Nanotubes of the disulfides of groups 4 and 5 metals

The layered chalcogenides, having structures analogous to graphite, are known to be unstable toward bending and show high propensity to form curved structures, thus eliminating dangling bonds at the edges. Since the discovery of fullerene and nanotube structures of WS2 and MoS2 by Tenne et al. [1-3], there have been attempts to prepare and characterize nanotubes of other layered dichalcogenides with structures analogous to MoS2. Nanotubes of MoS2 and WS2 were prepared by Tenne et al. by reducing the corresponding oxides to the suboxides followed by heating in an atmosphere of forming gas (5 % H-2 + 95 % N-2) and H2S at 700-900 degreesC [1-3]. Alternative methods of synthesis of MoS2 and WS2 nanotubes have since been proposed by employing the decomposition of the ammonium thiometallates or the corresponding trisulfide precursors. This alternative procedure was based on the observation that the trisulfide seems to be formed as an intermediate in the synthesis of the MoS2 and WS2 nanotubes [4]. Accordingly, the decomposition of the trisulfides of MoS2 and W in a reducing atmosphere directly yielded nanotubes of the disulfides MoS2 and WS2 [5]. In this article, we describe the synthesis, structure, and characterization of a few novel nanotubes of the disulfides of groups 4 and 5 metals. These include nanotubes of NbS2, TaS2, ZrS2, and HfS2. The study enlarges the scope of the inorganic nanotubes significantly and promises other interesting possibilities, including the synthesis of the diselenide nanotubes of these metals.

Stable and Potent Analogues Derived from the Modification of the Dicarbonyl Moiety of Curcumin

Curcumin has shown promising therapeutic utilities for many diseases, including cancer; however, its clinical application is severely limited because of its poor stability under physiological conditions. Here we find that curcumin also loses its activity instantaneously in a reducing environment. Curcumin can exist in solution as a tautomeric mixture of keto and enol forms, and the enol form was found to be responsible for the rapid degradation of the compound. To increase the stability of curcumin, several analogues were synthesized in which the diketone moiety of curcumin was replaced by isoxazole (compound 2) and pyrazole (compound 3) groups. Isoxazole and pyrazole curcumins were found to be extremely stable at physiological pH, in addition to reducing atmosphere, and they can kill cancer cells under serum-depleted condition. Using molecular modeling, we found that both compounds 2 and 3 could dock to the same site of tubulin as the parent molecule, curcumin. Interestingly, compounds 2 and 3 also show better free radical scavenging activity than curcumin. Altogether, these results strongly suggest that compounds 2 and 3 could be good replacements for curcumin in future drug development.

Two-step Synthesis of MoS2 Nanotubes using Shock Waves with Lead as Growth Promoter

A new two-step procedure for the synthesis of MoS2 nanotubes using lead as a growth promoter is reported. In the first step, molybdenum suboxide nanowhiskers containing a small amount of lead atoms were created by exposing a pressed MoS2+Pb mixture to highly compressed shock-heated argon gas, with estimated temperatures exceeding 9900 K. In the second step, these molybdenum suboxide nanowhiskers served as templates for the sulfidization of the oxide into MoS2 nanotubes (by using H2S gas in a reducing atmosphere at 820 degrees C). Unlike the case of WS2 nanotubes, the synthesis of a pure phase of MoS2 nanotubes from molybdenum oxide has proven challenging, due mostly to the volatile nature of the latter at the high requisite reaction temperatures (>800 degrees C). In contrast, the nature and apparent reaction mechanism of the method reported herein are amenable to future scale-up. The high-temperature shockwave system should also facilitate the synthesis of new nanostructures from other layered materials.

Synthesis of Hollow Nanotubes of Zn2SiO4 or SiO2: Mechanistic Understanding and Uranium Adsorption Behavior

We report a facile synthesis of Zn2SiO4 nanotubes using a two-step process consisting of a wet-chemical synthesis of core-shell ZnO@SiO2 nanorods followed by thermal annealing. While annealing in air leads to the formation of hollow Zn2SiO4, annealing under reducing atmosphere leads to the formation of SiO2 nanotubes. We rationalize the formation of the silicate phase at temperatures much lower than the temperatures reported in the literature based on the porous nature of the silica shell on the ZnO nanorods. We present results from in situ transmission electron microscopy experiments to clearly show void nucleation at the interface between ZnO and the silica shell and the growth of the silicate phase by the Kirkendall effect. The porous nature of the silica shell is also responsible for the etching of the ZnO leading to the formation of silica nanotubes under reducing conditions. Both the hollow silica and silicate nanotubes exhibit good uranium sorption at different ranges of pH making them possible candidates for nuclear waste management.

Climate response to physiological forcing of carbon dioxide simulated by the coupled Community Atmosphere Model (CAM3.1) and Community Land Model (CLM3.0)

Increasing concentrations of atmospheric CO2 decrease stomatal conductance of plants and thus suppress canopy transpiration. The climate response to this CO2-physiological forcing is investigated using the Community Atmosphere Model version 3.1 coupled to Community Land Model version 3.0. In response to the physiological effect of doubling CO2, simulations show a decrease in canopy transpiration of 8%, a mean warming of 0.1K over the land surface, and negligible changes in the hydrological cycle. These climate responses are much smaller than what were found in previous modeling studies. This is largely a result of unrealistic partitioning of evapotranspiration in our model control simulation with a greatly underestimated contribution from canopy transpiration and overestimated contributions from canopy and soil evaporation. This study highlights the importance of a realistic simulation of the hydrological cycle, especially the individual components of evapotranspiration, in reducing the uncertainty in our estimation of climatic response to CO2-physiological forcing. Citation: Cao, L., G. Bala, K. Caldeira, R. Nemani, and G.Ban-Weiss (2009), Climate response to physiological forcing of carbon dioxide simulated by the coupled Community Atmosphere Model (CAM3.1) and Community Land Model (CLM3.0).

Ocean atmosphere coupling over monsoon regions

In monsoon regions, the seasonal migration of the intertropical convergence zone (ITCZ) is manifested as a seasonal reversal of winds. Most of the summer monsoon rainfall over India occurs owing to synoptic and large-scale convection associated with the continental ITCZ (Fig. 1). We have investigated the interaction between these large-scale convective systems and the ocean over which they are generated1â3, concentrating on the relationship between organized convection over the Indian Ocean and sea surface temperature (SST). We report here that on a monthly basis the degree of cloudiness correlates well with SST for the relatively colder oceans, but when SST is maintained above 28 °C it ceases to be an important factor in determining the variability of cloudiness. Over the major regions of convection east of 70°E, which are warm year after year, the observed cloudiness cannot be correlated with variations in SST.

Oxygen-reducing electrodes for acid fuel cells

Electrochemical data are reported for oxygen reduction on platinized coconut-shell charcoal electrodes in 2.5M H*SO,, and 7M HsF’04. In both these media the electrodes exhibit good activity and can sustain currents up to 600 mA cm-* at a polarization of about 400 mV from their rest potentials. The overall performance is comparable with the best type of carbonsupported platinum electrodes reported in the literature.

Cooking in the ungra area: Fuel efficiency, energy losses, and opportunities for reducing firewood consumption

Cooking efficiency and related fuel economy issues have been studied in a particular rural area of India. Following a description of the cooking practices and conditions in this locale, cooking efficiency is examined. A cooking efficiency of only 6% was found. The use of aluminium rather than clay pots results in an increased efficiency. In addition, cooking efficiency correlates very well with specific fuel consumption. The latter parameter is much simpler to analyse than cooking efficiency. The energy losses during cooking are examined in the second part of this case study. The major energy losses are heating of excess air, heat carried away by the combustion products, heat transmitted to the stove body and floor, and the chemical energy in charcoal residue. The energy loss due to the evaporation of cooking water is also significant because it represents about one-third of the heat reaching the pots.

Long waves in inviscid compressible atmosphere II

Solitary waves have been found in an adiabatic compressible atmosphere which, in ambient state, has winds and temperature gradient, generalizing our earlier results for the isothermal atmosphere. Explicit results are obtained for the special case of linear temperature and linear wind distributions in the undisturbed conditions. An important result of the study is that the number of possible critical speeds of the flow depends crucially on whether the maximum Richardson number (which is variable in the present example) is greater or less than 1/4.

Lighting the way: Towards reducing misorientation of olive ridley hatchlings due to artificial lighting at Rushikulya, India

Sea-finding behavior in sea turtle hatchlings is modified by the visual cues provided by artificial beach front lighting. The consequent landward movement of hatchlings in response to coastal electric lighting reduces their survival rates. We assessed the potential impact of coastal lighting at Rushikulya, an important mass nesting site of the olive ridley sea turtle (Lepidochelys olivacea) in the Indian Ocean region. We examined the response of hatchlings to light characteristics in an experimental setup, as well as to the existing lighting regimes along the beach, using arena trials. Previous studies on other species indicate preferential orientation towards low wavelength and high intensity light. Our study confirms these preferences among hatchlings from the Indian Ocean population of olive ridleys. In addition we also found that wavelength and intensity could have an interactive effect upon hatchling orientation. Hatchlings at the study site respond both to visible point sources of light and to sheer glows of light. Though beach plantations of introduced Casuarina equisetifolia are generally considered to have negative impacts on sea turtle nesting beaches, we found that they acted as an effective light barrier when planted about 50 m away from the high tide line. We developed a model of the expected impact of artificial lighting on hatchling orientation during mass hatching events of previous years, and predict as much as 50% misorientation in some years. We also developed a map representing the misorientation of hatchlings due to artificial lighting based on arena trials in different regions of the beach. The results of the study helped identify focal areas for light management on the beach, which could be critical for the survival of this population.

Role of Thiobacillus ferrooxidans and sulphur (sulphide)-dependent ferric-ion-reducing activity in the oxidation of sulphide minerals

Thiobacillus ferrooxidans oxidized the sulphide minerals e.g., pyrite, pyrrhotite and copper concentrate under anaerobic conditions in the presence of ferric ion as sole electron acceptor. Copper and iron were solubilized from sulphide ores by the sulphur (sulphide)-dependent ferric-ion oxidoreductase activity. Treatment of resting cells of T. ferrooxidans with 0.5% phenol for 30 min completely destroyed the iron- and copper-solubilizing activity. The above treatment destroyed the sulphur(sulphide)-dependent ferric-ion-reducing activity completely but did not affect the iron-oxidizing activity. The results suggest that sulphur(sulphide)-dependent ferric-ion-reducing activity actively participates in the oxidation of sulphide minerals under anaerobic conditions. The activity of sulphur(sulphide)-dependent ferric ion reduction in the solubilization of iron and copper from the sulphide ores were also observed under aerobic conditions in presence of sodium azide (0.1 μmol), which completely inhibits the iron-oxidizing activity.

The effect of horizontal resolution on simulation of very extreme US precipitation events in a global atmosphere model

We investigate the ability of a global atmospheric general circulation model (AGCM) to reproduce observed 20 year return values of the annual maximum daily precipitation totals over the continental United States as a function of horizontal resolution. We find that at the high resolutions enabled by contemporary supercomputers, the AGCM can produce values of comparable magnitude to high quality observations. However, at the resolutions typical of the coupled general circulation models used in the Fourth Assessment Report of the Intergovernmental Panel on Climate Change, the precipitation return values are severely underestimated.

Importance of carbon dioxide physiological forcing to future climate change

An increase in atmospheric carbon dioxide (CO2) concentration influences climate both directly through its radiative effect (i.e., trapping longwave radiation) and indirectly through its physiological effect (i.e., reducing transpiration of land plants). Here we compare the climate response to radiative and physiological effects of increased CO2 using the National Center for Atmospheric Research (NCAR) coupled Community Land and Community Atmosphere Model. In response to a doubling of CO2, the radiative effect of CO2 causes mean surface air temperature over land to increase by 2.86 ± 0.02 K (± 1 standard error), whereas the physiological effects of CO2 on land plants alone causes air temperature over land to increase by 0.42 ± 0.02 K. Combined, these two effects cause a land surface warming of 3.33 ± 0.03 K. The radiative effect of doubling CO2 increases global runoff by 5.2 ± 0.6%, primarily by increasing precipitation over the continents. The physiological effect increases runoff by 8.4 ± 0.6%, primarily by diminishing evapotranspiration from the continents. Combined, these two effects cause a 14.9 ± 0.7% increase in runoff. Relative humidity remains roughly constant in response to CO2-radiative forcing, whereas relative humidity over land decreases in response to CO2-physiological forcing as a result of reduced plant transpiration. Our study points to an emerging consensus that the physiological effects of increasing atmospheric CO2 on land plants will increase global warming beyond that caused by the radiative effects of CO2.

Microbially induced separation of quartz from hematite using sulfate reducing bacteria

Cells and metabolic products of Desulfovibrio desulfuricans were successfully used to separate quartz from hematite through environmentally benign microbially induced flotation. Bacterial metabolic products such as extracellular proteins and polysaccharides were isolated from both unadapted and mineral-adapted bacterial metabolite and their basic characteristics were studied in order to get insight into the changes brought about on bioreagents during adaptation. Interaction between bacterial cells and metabolites with minerals like hematite and quartz brought about significant surface-chemical changes on both the minerals. Quartz was rendered more hydrophobic, while hematite became more hydrophilic after biotreatment.The predominance of bacterial polysaccharides on interacted hematite and of proteins on quartz was responsible for the above surface-chemical changes, as attested through adsorption studies. Surface-chemical changes were also observed on bacterial cells after adaptation to the above minerals. Selective separation of quartz from hematite was achieved through interaction with quartz-adapted bacterial cells and metabolite. Mineral-specific proteins secreted by quartz-adapted cells were responsible for conferment of hydrophobicity on quartz resulting in enhanced separation from hematite through flotation. (C) 2010 Elsevier B.V. All rights reserved.

Coupled ocean-atmosphere inter-decadal modes in the tropics

Homogencous upper air data for 50 years (1949-1998) from the National Centers for Environmental Prediction/National Center for Atmospheric Research (NCEP/NCAR) reanalysis project, sea surface temperatures and sea level pressure are used to bring out the three dimensional structure of two dominant decadal/multi-decadal variations in the tropics. The global three dimensional modes represent generalized forms of inter-decadal modes studied earlier only with surface data. In the vertical, both modes show approximate first baroclinic structures over the tropics. The Walker circulation associated with the multidecadal mode has a wavenumber two structure in the zonal direction. It is shown that the magnitude of major ascending and descending motions associated with the multi-decadal Hadley and Walker circulations, are comparable to those associated with the dominant inter-annual mode. Implications of these large scale global circulations associated with the low frequency oscillations in modulating regional climate on a inter-annual time scale are discussed.