Redox-linked conformation change and electron transfer between monoheme c-type cytochromes and oxides     

Nidhi Khare  Carrick M. Eggleston  Michael Swenson 《Geochimica et cosmochimica acta》2006,70(17):4332-4342

Electron transfer between redox active proteins and mineral oxides is important in a variety of natural as well as technological processes, including electron transfer from dissimilatory metal-reducing bacteria to minerals. One of the pathways that could trigger electron transfer between proteins and minerals is redox-linked conformation change. We present electrochemical evidence that mitochondrial cytochrome c (Mcc) undergoes significant conformation change upon interaction with hematite and indium-tin oxide (ITO) surfaces. The apparent adsorption-induced conformation change causes the protein to become more reducing, which makes it able to transfer electrons to the hematite conduction band. Although Mcc is not a protein thought to be involved in interaction with mineral surfaces, it shares (or can be conformed so as to share) some characteristics with multiheme outer-membrane cytochromes thought to be involved in the transfer of electrons from dissimilatory iron-reducing bacteria to ferric minerals during respiration. We present evidence that a 10.1 kDa monohoeme cytochrome isolated and purified from Acidiphilium cryptum, with properties similar to those of Mcc, also undergoes conformation change as a result of interaction with hematite surfaces.  相似文献   

Biosorption studies on shelled Moringa oleifera Lamarck seed powder: Removal and recovery of arsenic from aqueous system     

Pushpa Kumari  Parul SharmaShalini Srivastava  M.M. Srivastava 《International Journal of Mineral Processing》2006

The present study explores the unexploited sorption property of the shelled Moringa oleifera seeds (SMOS) for decontamination of arsenic from water bodies. Sorption studies (batch experiments) result into the standardization of optimum conditions for removal of 60.21% As(III) and 85.60% As(V) as follows: biomass dosage (2.0 g), metal concentration (25 mg/L), contact time (60 min) and volume of the test solution (200 ml) at pH 7.5 and 2.5, respectively. The adsorption data are fitted with Langmuir isotherm. Surface area has been measured using BET surface area analyzer. Morphological changes observed in scanning electron micrograph of native and treated SMOS indicates the existence of biosorption process. Fourier transform infrared spectrometry of exhausted seed biomass highlights protein/amino acid–arsenic interactions responsible for sorption phenomenon. Regeneration has also been attempted for several cycles with a view to restore the sorbent to its original state. The sorption capacity of the regenerated biomass remained almost constant after three cycles of sorption process, suggesting that the lifetime cycle was sufficient for continuous application. The findings open up new avenues in the decontamination of arsenic using SMOS from arsenic contaminated water, as domestic and environment-friendly safe technology.  相似文献   

Phosphate bonding configuration on ferrihydrite based on molecular orbital calculations and XANES fingerprinting     

Nidhi Khare  James D. Martin 《Geochimica et cosmochimica acta》2007,71(18):4405-4415

Sorption of phosphate by Fe(III)- and Al(III)-(hydr)oxide minerals regulates the mobility of this potential water pollutant in the environment. The objective of this research was to determine the molecular configuration of phosphate bound on ferrihydrite at pH 6 by interpreting P K-edge XANES spectra in terms of bonding mode. XANES and UV-visible absorption spectra for aqueous Fe(III)-PO₄ solutions (Fe/P molar ratio = 0-2.0) provided experimental trends for energies of P(3p)-O(2p) and Fe(3d)-O(2p) antibonding molecular orbitals. Molecular orbitals for Fe(III)-PO₄ or Al(III)-PO₄ complexes in idealized monodentate or bidentate bonding mode were generated by conceptual bonding arguments, and Extended-Hückel molecular orbital computations were used to understand and assign XANES spectral features to bound electronic states. The strong white line at the absorption edge in P K-edge XANES spectra for Fe-PO₄ or Al-PO₄ systems is attributable to an electronic transition from a P 1s atomic orbital into P(3p)-O(2p) or P(3p)-O(2p)-Al(3p) antibonding molecular orbitals, respectively. For Fe-PO₄ systems, a XANES peak at 2-5 eV below the edge was assigned to a P 1s electron transition into Fe(4p)-O(2p) antibonding molecular orbitals. Similarly, a shoulder on the low-energy side of the white line for variscite corresponds to a transition into Al(3p)-O(2p) orbitals. In monodentate-bonded phosphate, Fe-O bonding is optimized and P-O bonding is weakened, and the converse is true of bidentate-bonded phosphate. These differences explained an inverse correlation between energies of P(3p)-O(2p) and Fe(3d)-O(2p) antibonding molecular orbitals consistent with a monodentate-to-bidentate transition in aqueous Fe(III)-PO₄ solutions. The intensity of the XANES pre-edge feature in Fe(III)-bonded systems increased with increasing number of Fe(III)-O-P bonds. Based on the similarity of intensity and splitting of the pre-edge feature for phosphate sorbed on ferrihydrite at 750 mmol/kg at pH 6 and aqueous Fe-PO₄ solutions containing predominantly bidentate complexes, XANES results indicated that phosphate adsorbed on ferrihydrite was predominantly a bidentate-binuclear surface complex.  相似文献   

Multi-scale assessment of invasive plant species diversity using Pléiades 1A,RapidEye and Landsat-8 data     

Siddhartha Khare  Hooman Latifi  Sanjay Kumar Ghosh 《国际地球制图》2018,33(7):681-698

We used a full remote sensing-based approach to assess plant species diversity in large and inaccessible areas affected by Lantana camara L., a common invasive species within the deciduous forests of Western Himalayan region of India, using spectral heterogeneity information extracted from optical data. The spread of L. camara was precisely mapped by Pléiades 1A data, followed by comparing Pléiades 1A, RapidEye and Landsat-8 OLI – assessed plant species diversities in invaded areas. The single plant species analysis was improved by Pléiades 1A-based diversity analysis, and higher species diversity values were observed for mixed vegetation cover. Furthermore, lower Coefficient of Variation and Renyi diversity values were observed where L. camara was the only species, while higher variations were observed in areas with a mixed spectral reflectance. This study was concluded to add a crucial baseline to the previous studies on remote sensing-based solutions for rapid estimation of biodiversity attributes.  相似文献   

Spatial and temporal analysis of rainfall and temperature trend of India   总被引：3，自引：1，他引：2  

Arun Mondal  Deepak Khare  Sananda Kundu 《Theoretical and Applied Climatology》2015,122(1-2):143-158

  相似文献   

Do damped and sub-damped Lyman-alpha absorbers arise in galaxies of different masses?     

Varsha P. Kulkarni  Pushpa Khare  Debopam Som  Joseph Meiring  Donald G. York  Celine Péroux  James T. Lauroesch 《New Astronomy》2010,15(8):735-743

We consider the questions of whether the damped Lyman-alpha (DLA) and sub-DLA absorbers in quasar spectra differ intrinsically in metallicity, and whether they could arise in galaxies of different masses. Using the recent measurements of the robust metallicity indicators Zn and S in DLAs and sub-DLAs, we confirm that sub-DLAs have higher mean metallicities than DLAs, especially at z ? 2. We find that the intercept of the metallicity-redshift relation derived from Zn and S is higher than that derived from Fe by 0.5–0.6 dex. We also show that, while there is a correlation between the metallicity and the rest equivalent width of Mg II λ2796 or Fe II λ2599 for DLAs, no correlation is seen for sub-DLAs. Given this, and the similar Mg II or Fe II selection criteria employed in the discovery of both types of systems at lower redshifts, the difference between metallicities of DLAs and sub-DLAs appears to be real and not an artefact of selection. This conclusion is supported by our simulations of Mg II λ2796 and Fe II λ2599 lines for a wide range of physical conditions. On examining the velocity spreads of the absorbers, we find that sub-DLAs show somewhat higher mean and median velocity spreads (Δv), and an excess of systems with Δv > 150 km s^?1, than DLAs. Compared to DLAs, the [Mn/Fe] vs. [Zn/H] trend for sub-DLAs appears to be steeper and closer to the trend for Galactic bulge and thick disk stars, possibly suggesting different stellar populations. The absorber data appear to be consistent with galaxy down-sizing. The data are also consistent with the relative number densities of low-mass and high-mass galaxies. It is thus plausible that sub-DLAs arise in more massive galaxies on average than DLAs.  相似文献   

Prebiotic organic synthesis in early Earth and Mars atmospheres: Laboratory experiments with quantitative determination of products formed in a cold plasma flow reactor     

Michael N. Heinrich  Bishun N. Khare 《Icarus》2007,191(2):765-778

The goal of this study was to explore prebiotic chemistry in a range of plausible early Earth and Mars atmospheres. To achieve this laboratory continuous flow plasma irradiation experiments were performed on N₂/H₂/CO/CO₂ gas mixtures chosen to represent mildly reducing early Earth and Mars atmospheres derived from a secondary volcanic outgassing of volatiles in chemical equilibrium with magmas near present day oxidation state. Under mildly reducing conditions (91.79% N₂, 5.89% H₂, 2.21% CO, and 0.11% CO₂), simple nitriles are produced in the gas phase with yield (G in molecules per 100 eV), for the key prebiotic marker molecule HCN at G∼1×¹⁰⁻³ (0.1 nmol J⁻¹). In this atmosphere localized HCN concentrations possibly could approach the 10⁻² M needed for HCN oligomerization. Yields under mildly oxidizing conditions (45.5% N₂, 0.1% H₂, 27.2% CO, 27.2% CO₂) are significantly less as expected, with HCN at G∼3×¹⁰⁻⁵ (). Yields in a Triton atmosphere which can be plausibly extrapolated to represent what might be produced in trace CH₄ conditions (99.9% N₂, 0.1% CH₄) are significant with HCN at G∼1×¹⁰⁻² (1 nmol J⁻¹) and tholins produced. Recently higher methane abundance atmospheres have been examined for their greenhouse warming potential, and higher abundance hydrogen atmospheres have been proposed based on a low early Earth exosphere temperature. A reducing (64.04% N₂, 28.8% H₂, 3.60% CO₂, and 3.56% CH₄), representing a high CH₄ and H₂ abundance early Earth atmosphere had HCN yields of G∼5×¹⁰⁻³ (0.5 nmol J⁻¹). Tholins generated in high methane hydrogen gas mixtures is much less than in a similar mixture without hydrogen. The same mixture with the oxidizing component CO₂ removed (66.43% N₂, 29.88% H₂, 0% CO₂, and 3.69% CH₄) had HCN yields of G∼1×¹⁰⁻³ (0.1 nmol J⁻¹) but more significant tholin yields.  相似文献   

Electrochemical interaction of Shewanella oneidensis MR-1 and its outer membrane cytochromes OmcA and MtrC with hematite electrodes     

Leisa A. Meitl  Carrick M. Eggleston  Patricia J.S. Colberg  Nidhi Khare  Catherine L. Reardon  Liang Shi 《Geochimica et cosmochimica acta》2009,73(18):5292-5307

Bacterial metal reduction is an important biogeochemical process in anaerobic environments. An understanding of electron transfer pathways from dissimilatory metal-reducing bacteria (DMRB) to solid phase metal (hydr)oxides is important for understanding metal redox cycling in soils and sediments, for utilizing DMRB in bioremedation, and for developing technologies such as microbial fuel cells. Here we hypothesize that the outer membrane cytochromes OmcA and MtrC from Shewanella oneidensis MR-1 are the only terminal reductases capable of direct electron transfer to a hematite working electrode. Cyclic voltammetry (CV) was used to study electron transfer between hematite electrodes and protein films, S. oneidensis MR-1 wild-type cell suspensions, and cytochrome deletion mutants. After controlling for hematite electrode dissolution at negative potential, the midpoint potentials of adsorbed OmcA and MtrC were measured (−201 mV and −163 mV vs. Ag/AgCl, respectively). Cell suspensions of wild-type MR-1, deletion mutants deficient in OmcA (ΔomcA), MtrC (ΔmtrC), and both OmcA and MtrC (ΔmtrC–ΔomcA) were also studied; voltammograms for ΔmtrC–ΔomcA were indistinguishable from the control. When the control was subtracted from the single deletion mutant voltammograms, redox peaks were consistent with the present cytochrome (i.e., ΔomcA consistent with MtrC and ΔmtrC consistent with OmcA). The results indicate that OmcA and MtrC are capable of direct electron exchange with hematite electrodes, consistent with a role as terminal reductases in the S. oneidensis MR-1 anaerobic respiratory pathway involving ferric minerals. There was no evidence for other terminal reductases operating under the conditions investigated. A Marcus-based approach to electron transfer kinetics indicated that the rate constant for electron transfer k_et varies from 0.025 s⁻¹ in the absence of a barrier to 63.5 s⁻¹ with a 0.2 eV barrier.  相似文献   

Narrow associated quasi-stellar object absorbers: clustering, outflows and the line-of-sight proximity effect     

Vivienne Wild  Guinevere Kauffmann  Simon White  Donald York  Matthew Lehnert  Timothy Heckman  Patrick B. Hall  Pushpa Khare  Britt Lundgren  Donald P. Schneider  Daniel Vanden Berk 《Monthly notices of the Royal Astronomical Society》2008,388(1):227-241

Using data from the Sloan Digital Sky Survey data release 3 (SDSS DR3), we investigate how narrow (<700 km s⁻¹) C  iv and Mg  ii quasar absorption-line systems are distributed around quasars. The C  iv absorbers lie in the redshift range 1.6 < z < 4 and the Mg  ii absorbers in the range 0.4 < z < 2.2. By correlating absorbers with quasars on different but neighbouring lines of sight, we measure the clustering of absorbers around quasars on comoving scales between 4 and 30 Mpc. The observed comoving correlation lengths are   r _o∼ 5 h ⁻¹Mpc  , similar to those observed for bright galaxies at these redshifts. Comparing correlations between absorbers and the quasars, in whose spectra they are identified, then implies: (i) that quasars destroy absorbers to comoving distances of ∼300 kpc (C  iv ) and ∼800 kpc (Mg  ii ) along their lines of sight; (ii) that ≳40 per cent of C  iv absorbers within 3000 km s⁻¹ of the quasi-stellar object are not a result of large-scale clustering but rather are directly associated with the quasar itself; (iii) that this intrinsic absorber population extends to outflow velocities of the order of 12 000 km s⁻¹; (iv) that this outflow component is present in both radio-loud and radio-quiet quasars and (v) that a small high-velocity outflow component is also observed in the Mg  ii population. We also find an indication that absorption systems within 3000 km s⁻¹ are more abundant for radio-loud quasars than for radio-quiet quasars. This suggests either that radio-loud objects live in more massive haloes, or that their radio activity generates an additional low-velocity outflow, or both.  相似文献   

Detection and delineation of glacial lakes and identification of potentially dangerous lakes of Dhauliganga basin in the Himalaya by remote sensing techniques     

Lalan Kumar Jha  Deepak Khare 《Natural Hazards》2017,85(1):301-327

Glaciers are retreating and thinning in the high altitude of the Himalayas due to global warming, causing into formation of numerous glacial lakes. It is necessary to monitor these glacial lakes consistently to save properties and lives downstream from probable disastrous glacial lake outburst flood. In this study, image processing software ArcGIS and ERDAS Imagine have been used to analyse multispectral image obtained by Earth resource satellite Landsat for delineating the glacial lakes with the help of image enhancement technique like NDWI. Landsat data since 1972 through 2013 have been used and maximum seven glacial lakes (L1–L7) have been detected and delineated in Dhauliganga catchment, they are situated above 4000 masl. The Glacial Lake L2 (Lat 30°26′45″E and Long 80°23′16″N) is the largest whose surface area was 132,300 m² in Sept 2009, and L6 (Lat 30°23′27″E and Long 80°31′52″N) is highly unstable with variation rate ?55 to +145 % with increasing trend. Additionally, glacial lakes L2 (Lat 30°26′45″E and Long 80°23′16″N) and L6 (Lat 30°23′27″E and Long 80°31′52″N) have been identified as potentially hazardous. These lakes may probably burst; as a result, huge reserve of water and debris may be released all on a sudden. This may transform into hazardous flash flood in downstream causing loss of lives, as well as the destruction of houses, bridges, fields, forests, hydropower stations, roads, etc. It is to note that Dhauliganga river considered in this study is a tributary of Kaliganga river, and should not be confused with its namesake the Dhauliganga river, which is a tributary of Alaknanda river.  相似文献