structure (a=0.4708 nm and c=0.3017 nm) was detected. It coexists with Rh and Nb2O5. The standard Gibbs energy of formation of NbRhO4 from its component binary oxides measured using a solid-state electrochemical cell can be represented by the equation; Delta G(f,ox)(o)(J/mol) = -38,350 + 5.818 x T(+/- 96) Constructed on the basis of thermodynamic information of the various alloy and oxide phases are oxygen potential diagram for the system Nb-Rh-O at 1223 K and temperature-composition diagrams at constant partial pressures of oxygen.

Improved modeling of groundwater recharge in agricultural watersheds using a combination of crop model and remote sensing

For improved water management and efficiency of use in agriculture, studies dealing with coupled crop-surface water-groundwater models are needed. Such integrated models of crop and hydrology can provide accurate quantification of spatio-temporal variations of water balance parameters such as soil moisture store, evapotranspiration and recharge in a catchment. Performance of a coupled crop-hydrology model would depend on the availability of a calibrated crop model for various irrigated/rainfed crops and also on an accurate knowledge of soil hydraulic parameters in the catchment at relevant scale. Moreover, such a coupled model should be designed so as to enable the use/assimilation of recent satellite remote sensing products (optical and microwave) in order to model the processes at catchment scales. In this study we present a framework to couple a crop model with a groundwater model for applications to irrigated groundwater agricultural systems. We discuss the calibration of the STICS crop model and present a methodology to estimate the soil hydraulic parameters by inversion of crop model using both ground and satellite based data. Using this methodology we demonstrate the feasibility of estimation of potential recharge due to spatially varying soil/crop matrix.

Characterization of groundwater chemistry under the influence of lithologic and anthropogenic factors along a climatic gradient in Upper Cauvery basin, South India

Hydrogeological and climatic effect on chemical behavior of groundwater along a climatic gradient is studied along a river basin. `Semi-arid' (500-800 mm of mean annual rainfall), `sub-humid' (800-1,200 mm/year) and `humid' (1,200-1,500 mm/year) are the climatic zones chosen along the granito-gneissic plains of Kabini basin in South India for the present analysis. Data on groundwater chemistry is initially checked for its quality using NICB ratio (<+/- 5 %), EC versus TZ+ (similar to 0.85 correlation), EC versus TDS and EC versus TH analysis. Groundwater in the three climatic zones is `hard' to `very hard' in terms of Ca-Mg hardness. Polluted wells are identified (> 40 % of pollution) and eliminated for the characterization. Piper's diagram with mean concentrations indicates the evolution of CaNaHCO3 (semi-arid) from CaHCO3 (humid zone) along the climatic gradient. Carbonates dominate other anions and strong acids exceeded weak acids in the region. Mule Hole SEW, an experimental watershed in sub-humid zone, is characterized initially using hydrogeochemistry and is observed to be a replica of entire sub-humid zone (with 25 wells). Extension of the studies for the entire basin (120 wells) showed a chemical gradient along the climatic gradient with sub-humid zone bridging semi-arid and humid zones. Ca/Na molar ratio varies by more than 100 times from semi-arid to humid zones. Semi-arid zone is more silicaceous than sub-humid while humid zone is more carbonaceous (Ca/Cl similar to 14). Along the climatic gradient, groundwater is undersaturated (humid), saturated (sub-humid) and slightly supersaturated (semi-arid) with calcite and dolomite. Concentration-depth profiles are in support of the geological stratification i.e., not approximate to 18 m of saprolite and similar to 25 m of fracture rock with parent gneiss beneath. All the wells are classified into four groups based on groundwater fluctuations and further into `deep' and `shallow' based on the depth to groundwater. Higher the fluctuations, larger is its impact on groundwater chemistry. Actual seasonal patterns are identified using `recharge-discharge' concept based on rainfall intensity instead of traditional monsoon-non-monsoon concept. Non-pumped wells have low Na/Cl and Ca/Cl ratios in recharge period than in discharge period (Dilution). Few other wells, which are subjected to pumping, still exhibit dilution chemistry though water level fluctuations are high due to annual recharge. Other wells which do not receive sufficient rainfall and are constantly pumped showed high concentrations in recharge period rather than in discharge period (Anti-dilution). In summary, recharge-discharge concept demarcates the pumped wells from natural deep wells thus, characterizing the basin.

Synergistic effect of reactor chemistry and compressive stress on dislocation bending during GaN growth

The synergistic effect of compressive growth stresses and reactor chemistry, silane presence, on dislocation bending at the very early stages of GaN growth has been studied using in-situ stress measurements and cross-sectional transmission electron microscopy. A single 100 nm Si-doped GaN layer is found to be more effective than a 1 mu m linearly graded AlGaN buffer layer in reducing dislocation density and preventing the subsequent layer from transitioning to a tensile stress. 1 mu m crack-free GaN layers with a dislocation density of 7 x 10(8)/cm(2), with 0.13 nm surface roughness and no enhancement in n-type background are demonstrated over 2 inch substrates using this simple transition scheme. (C) 2013 AIP Publishing LLC.

Role of electrolyte chemistry on electronic and in vitro electrochemical properties of micro-arc oxidized titania films on Cp Ti

The primary objective of the present work was to study the electronic and in vitro electrochemical properties of micro-arc oxidized titania films on Cp Ti, fabricated independently in various electrolyte solutions consisting of anions such as phosphate (PO43-), borate (B4O72-), citrate (C6H5O73-) and silicate (SiO32-). Further the role of anions on the structural, morphological and compositional properties of the fabricated films was studied. All the titania films were developed by micro-arc oxidation (MAO) technique for a fixed treatment time of 8 min under constant current mode. The surface morphology, elemental distribution, composition and structural characteristics of the films were assessed by scanning electron microscope (SEM) equipped with energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) techniques. The thermodynamic and kinetic corrosion properties of the films were studied under simulated body fluid (SBF) conditions (pH 7.4 and 37 degrees C) by conducting chronopotentiometric and potentiodynamic polarization tests. Electrochemical impedance spectroscopy (EIS) coupled with equivalent circuit modelling was carried out to analyse the frequency response and Mott-Schottky analysis was performed to study the semiconducting (electronic) properties of the films. Salt spray fog accelerated corrosion test was conducted for 168h as per ASTM B117 standard to corroborate the corrosion and semiconducting properties of the samples based on the visual examination. The XRD results showed that the transformation from the metastable anatase phase to the thermodynamically stable rutile phase and the crystalline growth of the respective phases were strongly influenced by the addition of anions. The SEM-EDS results demonstrated that the phosphorous (P) content in the films varied from 2.4 at% to 5.0 at% indicating that the amount of P in the films could be modified by adding an appropriate electrolyte additive. The electrochemical corrosion test results showed that the film fabricated in citrate (C6H5O73-) containing electrolyte is thermodynamically and kinetically more stable compared to that of all the others. The results of the Mott-Schottky analysis indicated that all the fabricated films showed an n-type semiconducting behaviour and the film developed in citrate (C6H5O73-) containing electrolyte exhibited the lowest donor concentration and the most negative flat band potential that contributed to its highest corrosion resistance in SBF solution. The results of the salt spray accelerated corrosion tests were in agreement with those obtained from the electrochemical and Mott-Schottky analysis.

Integrating biodiversity and conservation with modern agricultural landscapes

To achieve food security and meet the demands of the ever-growing human populations, farming systems have assumed unsustainable practices to produce more from a finite land area. This has been cause for concern mainly due to the often-irreversible damage done to the otherwise productive agricultural landscapes. Agro-ecology is proclaimed to be deteriorating due to eroding integrity of connected ecological mosaics and vulnerability to climate change. This has contributed to declining species diversity, loss of buffer vegetation, fragmentation of habitats, and loss of natural pollinators or predators, which eventually leads to decline in ecosystem services. Currently, a hierarchy of conservation initiatives is being considered to restore ecological integrity of agricultural landscapes. However, the challenge of identifying a suitable conservation strategy is a daunting task in view of socio-ecological factors that may constrain the choice of available strategies. One way to mitigate this situation and integrate biodiversity with agricultural landscapes is to implement offset mechanisms, which are compensatory and balancing approaches to restore the ecological health and function of an ecosystem. This needs to be tailored to the history of location specific agricultural practices, and the social, ecological and environmental conditions. The offset mechanisms can complement other initiatives through which farmers are insured against landscape-level risks such as droughts, fire and floods. For countries in the developing world with significant biodiversity and extensive agriculture, we should promote a comprehensive model of sustainable agricultural landscapes and ecosystem services, replicable at landscape to regional scales. Arguably, the model can be a potential option to sustain the integrity of biodiversity mosaic in agricultural landscapes.

Glycidyl azide polymer crosslinked through triazoles by click chemistry: curing, mechanical and thermal properties

Glycidyl azide polymer (GAP) was cured through click chemistry by reaction of the azide group with bispropargyl succinate (BPS) through a 1,3-dipolar cycloaddition reaction to form 1,2,3-triazole network. The properties of GAP-based triazole networks are compared with the urethane cured GAP-systems. The glass transition temperature (T-g), tensile strength, and modulus of the system increased with crosslink density, controlled by the azide to propargyl ratio. The triazole incorporation has a higher T-g in comparison to the GAP-urethane system (T-g-20 degrees C) and the networks exhibit biphasic transitions at 61 and 88 degrees C. The triazole curing was studied using Differential Scanning Calorimetry (DSC) and the related kinetic parameters were helpful for predicting the cure profile at a given temperature. Density functional theory (DFT)-based theoretical calculations implied marginal preference for 1,5-addition over 1,4-addition for the cycloaddition between azide and propargyl group. Thermogravimetic analysis (TG) showed better thermal stability for the GAP-triazole and the mechanism of decomposition was elucidated using pyrolysis GC-MS studies. The higher heat of exothermic decomposition of triazole adduct (418kJmol(-1)) against that of azide (317kJmol(-1)) and better mechanical properties of the GAP-triazole renders it a better propellant binder than the GAP-urethane system.