A Novel Approach to the Study of Surface Oxidation States and Oxidation of Transition Metals by Auger Electron Spectroscopy

L$_{23}$ M$_{45}$ M$_{45}$/L$_{23}$ M$_{23}$ M$_{45}$, L$_{23}$ M$_{45}$ M$_{45}$/L$_{23}$ M$_{23}$ M$_{23}$ and L$_{23}$ M$_{23}$ M$_{45}$/L$_{23}$ M$_{23}$ M$_{23}$ Auger intensity ratios in transition metal oxides and sulphides are shown to be directly related to the number of valence electrons in the metal as well as to its oxidation state. The metal Auger intensity ratios provide a unique probe, independent of O (KLL) intensity, to study surface oxidation states of metals. These intensity ratios have been effectively employed to investigate surface oxidation of nickel, iron and copper. The oxidation studies have unravelled some interesting aspects of surface oxidation.

Transcriptional events during early phase of germination of rice embryos

GERMINATION transfers a metabolically inert embryo into an active state of growth and development. The presence of conserved mRNAs has been demonstrated in different species of eggs and seeds1–4. In rice embryos, germination was shown to be independent of the synthesis of RNA up to 18–24 h after the start of imbibition5, although RNA synthesis was detected as early as 9 h after the start of imbibition. In this report, the sequence of the transcriptional events taking place during the early phase of the germination of rice embryos are presented.

Proteomics and mass spectrometric studies reveal planktonic growth of Mycobacterium smegmatis in biofilm cultures in the absence of rpoZ

Mycobacterium smegmatis is known to form biofilms and many cell surface molecules like core glycopeptidolipids and short-chain mycolates appear to play important role in the process. However, the involvement of the cell surface molecules in mycobacteria towards complete maturation of biofilms is still not clear. This work demonstrates the importance of the glycopeptidolipid species with hydroxylated alkyl chain and the epoxylated mycolic acids, during the process of biofilm development. In our previous study, we reported the impairment of biofilm formation in rpoZ-deleted M. smegmatis, where rpoZ codes for the ω subunit of RNA polymerase (R. Mathew, R. Mukherjee, R. Balachandar, D. Chatterji, Microbiology 152 (2006) 1741). Here we report the occurrence of planktonic growth in a mc2155 strain which is devoid of rpoZ gene. This strain is deficient in selective incorporation of the hydroxylated glycopeptidolipids and the epoxy mycolates to their respective locations in the cell wall. Hence it forms a mutant biofilm defective in maturation, wherein the cells undertake various alternative metabolic pathways to survive in an environment where oxygen, the terminal electron acceptor, is limiting.

Rationalizing the effects of amino acid side chain, pyridine, and imidazole on the assembly and reversible disassembly of a octanuclear Cu(III) complex

This paper reports the observation of a reversible disassembly process for a previously reported octanuclear Cu(II) complex with imidazole. To identify the factors responsible for the process, five Cu(II) complexes of different nuclearity with different amino acid-derived tetradentate ligands were structurally characterized. The results show that the coordination geometry preference of Cu(II), the tendency of imidazole to act as in-plane ligand, and H-bonding played important role in the formation and disassembly of the octanuclear complex. A general scheme describing the effect of different amino acid side arms, solvents, and exogenous ligands on the nuclearity of the Cu(II) complexes has been presented. The crystals of the complexes also showed formation of multifaceted networks in the resulting complexes.

The role of sustainable agriculture and renewable-resource management in reducing greenhouse-gas emissions and increasing sinks in China and India

This paper contains an analysis of the technical options in agriculture for reducing greenhouse-gas emissions and increasing sinks, arising from three distinct mechanisms: (i) increasing carbon sinks in soil organic matter and above-ground biomass; (ii) avoiding carbon emissions from farms by reducing direct and indirect energy use; and (iii) increasing renewable-energy production from biomass that either substitutes for consumption of fossil fuels or replaces inefficient burning of fuelwood or crop residues, and so avoids carbon emissions, together with use of biogas digesters and improved cookstoves. We then review best-practice sustainable agriculture and renewable-resource-management projects and initiatives in China and India, and analyse the annual net sinks being created by these projects, and the potential market value of the carbon sequestered. We conclude with a summary of the policy and institutional conditions and reforms required for adoption of best sustainability practice in the agricultural sector to achieve the desired reductions in emissions and increases in sinks. A review of 40 sustainable agriculture and renewable-resource-management projects in China and India under the three mechanisms estimated a carbon mitigation potential of 64.8 MtC yr(-1) from 5.5 Mha. The potential income for carbon mitigation is $324 million at $5 per tonne of carbon. The potential exists to increase this by orders of magnitude, and so contribute significantly to greenhouse-gas abatement. Most agricultural mitigation options also provide several ancillary benefits. However, there are many technical, financial, policy, legal and institutional barriers to overcome.

State of bismuth in BaBiO3 and BaBi1-xPbxO3: Bi 4f photoemission and Bi L3 absorption spectroscopic studies

The 2p 6d feature in the Bi L3 spectra has different energies in the semiconducting (0.0≤x<0.7) and the superconducting (x=0.75) compositions of BaBi1−xPbxO3. The Bi 4f core level spectrum shows distinct features ascribable to Bi III and Bi V in BaBiO3 and in the semiconducting compositions; the width of the 4f peaks is also considerably larger in these compositions compared to that in BaBi0.25Pb0.75O3, which shows a single sharp Bi 4f feature.

Study of molecular structure and vibrational spectra of poly (beta,-1-malic acid) PMLA] using DFT approach

Poly (beta-L-malic acid) (PMLA) is a biodegradable polymer and it has various important applications in the biomedical field. In the present work the structural and spectral characteristics of PMLA have been studied by methods of infrared. Raman spectroscopy and quantum chemistry. Electrostatic potential surface, optimized geometry, harmonic vibrational frequencies, infrared intensities and activities of Raman scattering were calculated by density functional theory (DFT) using oligomeric approach employing B3LYP with complete relaxation in the potential energy surface using 6-311++G (d, p) basis set. Based on results, we have discussed the correlation between the vibrational modes and the structure of the PMLA. A complete analysis of the experimental infrared and Raman spectra has been reported on the basis of wavenumber of the vibrational bands and potential energy distribution. The calculated HOMO and LUMO energies shows that charge transfer occur within the molecule. The calculated infrared and the Raman spectra of the polymer based on DFT calculations show reasonable agreement with the experimental results. (c) 2012 Elsevier Ltd. All rights reserved.

Inter-domain interactions influence the stability and catalytic activity of the bi-domain protein tyrosine phosphatase PTP99A

The two protein tyrosine phosphatase (PTP) domains in bi-domain PTPs share high sequence and structural similarity. However, only one of the two PIP domains is catalytically active. Here we describe biochemical studies on the two tandem PTP domains of the bi-domain PTP, PTP99A. Phosphatase activity, monitored using small molecule as well as peptide substrates, revealed that the inactive (D2) domain activates the catalytic (D1) domain. Thermodynamic measurements suggest that the inactive D2 domain stabilizes the bi-domain (D1-D2) protein. The mechanism by which the D2 domain activates and stabilizes the bi-domain protein is governed by few interactions at the inter-domain interface. In particular, mutating Lys990 at the interface attenuates inter-domain communication. This residue is located at a structurally equivalent location to the so-called allosteric site of the canonical single domain PIP, PTP1B. These observations suggest functional optimization in bi-domain PTPs whereby the inactive PTP domain modulates the catalytic activity of the bi-domain enzyme. (C) 2012 Elsevier B.V. All rights reserved.

Averting biodiversity collapse in tropical forest protected areas

The rapid disruption of tropical forests probably imperils global biodiversity more than any other contemporary phenomenon(1-3). With deforestation advancing quickly, protected areas are increasingly becoming final refuges for threatened species and natural ecosystem processes. However, many protected areas in the tropics are themselves vulnerable to human encroachment and other environmental stresses(4-9). As pressures mount, it is vital to know whether existing reserves can sustain their biodiversity. A critical constraint in addressing this question has been that data describing a broad array of biodiversity groups have been unavailable for a sufficiently large and representative sample of reserves. Here we present a uniquely comprehensive data set on changes over the past 20 to 30 years in 31 functional groups of species and 21 potential drivers of environmental change, for 60 protected areas stratified across the world's major tropical regions. Our analysis reveals great variation in reserve `health': about half of all reserves have been effective or performed passably, but the rest are experiencing an erosion of biodiversity that is often alarmingly widespread taxonomically and functionally. Habitat disruption, hunting and forest-product exploitation were the strongest predictors of declining reserve health. Crucially, environmental changes immediately outside reserves seemed nearly as important as those inside in determining their ecological fate, with changes inside reserves strongly mirroring those occurring around them. These findings suggest that tropical protected areas are often intimately linked ecologically to their surrounding habitats, and that a failure to stem broad-scale loss and degradation of such habitats could sharply increase the likelihood of serious biodiversity declines.

Analysis of integrated optofluidic lab-on-a-chip sensor based on refractive index and absorbance sensing

The analysis of a fully integrated optofluidic lab-on-a-chip sensor is presented in this paper. This device is comprised of collinear input and output waveguides that are separated by a microfluidic channel. When light is passed through the analyte contained in the fluidic gap, optical power loss occurs owing to absorption of light. Apart from absorption, a mode-mismatch between the input and output waveguides occurs when the light propagates through the fluidic gap. The degree of mode-mismatch and quantum of optical power loss due to absorption of light by the fluid form the basis of our analysis. This sensor can detect changes in refractive index and changes in concentration of species contained in the analyte. The sensitivity to detect minute changes depends on many parameters. The parameters that influence the sensitivity of the sensor are mode spot size, refractive index of the fluid, molar concentration of the species contained in the analyte, width of the fluidic gap, and waveguide geometry. By correlating various parameters, an optimal fluidic gap distance corresponding to a particular mode spot size that achieves the best sensitivity is determined both for refractive index and absorbance-based sensing.

Demodulation of Narrowband Speech Spectrograms Using the Riesz Transform

We propose a two-dimensional (2-D) multicomponent amplitude-modulation, frequency-modulation (AM-FM) model for a spectrogram patch corresponding to voiced speech, and develop a new demodulation algorithm to effectively separate the AM, which is related to the vocal tract response, and the carrier, which is related to the excitation. The demodulation algorithm is based on the Riesz transform and is developed along the lines of Hilbert-transform-based demodulation for 1-D AM-FM signals. We compare the performance of the Riesz transform technique with that of the sinusoidal demodulation technique on real speech data. Experimental results show that the Riesz-transform-based demodulation technique represents spectrogram patches accurately. The spectrograms reconstructed from the demodulated AM and carrier are inverted and the corresponding speech signal is synthesized. The signal-to-noise ratio (SNR) of the reconstructed speech signal, with respect to clean speech, was found to be 2 to 4 dB higher in case of the Riesz transform technique than the sinusoidal demodulation technique.

A flame particle tracking analysis of turbulence-chemistry interaction in hydrogen-air premixed flames

Interactions of turbulence, molecular transport, and energy transport, coupled with chemistry play a crucial role in the evolution of flame surface geometry, propagation, annihilation, and local extinction/re-ignition characteristics of intensely turbulent premixed flames. This study seeks to understand how these interactions affect flame surface annihilation of lean hydrogen-air premixed turbulent flames. Direct numerical simulations (DNSs) are conducted at different parametric conditions with a detailed reaction mechanism and transport properties for hydrogen-air flames. Flame particle tracking (FPT) technique is used to follow specific flame surface segments. An analytical expression for the local displacement flame speed (S-d) of a temperature isosurface is considered, and the contributions of transport, chemistry, and kinematics on the displacement flame speed at different turbulence-flame interaction conditions are identified. In general, the displacement flame speed for the flame particles is found to increase with time for all conditions considered. This is because, eventually all flame surfaces and their resident flame particles approach annihilation by reactant island formation at the end of stretching and folding processes induced by turbulence. Statistics of principal curvature evolving in time, obtained using FPT, suggest that these islands are ellipsoidal on average enclosing fresh reactants. Further examinations show that the increase in S-d is caused by the increased negative curvature of the flame surface and eventual homogenization of temperature gradients as these reactant islands shrink due to flame propagation and turbulent mixing. Finally, the evolution of the normalized, averaged, displacement flame speed vs. stretch Karlovitz number are found to collapse on a narrow band, suggesting that a unified description of flame speed dependence on stretch rate may be possible in the Lagrangian description. (C) 2015 The Combustion Institute. Published by Elsevier Inc. All rights reserved.