A non-metal catalysed oxidation of primary azides to nitriles at ambient temperature

A novel non-metal catalyzed oxidation of organic azides to nitriles under solvent-free conditions is presented employing catalytic amounts of KI, and DABCO in aq. TBHP at room temperature. This nonmetal catalyzed oxidation of azides provides good selectivity as double and triple bonds were not oxidized under the present reaction conditions.

Observation of high pressure o-GeTe phase at ambient pressure in Si-Te-Ge glasses

Te-rich Si15Te85-xGex (1 <= x <= 11) glasses are found to exhibit an anomalous phase separations with germanium composition. The structural transformation of o-GeTe crystalline phase from o-GeTe with a = 11.76 angstrom, b = 16.59 angstrom, c = 17.44 angstrom, to high pressure o-GeTe with a new reduced lattice parameters a = 10.95 angstrom, b = 4.03 angstrom, c = 4.45 angstrom, is observed at T-c3 in the composition range 6 <= x <= 11. Raman studies support the possible existence of high pressure o-GeTe phase which is observed in X-ray diffraction experiments. Copyright 2012 Author(s). This article is distributed under a Creative Commons Attribution 3.0 Unported License. http://dx.doi.org/10.1063/1.3696862]

Iron(III) Chloride-Catalysed Aerobic Reduction of Olefins using Aqueous Hydrazine at Ambient Temperature

A chemoselective reduction of olefins and acetylenes is demonstrated by employing catalytic amounts of ferric chloride hexahydrate (FeCl3 center dot 6H(2)O) and aqueous hydrazine (NH2NH2 center dot H2O) as hydrogen source at room temperature. The reduction is chemoselective and tolerates a variety of reducible functional groups. Unlike other metal-catalysed reduction methods, the present method employs a minimum amount of aqueous hydrazine (1.5-2 equiv.). Also, the scope of this method is demonstrated in the synthesis of ibuprofen in aqueous medium.

Monsoon sensitivity to aerosol direct radiative forcing in the community atmosphere model

Aerosol forcing remains a dominant uncertainty in climate studies. The impact of aerosol direct radiative forcing on Indian monsoon is extremely complex and is strongly dependent on the model, aerosol distribution and characteristics specified in the model, modelling strategy employed as well as on spatial and temporal scales. The present study investigates (i) the aerosol direct radiative forcing impact on mean Indian summer monsoon when a combination of quasi-realistic mean annual cycles of scattering and absorbing aerosols derived from an aerosol transport model constrained with satellite observed Aerosol Optical Depth (AOD) is prescribed, (ii) the dominant feedback mechanism behind the simulated impact of all-aerosol direct radiative forcing on monsoon and (iii) the relative impacts of absorbing and scattering aerosols on mean Indian summer monsoon. We have used CAM3, an atmospheric GCM (AGCM) that has a comprehensive treatment of the aerosol-radiation interaction. This AGCM has been used to perform climate simulations with three different representations of aerosol direct radiative forcing due to the total, scattering aerosols and black carbon aerosols. We have also conducted experiments without any aerosol forcing. Aerosol direct impact due to scattering aerosols causes significant reduction in summer monsoon precipitation over India with a tendency for southward shift of Tropical Convergence Zones (TCZs) over the Indian region. Aerosol forcing reduces surface solar absorption over the primary rainbelt region of India and reduces the surface and lower tropospheric temperatures. Concurrent warming of the lower atmosphere over the warm oceanic region in the south reduces the land-ocean temperature contrast and weakens the monsoon overturning circulation and the advection of moisture into the landmass. This increases atmospheric convective stability, and decreases convection, clouds, precipitation and associated latent heat release. Our analysis reveals a defining negative moisture-advection feedback that acts as an internal damping mechanism spinning down the regional hydrological cycle and leading to significant circulation changes in response to external radiative forcing perturbations. When total aerosol loading (both absorbing and scattering aerosols) is prescribed, dust and black carbon aerosols are found to cause significant atmospheric heating over the monsoon region but the aerosol-induced weakening of meridional lower tropospheric temperature gradient (leading to weaker summer monsoon rainfall) more than offsets the increase in summer-time rainfall resulting from the atmospheric heating effect of absorbing aerosols, leading to a net decrease of summer monsoon rainfall. Further, we have carried out climate simulations with globally constant AODs and also with the constant AODs over the extended Indian region replaced by realistic AODs. Regional aerosol radiative forcing perturbations over the Indian region is found to have impact not only over the region of loading but over remote tropical regions as well. This warrants the need to prescribe realistic aerosol properties in strategic regions such as India in order to accurately assess the aerosol impact.

On the linkage of mesospheric planetary waves with those of the lower atmosphere and ionosphere: A case study from Indian low latitudes

In this paper we study the planetary-scale wave features using concurrent observations of mesospheric wind and temperature, ionospheric h'F, and tropospheric wind from Tirunelveli, Gadanki, and Kolhapur, all located in the Indian low latitudes, made during February 2009. Our investigations reveal that 3 to 5 day periodicity, characterized as ultrafast Kelvin (UFK) waves, was persistent throughout the atmosphere during this period. These waves show clear signatures of upward wave propagation from troposphere to the upper mesosphere, linking the ionosphere through a clear correlation between mesospheric winds and h'F variations. We also note that the amplitude of this wave decreased as we moved away from the equator. These results are the first of their kind from Indian sector, portraying the vertical as well as latitudinal characteristics of the 3 to 5 day UFK waves simultaneously from the troposphere to the ionosphere.

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.

A tuned rectifier for RF energy harvesting from ambient radiations

A circuit topology based on accumulate-and-use philosophy has been developed to harvest RF energy from ambient radiations such as those from cellular towers. Main functional units of this system are antenna, tuned rectifier, supercapacitor, a gated boost converter and the necessary power management circuits. Various RF aspects of the design philosophy for maximizing the conversion efficiency at an input power level of 15 mu W are presented here. The system is characterized in an anechoic chamber and it has been established that this topology can harvest RF power densities as low as 180 mu W/m(2) and can adaptively operate the load depending on the incident radiation levels. The output of this system can be easily configured at a desired voltage in the range 2.2-4.5 V. A practical CMOS load - a low power wireless radio module has been demonstrated to operate intermittently by this approach. This topology can be easily modified for driving other practical loads, from harvested RF energy at different frequencies and power levels.

On the epochal variation of intensity of tropical cyclones in the Arabian Sea

During recent years, an increase in the intensity of pre-monsoon tropical cyclones (TCs) is observed over the Arabian Sea. This study suggests that this increase is due to epochal variability in the intensity of TCs and is associated with epochal variability in the storm-ambient vertical wind shear and tropical cyclone heat potential (TCHP). There is a significant increase (0.53kJcm(-2)year(-1)) of TCHP during recent years. The warmer upper ocean helps TCs to sustain or increase their intensity by an uninterrupted supply of sensible and latent heat fluxes from the ocean surface to the atmosphere.

A molecular dynamics study of ambient and high pressure phases of silica: Structure and enthalpy variation with molar volume

Extensive molecular dynamics studies of 13 different silica polymorphs are reported in the isothermal-isobaric ensemble with the Parrinello-Rahman variable shape simulation cell. The van Beest-Kramer-van Santen (BKS) potential is shown to predict lattice parameters for most phases within 2%-3% accuracy, as well as the relative stabilities of different polymorphs in agreement with experiment. Enthalpies of high-density polymorphs - CaCl2-type, alpha-PbO2-type, and pyrite-type for which no experimental data are available as yet, are predicted here. Further, the calculated enthalpies exhibit two distinct regimes as a function of molar volume-for low and medium-density polymorphs, it is almost independent of volume, while for high-pressure phases a steep dependence is seen. A detailed analysis indicates that the increased short-range contributions to enthalpy in the high-density phases arise not only from an increased coordination number of silicon but also shorter Si-O bond lengths. Our results indicate that amorphous phases of silica exhibit better optimization of short-range interactions than crystalline phases at the same density while the magnitude of Coulombic contributions is lower in the amorphous phase. (C) 2014 AIP Publishing LLC.

Estimates of site response based on spectral ratio between horizontal and vertical components of ambient vibrations in the source zone of 2001 Bhuj earthquake

We investigated the site response characteristics of Kachchh rift basin over the meizoseismal area of the 2001, Mw 7.6, Bhuj (NW India) earthquake using the spectral ratio of the horizontal and vertical components of ambient vibrations. Using the available knowledge on the regional geology of Kachchh and well documented ground responses from the earthquake, we evaluated the H/V curves pattern across sediment filled valleys and uplifted areas generally characterized by weathered sandstones. Although our HIV curves showed a largely fuzzy nature, we found that the hierarchical clustering method was useful for comparing large numbers of response curves and identifying the areas with similar responses. Broad and plateau shaped peaks of a cluster of curves within the valley region suggests the possibility of basin effects within valley. Fundamental resonance frequencies (f(0)) are found in the narrow range of 0.1-2.3 Hz and their spatial distribution demarcated the uplifted regions from the valleys. In contrary, low HIV peak amplitudes (A(0) = 2-4) were observed on the uplifted areas and varying values (2-9) were found within valleys. Compared to the amplification factors, the liquefaction indices (kg) were able to effectively indicate the areas which experienced severe liquefaction. The amplification ranges obtained in the current study were found to be comparable to those obtained from earthquake data for a limited number of seismic stations located on uplifted areas; however the values on the valley region may not reflect their true amplification potential due to basin effects. Our study highlights the practical usefulness as well as limitations of the HIV method to study complex geological settings as Kachchh. (C) 2014 Elsevier Ltd. All rights reserved.

Effect of ambient on the resistance fluctuations of graphene

In this letter, we present the results of systematic experimental investigations of the effect of different chemical environments on the low frequency resistance fluctuations of single layer graphene field effect transistors. The shape of the power spectral density of noise was found to be determined by the energetics of the adsorption-desorption of molecules from the graphene surface making it the dominant source of noise in these devices. We also demonstrate a method of quantitatively determining the adsorption energies of chemicals on graphene surface based on noise measurements. We find that the magnitude of noise is extremely sensitive to the nature and amount of the chemical species present. We propose that a chemical sensor based on the measurement of low frequency resistance fluctuations of single layer graphene field effect transistor devices will have extremely high sensitivity, very high specificity, high fidelity, and fast response times. (c) 2015 AIP Publishing LLC.

Single-step synthesis of carbon nanotubes/iron/iron oxide composite films through inert-ambient CVD using ferric acetylacetonate as a precursor

We have developed a unique single-step chemical vapor deposition (CVD) route for the synthesis of composite thin films containing carbon nanotubes (CNTs). CVD was carried out in an inert ambient using only iron(III) acetylacetonate as the precursor. Depositions were conducted at 700 degrees C on stainless steel substrates in argon ambient in the absence of any reactive gases (such as oxygen, hydrogen). By changing the deposition parameters, especially the pressure in the CVD reactor, the form of carbon deposited could be changed from amorphous to carbon nanotubes, the latter resulting in Fe-Fe3O4-CNT films. X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, and electron microscopy together confirm the formation of the three-component composite and illustrate the nanoscale mixing of the components. Elemental iron formed in this process was protected from oxidation by the co-deposited carbon surrounding it. Irrespective of the substrate used, a composite coating with CNTs was formed under optimum conditions, as verified by analyses of the film formed on polycrystalline alumina and silicon substrates.

Influence of a Counterion on the Ion Atmosphere of an Anion: A Molecular Dynamics Study of LiX and CsX (X = F-, Cl-, I-) in Methanol

We report molecular dynamics (MD) simulations to explore the influence of a counterion on the structure and dynamics of cationic and anionic solvation shells for various ions in methanol at 298 K. We show that the variation in ionic size of either the cation or the anion in an ion pair influences the solvation structure of the other ion as well as the diffusivity in an electrolyte solution of methanol. The extent of ionic association between the cation and its counteranion of different ionic sizes has been investigated by analyzing the radial distribution functions (RDFs) and the orientation of methanol molecules in the first solvation shell (FSS) of ions. It is shown that the methanol in the FSS of the anion as well the cation exhibit quite different radial and orientational structures as compared to methanol which lie in the FSS of either the anion or the cation but not both. We find that the coordination number (CN) of F-, Cr-, and I- ions decreases with increasing size of the anion which is contrary to the trend reported for the anions in H2O. The mean residence time (MRT) of methanol molecules in the FSS of ions has been calculated using the stable states picture (SSP) approach. It is seen that the ion-counterion interaction has a considerable influence on the MRT of methanol molecules in the FSS of ions. We also discuss the stability order of the ion-counterion using the potentials of mean force (PMFs) for ion pairs with ions of different sizes. The PMF plots reveal that the Li+-F- pair (small-small) is highly stable and the Li+-I- pair is least stable (small-large) in electrolyte solutions.