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.

Photoactivated DNA cleavage and anticancer activity of oxovanadium(IV) complexes of curcumin

Oxovanadi um(IV) complexes VO(Fc-pic)(acac)](ClO4) (1), VO(Fc-pic)(cur)](ClO4) (2), VO(Ph-pic)(acac)](ClO4) (3) and VO(Ph-pic)(cur)](ClO4) (4), where Fc-pic and Ph-pic are ferrocenylmethyl-bis-(2-pyridylmethylamine) (in 1, 2) and bis-(2-pyridylmethyl)benzylamine (in 3, 4), respectively, acac is acetylacetonate anion (in 1, 3) and cur is curcumin anion (in 2, 4) were prepared, characterized and their photo-induced DNA cleavage and anticancer activity studied. The crystal structure of 1 as its PF6 salt (1a) shows the presence of a VO2+ moiety in VO3N3 coordination geometry. The complexes show a d-d band at similar to 790 nm in DMF and display V(IV)/V(III) redox couple near -1.45 V vs. SCE in DMF-0.1 M TBAP. The complexes are avid binders to calf thymus DNA. Complex 2 efficiently photo-cleaves plasmid DNA in near-IR light of 785 nm forming (OH)-O-center dot radicals. The curcumin complexes show photocytotoxicity in HeLa cancer cells in visible light of 400-700 nm with significant cellular uptake within 4 h of incubation time.

Photocytotoxic ferrocene-appended (L-tyrosine)copper(II) complexes of phenanthroline bases

Copper(II) complexes of ferrocene(Fc)-conjugated reduced Schiff base of L-tyrosine (Fc-TyrH), viz., Cu(Fc-Tyr)(L)](ClO4), where L is 1,10-phenanthroline (phen, 1), dipyrido3,2-d:2',3'-f]quinoxaline (dpq, 2), dipyrido3,2-a:2',3'-c]phenazine (dppz, 3) and 2-(naphthalen-1-yl)-1H-imidazo4,5-f]1,10]phenanthroline (nip, 4), were prepared and tested for their photocytotoxicity in cancer cells. Cu(Fc-Phe)(phen)](-ClO4) (5) of L-phenylalanine and Cu(Ph-Tyr)(L)(ClO4)] of the reduced Schiff base Ph-TyrH derived from benzaldehyde and L-tyrosine having phen (6) and dppz (7), and Cu(Ph-Phe)(phen)(ClO4)] (8) using L-phenylalanine were prepared and used as controls. Complexes 5 and 6 were structurally characterized by X-ray crystallography. A copper(II)-based d-d band near 600 nm and a ferrocenyl band at similar to 450 nm were observed in DMF-Tris-HCI buffer (1:4 v/v) in respective complexes. The complexes are photocleavers of pUC19 DNA in visible light forming (OH)-O-center dot radicals. They are cytotoxic in HeLa (human cervical cancer) and MCF-7 (human breast cancer) cells showing an enhancement of cytotoxicity in visible light. Fluorescence imaging shows nuclear localization of the complexes.

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.

Cyclic AMP-dependent protein lysine acylation in mycobacteria regulates fatty acid and propionate metabolism

Acetylation of lysine residues is a posttranslational modification that is used by both eukaryotes and prokaryotes to regulate a variety of biological processes. Here we identify multiple substrates for the cAMP-dependent protein lysine acetyltransferase from Mycobacterium tuberculosis (KATmt). We demonstrate that a catalytically important lysine residue in a number of FadD (fatty acyl CoA synthetase) enzymes is acetylated by KATmt in a cAMP-dependent manner and that acetylation inhibits the activity of FadD enzymes. A sirtuin-like enzyme can deacetylate multiple FadDs, thus completing the regulatory cycle. Using a strain deleted for the KATmt ortholog in Mycobacterium bovis Bacillus Calmette-Guerin (BCG), we show for the first time that acetylation is dependent on intracellular cAMP levels. KATmt can utilize propionyl CoA as a substrate and, therefore, plays a critical role in alleviating propionyl CoA toxicity in mycobacteria by inactivating acyl CoA synthetase (ACS). The precision by which mycobacteria can regulate the metabolism of fatty acids in a cAMP-dependent manner appears to be unparalleled in other biological organisms and is ideally suited to adapt to the complex environment that pathogenic mycobacteria experience in the host.

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.

Nitric oxide and KLF4 protein epigenetically modify class II transactivator to repress Major histocompatibility complex II expression during Mycobacterium bovis Bacillus Calmette-Guerin infection

Pathogenic mycobacteria employ several immune evasion strategies such as inhibition of class II transactivator (CIITA) and MHC-II expression, to survive and persist in host macrophages. However, precise roles for specific signaling components executing down-regulation of CIITA/MHC-II have not been adequately addressed. Here, we demonstrate that Mycobacterium bovis bacillus Calmette-Guerin (BCG)-mediated TLR2 signaling-induced iNOS/NO expression is obligatory for the suppression of IFN-gamma-induced CIITA/MHC-II functions. Significantly, NOTCH/PKC/MAPK-triggered signaling cross-talk was found critical for iNOS/NO production. NO responsive recruitment of a bifunctional transcription factor, KLF4, to the promoter of CIITA during M. bovis BCG infection of macrophages was essential to orchestrate the epigenetic modifications mediated by histone methyltransferase EZH2 or miR-150 and thus calibrate CIITA/MHC-II expression. NO-dependent KLF4 regulated the processing and presentation of ovalbumin by infected macrophages to reactive T cells. Altogether, our study delineates a novel role for iNOS/NO/KLF4 in dictating the mycobacterial capacity to inhibit CIITA/MHC-II-mediated antigen presentation by infected macrophages and thereby elude immune surveillance.

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.

Naphthalene Carbohydrazone Based Dizinc(II) Chemosensor for a Pyrophosphate Ion and Its DNA Assessment Application in Polymerase Chain Reaction Products

A new naphthalene carbohydrazone based dizinc(II) complex has been synthesized and investigated to act as a highly selective fluorescence and visual sensor for a pyrophosphate ion with a quite low detection limit of 155 ppb; this has also been used to detect the pyrophosphate ion released from polymerase-chain-reaction.

Synthesis and evaluation of 2,5-di(4-aryloylaryloxymethyl)-1,3,4-oxadiazoles as anti-cancer agents

A series of 2,5-di(4-aryloylaryloxymethyl)-1,3,4-oxadiazoles 9a-j were obtained via multistep synthesis from hydroxybenzophenones 4a-e. The cytotoxicity of compounds 9a-j was evaluated against human leukemia cell lilies (K562 and CEM). The compounds exhibited moderate to good anti-cancer activity with compounds 9b and 9i having a chloro group exhibiting the best activity (IC50 = 10 mu M). Compound 9i exhibited activity against both the cell lines and 9b only exhibited activity against CEM. Further, a lactate dehydrogenase (LDH) assay and DNA fragmentation studies of the compounds 9a-j were also performed. (C) 2013 Elsevier Masson SAS. All rights reserved.

Photocytotoxicity of copper(II) complexes of curcumin and N-ferrocenylmethyl-L-amino acids

Copper(II) complexes Cu(Fc-aa)(cur)] (1-3) of curcumin (Hcur) and N-ferrocenylmethyl-L-amino acids (Fc-aa), viz., ferrocenylmethyl-L-tyrosine (Fc-TyrH), ferrocenylmethyl-L-tryptophan (Fc-TrpH) and ferrocenylmethyl-L-methionine (Fc-MetH), were prepared and characterized. The DNA photocleavage activity, photocytotoxicity and cellular localization in HeLa and MCF-7 cancer cells of these complexes were studied. Acetylacetonate (acac) complexes Cu(Fc-aa)(acac)] (4-6) were prepared and used as controls. The chemical nuclease inactive complexes showed efficient pUC19 DNA cleavage activity in visible light. Complexes 1-3 showed high photocytotoxicity with low dark toxicity thus giving remarkable photodynamic effect. FACScan analysis showed apoptosis of the cancer cells. Fluorescence microscopic studies revealed primarily cytosolic localization of the complexes. (C) 2013 Elsevier Masson SAS. All rights reserved.

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.

NOD2-Nitric Oxide-responsive MicroRNA-146a Activates Sonic Hedgehog Signaling to Orchestrate Inflammatory Responses in Murine Model of Inflammatory Bowel Disease

Background: Genetic variants of NOD2 are linked to inflammatory bowel disease (IBD) etiology. Results: DSS model of colitis in wild-type and inducible nitric-oxide synthase (iNOS) null mice revealed that NOD2-iNOS/NO-responsive microRNA-146a targets NUMB gene facilitating Sonic hedgehog (SHH) signaling. Conclusion: miR-146a-mediated NOD2-SHH signaling regulates gut inflammation. Significance: Identification of novel regulators of IBD provides new insights into pathophysiology and development of new therapy concepts. Inflammatory bowel disease (IBD) is a debilitating chronic inflammatory disorder of the intestine. The interactions between enteric bacteria and genetic susceptibilities are major contributors of IBD etiology. Although genetic variants with loss or gain of NOD2 functions have been linked to IBD susceptibility, the mechanisms coordinating NOD2 downstream signaling, especially in macrophages, during IBD pathogenesis are not precisely identified. Here, studies utilizing the murine dextran sodium sulfate model of colitis revealed the crucial roles for inducible nitric-oxide synthase (iNOS) in regulating pathophysiology of IBDs. Importantly, stimulation of NOD2 failed to activate Sonic hedgehog (SHH) signaling in iNOS null macrophages, implicating NO mediated cross-talk between NOD2 and SHH signaling. NOD2 signaling up-regulated the expression of a NO-responsive microRNA, miR-146a, that targeted NUMB gene and alleviated the suppression of SHH signaling. In vivo and ex vivo studies confirmed the important roles for miR-146a in amplifying inflammatory responses. Collectively, we have identified new roles for miR-146a that established novel cross-talk between NOD2-SHH signaling during gut inflammation. Potential implications of these observations in therapeutics could increase the possibility of defining and developing better regimes to treat IBD pathophysiology.