Efficient visible light induced nuclease activity of a ternary mono-1,10-phenanthroline copper(II) complex containing 2-(methylthio)ethylsalicylaidimine

Ternary Schiff base copper(II) complex [CuL(phen)](ClO4), where HL is 2-(methylthio)ethylsalicylaldimine and phen is 1,10-phenanthroline, has been prepared and structurally characterized by X-ray crystallography. The complex shows a CuN3OS coordination in a square-pyramidal (4 + 1) geometry with the sulfur as an equatorial ligand. The complex is an avid binder to double-stranded DNA in the minor groove and exhibits both photonuclease and chemical nuclease activity. When exposed to UV light of 312 nm (96 W) or visible light of 532 nm (125 W) under aerobic conditions, the complex causes significant cleavage of supercoiled pUC19 DNA in the absence of any externally added reducing agent or H2O2.

On breaks of the Indian monsoon

For over a century, the term break has been used for spells in which the rainfall over the Indian monsoon zone is interrupted. The phenomenon of 'break monsoon' is of great interest because long intense breaks are often associated with poor monsoon seasons. Such breaks have distinct circulation characteristics (heat trough type circulation) and have a large impact on rainfed agriculture. Although interruption of the monsoon rainfall is considered to be the most important feature of the break monsoon, traditionally breaks have been identified on the basis of the surface pressure and wind patterns over the Indian region. We have defined breaks (and active spells) on the basis of rainfall over the monsoon zone. The rainfall criteria are chosen so as to ensure a large overlap with the traditional breaks documented by Ramamurthy (1969) and De et al (1998). We have identified these rainbreaks for 1901-89. We have also identified active spells on the basis of rainfall over the Indian monsoon zone. We have shown that the all-India summer monsoon rainfall is significantly negatively correlated with the number of rainbreak days (correlation coefficient -0.56) and significantly positively correlated with the number of active days (correlation coefficient 0.47). Thus the interannual variation of the all-India summer monsoon rainfall is shown to be related to the number of days of rainbreaks and active spells identified here. There have been several studies of breaks (and also active spells in several cases) identified on the basis of different criteria over regions differing in spatial scales (e.g., Webster et al 1998; Krishnan et al 2000; Goswami and Mohan 2000; and Annamalai and Slingo 2001). We find that there is considerable overlap between the rainbreaks we have identified and breaks based on the traditional definition. There is some overlap with the breaks identified by Krishnan et al (2000) but little overlap with breaks identified by Webster et al (1998). Further, there are three or four active-break cycles in a season according to Webster et al (1998) which implies a time scale of about 40 days for which Goswami and Mohan (2000), and Annamalai and Slingo'(2001) have studied breaks and active minus break fluctuations. On the other hand, neither the traditional breaks (Ramamurthy 1969; and De et al 1998) nor the rainbreaks occur every year. This suggests that the 'breaks' in these studies axe weak spells of the intraseasonal variation of the monsoon, which occur every year. We have derived the OLR and circulation patterns associated with rainbreaks and active spells and compared them with the patterns associated with breaks/active minus break spells from these studies. Inspite of differences in the patterns over the Indian region, there is one feature which is seen in the OLR anomaly patterns of breaks identified on the basis of different criteria as well as the rainbreaks identified in this paper viz., a quadrapole over the Asia-west Pacific region arising from anomalies opposite (same) in sign to those over the Indian region occurring over the equatorial Indian Ocean and northern tropical (equatorial) parts of the west Pacific. Thus it appears that this quadrapole is a basic feature of weak spells of the intraseasonal,variation over the Asia-west Pacific region. Since the rainbreaks are intense weak spells, this basic feature is also seen in the composite patterns of these breaks. We find that rainbreaks (active spells) are also associated with negative (positive) anomalies over a part of the cast Pacific suggesting that the convection over the Indian region is linked to that over the east Pacific not only on the interannual scale (as evinced by the link between the Indian summer monsoon rainfall and ENSO) but on the intraseasonal scale as well.

Ternary copper(II) complexes of thiosemicarbazones and heterocyclic bases showing N3OS coordination as models for the type-2 centers of copper monooxygenases

Six ternary copper(II) complexes of general formulation [CuLB] (1-6), where L is dianionic ONS-donor thiosemicarbazones derived from the condensation of salicylaldehyde with thiosemicarbazides and B is NN-donor heterocyclic bases like 2,2'-bipyridine, 1,10-phenanthroline and 2,9-dimethyl-1,10-phenanthroline, are prepared from a reaction of copper(II) acetate hydrate with the heterocyclic base (B) and the thiosemicarbazone (H2L) in MeOH, and structurally characterized by X-ray diffraction technique. Crystal structures of the complexes display a distorted square-pyramidal (4 + 1) coordination geometry having the ONS-donor thiosemicarbazone bonded at the basal plane. The chelating heterocyclic bases exhibit axial-equatorial mode of bonding. The complexes are one-electron paramagnetic and they show axial X-band EPR spectra in DMF-toluene glass at 77 K giving g(parallel to)(A(parallel to)) and g(perpendicular to) values of similar to2.2 (175 x 10(-4) cm(-1)) and similar to2.0 indicating a {d(x2-y2)}(1) ground state. The complexes show a d-d band near 570 nm and a charge transfer band near 400 nm in DMF. The complexes are redox active and exhibit a quasireversible Cu(II)-Cu(I) couple in DMF-0.1 M tetrabutylammonium perchlorate near 0.1 V vs. SCE. They are catalytically active in the oxidation of ascorbic acid in presence of dioxygen. The complexes with a CuN3OS coordination model the ascorbate oxidation property of dopamine beta-hydroxylase and peptidylglycine a-hydroxylating monooxygeanase. (C) 2003 Elsevier Science B.V. All rights reserved.

DeNOx Study in Diesel Engine Exhaust Using Barrier Discharge Corona Assisted by V2O5/TiO2 Catalyst

A plasma-assisted catalytic reactor was used to remove nitrogen oxides (NOx) from diesel engine exhaust operated under different load conditions. Initial studies were focused on plasma reactor (a dielectric barrier discharge reactor) treatment of diesel exhaust at various temperatures. The nitric oxide (NO) removal efficiency was lowered when high temperature exhaust was treated using plasma reactor. Also, NO removal efficiency decreased when 45% load exhaust was treated. Studies were then made with plasma reactor combined with a catalytic reactor consisting of a selective catalytic reduction (SCR) catalyst, V2O5/TiO2. Ammonia was used as a reducing agent for SCR process in a ratio of 1:1 to NOx. The studies were focused on temperatures of the SCR catalytic reactor below 200°C. The plasma-assisted catalytic reactor was operated well to remove NOx under no-load and load conditions. For an energy input of 96 J/l, the NOx removal efficiencies obtained under no-load and load conditions were 90% and 72% respectively at an exhaust temperature of 100°C.

Ferrocene-Conjugated Oxidovanadium(IV) Complexes as Potent Near-IR Light Photocytotoxic Agents

Ferrocene-conjugated oxidovanadium(IV) complexes [VO(Fc-tpy)(B)](ClO4)(2) (1-4) and [VO(Ph-tpy)(dppz)](ClO4)(2) (5) as a control [Fc = (eta(5)-C5H4)Fe-II(eta(5)-C5H5), Fc-tpy = 4'-ferrocenyl-2,2':6',2 `'-terpyridine, Ph-tpy = 4'-phenyl-2,2':6',2 `'-terpyridine, B = heterocyclic base: 2,2'-bipyridine (bpy in 1), 1,10-phenanthroline (phen in 2), dipyridoquinoxaline (dpq in 3), dipyridophenazine (dppz in 4)] were prepared and their DNA binding, DNA photocleavage activity and photocytotoxicity studied. The crystal structure of [VO(Fc-tpy)(bpy)](PF6)(2)center dot 3Me(2)CO shows a vanadyl group in six-coordinate (VON5)-O-IV coordination geometry, in which Fc-tpy and bpy display tridentate meridional and bidentate N-donor axial-equatorial binding modes, respectively. The one-electron paramagnetic complexes exhibit a charge-transfer band near 590 nm in DMF. The V-IV/V-III redox couple in 1-4 appears near -0.7 V, whereas the Fc moiety shows a response near 0.6 V vs. SCE in DMF/0.1 M TBAP. The complexes are good binders to calf thymus DNA with K-b values of 10(4)-10(6) M-1. DNA melting and viscometric data suggest groove and/or partial intercalative DNA binding of the complexes. Complexes 3-5 display DNA photocleavage activity in nearIR light of 785 nm. Complex 4 shows significant photocytotoxicity in visible light (400-700 nm) in HeLa cells with low dark toxicity.

Synthesis and characterization of cobalt(II), nickel(II), copper(II) and zinc(II) complexes of 2-nitrobenzoic acid with methyl carbazate as ancillary ligand. Crystal structure of the copper(II) complex

Divalent metal complexes of general formula M(2-nb)(2)(mc)(2)].2(2-nbH), where M = Co(II), Ni(II), Cu(II) or Zn(II), 2-nbH = 2-nitrobenzoic acid and mc = methyl carbazate (NH2NHCOOCH3), have been prepared and characterized by physicochemical and spectroscopic methods. Single-crystal X-ray study of the Cu(II) complex revealed that the molecule is centrosymmetric, with two N,O-chelating mc ligands in equatorial positions and a pair of monodentate 2-nb anions in the axial positions. The lattice 2-nbH molecules help to establish the packing of monomers through hydrogen-bonding interactions. Thermal stability and reactivity of the complexes were studied by TG-DTA. Emission studies show that these complexes are fluorescent.

Thermoluminescence, photoluminescence and EPR studies on Mn2+ activated yttrium aluminate (YAlO3) perovskite

Thermoluminescence (TL) measurements were carried out on undoped and Mn2+ doped (0.1 mol%) yttrium aluminate (YAlO3) nanopowders using gamma irradiation in the dose range 1-5 kGy. These phosphors have been prepared at furnace temperatures as low as 400 degrees C by using the combustion route. Powder X-ray diffraction confirms the orthorhombic phase. SEM micrographs show that the powders are spherical in shape, porous with fused state and the size of the particles appeared to be in the range 50-150 nm. Electron Paramagnetic Resonance (EPR) studies reveal that Mn ions occupy the yttrium site and the valency of manganese remains as Mn2+. The photoluminescence spectrum shows a typical orange-to-red emission at 595 nm and suggests that Mn2+ ions are in strong crystalline environment. It is observed that TL intensity increases with gamma dose in both undoped and Mn doped samples. Four shouldered TL peaks at 126, 240, 288 and 350 degrees C along with relatively resolved glow peak at 180 degrees C were observed in undoped sample. However, the Mn doped samples show a shouldered peak at 115 degrees C along with two well defined peaks at similar to 215 and 275 degrees C. It is observed that TL glow peaks were shifted in Mn doped samples. The kinetic parameters namely activation energy (E), order of kinetics (b), frequency factor (s) of undoped, and Mn doped samples were determined at different gamma doses using the Chens glow peak shape method and the results are discussed in detail. (C) 2012 Elsevier B.V. All rights reserved.

Novel tetranuclear distorted open-cubane copper complex containing oximate bridges: Synthesis, crystal structure, DNA binding and cleavage activity

The synthesis, molecular structure, DNA binding and nuclease activity of Cu4O4 open-cubane tetranuclear copper(II) complex with 3-2-(ethyl amino)ethyl]imino]-2-butanoneoxime (HL) are reported for the first time. The neutral tetranuclear Cu4L4(ClO4)(4)] complex crystallizes in tetragonal space group P (4) over bar2(1)c with the unit cell parameters; a = 13.798(4) angstrom, b = 13.798(4) angstrom, c = 14.119(6) angstrom, V = 2688(16) angstrom(3), Z = 8, R = 0.0636. Symmetrically equivalent copper atoms exhibit a CuN3O3 elongated distorted octahedral coordination environment, with three nitrogen atoms of the L ligand and one oxime-oxygen atom of second L ligand at equatorial positions, one oxime-oxygen atom of the third L ligand and perchlorate oxygen at axial positions. The complex shows quasireversible cyclic voltammetric response at 0.805 V (Delta E-p = 277 mV) at 100 mV s (1) in DMF for the Cu(II)/Cu(I) redox couple. The binding study of the complex with calf-thymus DNA has been investigated using absorption spectrophotometry. The complex shows strong nuclease activity on stranded pBR 322 plasmid DNA in the presence of hydrogen peroxide and marginal nuclease activity in the presence of reducing agent (dithiothreitol). (C) 2012 Elsevier B. V. All rights reserved.

Spirodiazaselenuranes: synthesis, structure and antioxidant activity

In this paper, the synthesis, characterization and glutathione peroxidase and peroxynitrite scavenging activities of a series of stable spirodiazaselenuranes are described. The spiro compounds were synthesized in good yields by oxidative cyclization of diaryl selenides bearing amide moieties. All the selenides and spiro derivatives were characterized by H-1, C-13 and Se-77 NMR spectroscopy, mass spectral techniques and the structures of some of the spirodiazaselenuranes were confirmed by single crystal X-ray crystallography. The structures reveal that the selenium atom occupies the center of a distorted trigonal bipyramid core with two nitrogen atoms occupying the apical positions and two carbon atoms and the selenium lone pair occupying the equatorial positions. Mechanistic investigations indicate that the spirocyclization occurs via the formation of selenoxide intermediates. The new compounds were evaluated for their glutathione peroxidase (GPx) mimetic activity by using H2O2 as a substrate and glutathione (GSH) as a co-substrate. It was found that the substituents attached to the nitrogen atom of the selenazole ring have a significant effect on the GPx activity. While the introduction of electron withdrawing groups such as -Cl, -Br etc. to the phenyl ring decreases the activity, the introduction of electron donating groups such as -OH, -OMe significantly enhances the GPx activity of both diaryl selenides and spirodiazaselenuranes. In addition to GPx activity, the selenides and spiro derivatives were studied for their ability to inhibit peroxynitrite (PN)-mediated nitration of bovine serum albumin (BSA) and oxidation of dihydrorhodamine 123. These studies indicate that the diarylselenides effectively inhibit the PN-mediated nitration and oxidation reactions by reacting with PN to produce the corresponding spirodiazaselenuranes.

All flavours of El Nino have similar early subsurface origins

The El Nino/Southern Oscillation phenomenon, characterized by anomalous sea surface temperatures and winds in the tropical Pacific, affects climate across the globe(1). El Ninos occur every 2-7 years, whereas the El Nino/Southern Oscillation itself varies on decadal timescales in frequency and amplitude, with a different spatial pattern of surface anomalies(2) each time the tropical Pacific undergoes a regime shift. Recent work has shown that Bjerknes feedback(3,4) (coupling of the atmosphere and the ocean through changes in equatorial winds driven by changes in sea surface temperature owing to suppression of equatorial upwelling in the east Pacific) is not necessary(5) for the development of an El Nino. Thus it is unclear what remains constant through regimes and is crucial for producing the anomalies recognized as El Nino. Here we show that the subsurface process of discharging warm waters always begins in the boreal summer/autumn of the year before the event (up to 18 months before the peak) independent of regimes, identifying the discharge process as fundamental to the El Nino onset. It is therefore imperative that models capture this process accurately to further our theoretical understanding, improve forecasts and predict how the El Nino/Southern Oscillation may respond to climate change.

A study of vertical cloud structure of the Indian summer monsoon using CloudSat data

Precise specification of the vertical distribution of cloud optical properties is important to reduce the uncertainty in quantifying the radiative impacts of clouds. The new global observations of vertical profiles of clouds from the CloudSat mission provide opportunities to describe cloud structures and to improve parameterization of clouds in the weather and climate prediction models. In this study, four years (2007-2010) of observations of vertical structure of clouds from the CloudSat cloud profiling radar have been used to document the mean vertical structure of clouds associated with the Indian summer monsoon (ISM) and its intra-seasonal variability. Active and break monsoon spells associated with the intra-seasonal variability of ISM have been identified by an objective criterion. For the present analysis, we considered CloudSat derived column integrated cloud liquid and ice water, and vertically profiles of cloud liquid and ice water content. Over the South Asian monsoon region, deep convective clouds with large vertical extent (up to 14 km) and large values of cloud water and ice content are observed over the north Bay of Bengal. Deep clouds with large ice water content are also observed over north Arabian Sea and adjoining northwest India, along the west coast of India and the south equatorial Indian Ocean. The active monsoon spells are characterized by enhanced deep convection over the Bay of Bengal, west coast of India and northeast Arabian Sea and suppressed convection over the equatorial Indian Ocean. Over the Bay of Bengal, cloud liquid water content and ice water content is enhanced by similar to 90 and similar to 200 % respectively during the active spells. An interesting feature associated with the active spell is the vertical tilting structure of positive CLWC and CIWC anomalies over the Arabian Sea and the Bay of Bengal, which suggests a pre-conditioning process for the northward propagation of the boreal summer intra-seasonal variability. It is also observed that during the break spells, clouds are not completely suppressed over central India. Instead, clouds with smaller vertical extent (3-5 km) are observed due to the presence of a heat low type of circulation. The present results will be useful for validating the vertical structure of clouds in weather and climate prediction models.

Longitudinal localization of tropical intraseasonal variability

Intraseasonal time-scales play an important role in tropical variability. Two modes that contribute significantly to tropical intraseasonal variability (ISV) are the eastward-propagating MaddenJulian Oscillation (MJO), and westward-moving moist equatorial Rossby waves. This note reports on a correspondence between the longitudinal gradient of mean tropical precipitable water (PW), and the geographical regions of genesis, and convective activity, of both these large-scale tropical systems. Our finding is based on an analysis of PW from the MERRA reanalysis product. The data indicate that the mean tropical PW has a dominant wavenumber two (three) structure in longitude in the Northern (Southern) Hemisphere. Departures from a longitudinally homogeneous state are attributed to the influence of subtropical anticyclones, and are accentuated by monsoonal regions of both hemispheres. This mean structure results in a sharply localized longitudinal gradient of PW. Remarkably, regions with positive gradients (such as the Northern and Southern Hemisphere western Indian Ocean), i.e. they have larger PW to the east, are the very zones that are implicated in the formation, and show high levels of convective activity, of the eastward-moving MJO. On the other hand, regions with negative gradients (such as the Southern Hemisphere central Pacific) are the very regions where genesis, and maxima in variance, of westward-moving moist equatorial Rossby waves are known to occur. Apart from providing a first-order longitudinal footprint of the convective phase of these systems, this correspondence reinforces the role of the mean climatic state in tropical ISV. Copyright (c) 2012 Royal Meteorological Society

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.

The Indian Ocean forecast system

In order to meet the ever growing demand for the prediction of oceanographic parametres in the Indian Ocean for a variety of applications, the Indian National Centre for Ocean Information Services (INCOIS) has recently set-up an operational ocean forecast system, viz. the Indian Ocean Forecast System (INDOFOS). This fully automated system, based on a state-of-the-art ocean general circulation model issues six-hourly forecasts of the sea-surface temperature, surface currents and depths of the mixed layer and the thermocline up to five-days of lead time. A brief account of INDOFOS and a statistical validation of the forecasts of these parametres using in situ and remote sensing data are presented in this article. The accuracy of the sea-surface temperature forecasts by the system is high in the Bay of Bengal and the Arabian Sea, whereas it is moderate in the equatorial Indian Ocean. On the other hand, the accuracy of the depth of the thermocline and the isothermal layers and surface current forecasts are higher near the equatorial region, while it is relatively lower in the Bay of Bengal.

Predicting the extremes of Indian summer monsoon rainfall with coupled ocean-atmosphere models

An analysis of the retrospective predictions by seven coupled ocean atmosphere models from major forecasting centres of Europe and USA, aimed at assessing their ability in predicting the interannual variation of the Indian summer monsoon rainfall (ISMR), particularly the extremes (i.e. droughts and excess rainfall seasons) is presented in this article. On the whole, the skill in prediction of extremes is not bad since most of the models are able to predict the sign of the ISMR anomaly for a majority of the extremes. There is a remarkable coherence between the models in successes and failures of the predictions, with all the models generating loud false alarms for the normal monsoon season of 1997 and the excess monsoon season of 1983. It is well known that the El Nino and Southern Oscillation (ENSO) and the Equatorial Indian Ocean Oscillation (EQUINOO) play an important role in the interannual variation of ISMR and particularly the extremes. The prediction of the phases of these modes and their link with the monsoon has also been assessed. It is found that models are able to simulate ENSO-monsoon link realistically, whereas the EQUINOO-ISMR link is simulated realistically by only one model the ECMWF model. Furthermore, it is found that in most models this link is opposite to the observed, with the predicted ISMR being negatively (instead of positively) correlated with the rainfall over the western equatorial Indian Ocean and positively (instead of negatively) correlated with the rainfall over the eastern equatorial Indian Ocean. Analysis of the seasons for which the predictions of almost all the models have large errors has suggested the facets of ENSO and EQUINOO and the links with the monsoon that need to be improved for improving monsoon predictions by these models.