Sulfate-associated liquid water amplifies the formation of oxalic acid at a semi-arid tropical location over peninsular India during winter.

Aerosol liquid water (ALW) can serve as an aqueous-phase medium for numerous chemical reactions and consequently enhance the formation of secondary aerosols in a highly humid atmosphere. However, the aqueous-phase formation of secondary organic aerosols (SOAs) is not well understood in the Indian regions, particularly in tropical peninsular India. In this study, we collected total suspended particulate samples (n = 30) at a semiarid station (Ballari; 15.15°N, 76.93°E; 495 m asl) in tropical peninsular India during the winter of 2016. Homologous series of dicarboxylic acids (C2-C12), oxoacids (ωC2-ωC9), pyruvic acid (Pyr), and glyoxal (Gly) were determined by employing a water-extraction of aerosol and analyzed using capillary gas chromatography (GC). Results show that oxalic acid (C2) was the most abundant organic acid, followed by succinic (C4), malonic (C3), azelaic (C9), and glyoxylic (ωC2) or phthalic (Ph) acids. Total diacids-C accounted for 1.7-5.8 % of water-soluble organic carbon (WSOC) and 0.6-3.6 % of total carbon (TC). ALW, estimated from the ISORROPIA 2.1 model, showed a strong linear relationship with sulfate (SO42-), C2, C3, C4, ωC2, Pyr, and Gly. Based on molecular distribution, specific mass ratios (C2/C3, C2/C4, C2/Gly, and Ph/C9), linear relationships among the measured organic acids, ALW, organic (levoglucosan and oleic acid), and inorganic (SO42-) marker compounds, we emphasize that diacids and related organic compounds, especially C2, majorly form via aqueous-phase oxidation of precursor compounds including aromatic hydrocarbons (HCs) and unsaturated fatty acids (FAs) originated from biomass burning and combustion-related sources. The present study demonstrates that sulfate driven ALW largely enhances the formation of SOAs via the aqueous-phase reactions over tropical peninsular India during winter.

A novel sampling-based visual topic models with computational intelligence for big social health data clustering.

Twitter is a popular social network for people to share views or opinions on various topics. Many people search for health topics through Twitter; thus, obtaining a vast amount of social health data from Twitter is possible. Topic models are widely used for social health-care data clustering. These models require prior knowledge about the clustering tendency. Determining the number of clusters of given social health data is known as the health cluster tendency. Visual techniques, including visual assessment of the cluster tendency, cosine-based, and multiviewpoint-based cosine similarity features VAT (MVCS-VAT), are used to identify social health cluster tendencies. The recent MVCS-VAT technique is superior to others; however, it is the most expensive technique for big social health data cluster assessment. Thus, this paper aims to enhance the work of the MVCS-VAT using a sampling technique to address the big social health data assessment problem. Experimental is conducted on different health datasets for demonstrating an efficiency of proposed work. Accuracy of social health data clustering is improved at a rate of 5 to 10% in the proposed S-MVCS-VAT when compared to MVCS-VAT. From obtained results, it also proved that the proposed S-MVCS-VAT is a faster and memory efficient for discovering social health data clusters.

Mycobacterium tuberculosis WhiB4 regulates oxidative stress response to modulate survival and dissemination in vivo.

Host-generated oxidative stress is considered one of the main mechanisms constraining Mycobacterium tuberculosis (Mtb) growth. The redox-sensing mechanisms in Mtb are not completely understood. Here we show that WhiB4 responds to oxygen (O2) and nitric oxide (NO) via its 4Fe-4S cluster and controls the oxidative stress response in Mtb. The WhiB4 mutant (MtbΔwhiB4) displayed an altered redox balance and a reduced membrane potential. Microarray analysis demonstrated that MtbΔwhiB4 overexpresses the antioxidant systems including alkyl hydroperoxidase (ahpC-ahpD) and rubredoxins (rubA-rubB). DNA binding assays showed that WhiB4 [4Fe-4S] cluster is dispensable for DNA binding. However, oxidation of the apo-WhiB4 Cys thiols induced disulphide-linked oligomerization, DNA binding and transcriptional repression, whereas reduction reversed the effect. Furthermore, WhiB4 binds DNA with a preference for GC-rich sequences. Expression analysis showed that oxidative stress repressed whiB4 and induced antioxidants in Mtb, while their hyper-induction was observed in MtbΔwhiB4. MtbΔwhiB4 showed increased resistance to oxidative stress in vitro and enhanced survival inside the macrophages. Lastly, MtbΔwhiB4 displayed hypervirulence in the lungs of guinea pigs, but showed a defect in dissemination to their spleen. These findings suggest that WhiB4 systematically calibrates the activation of oxidative stress response in Mtb to maintain redox balance, and to modulate virulence.

Size segregated mass concentration and size distribution of near surface aerosols over a tropical Indian semi-arid station, Anantapur: Impact of long range transport.

Regular measurements of size segregated as well as total mass concentration and size distribution of near surface composite aerosols, made using a ten-channel Quartz Crystal Microbalance (QCM) cascade impactor during the period of September 2007-May 2008 are used to study the aerosol characteristics in association with the synoptic meteorology. The total mass concentration varied from 59.70+/-1.48 to 41.40+/-1.72 microg m(-3), out of which accumulation mode dominated by approximately 50%. On a synoptic scale, aerosol mass concentration in the accumulation (submicron) mode gradually increased from an average low value of approximately 26.92+/-1.53 microg m(-3) during the post monsoon season (September-November) to approximately 34.95+/-1.32 microg m(-3) during winter (December-February) and reaching a peak value of approximately 43.56+/-1.42 microg m(-3) during the summer season (March-May). On the contrary, mass concentration of aerosols in the coarse (supermicron) mode increased from approximately 9.23+/-1.25 microg m(-3)during post monsoon season to reach a comparatively high value of approximately 25.89+/-1.95 microg m(-3) during dry winter months and a low value of approximately 8.07+/-0.76 microg m(-3) during the summer season. Effective radius, a parameter important in determining optical (scattering) properties of aerosol size distribution, varied between 0.104+/-0.08 microm and 0.167+/-0.06 microm with a mean value of 0.143+/-0.01 microm. The fine mode is highly reduced during the post monsoon period and the large and coarse modes continue to remain high (replenished) so that their relative dominance increases. It can be seen that among the two parameters measured, correlation of total mass concentration with air temperature is positive (R(2)=0.82) compared with relative humidity (RH) (R(2)=0.75).

Temporal and spectral characteristics of aerosol optical depths in a semi-arid region of southern India.

The spectral and temporal variations of aerosol optical depths (AOD) observed over Anantapur (a semi-arid region) located in the Southern part of India are investigated by analyzing the data obtained from a Multiwavelength Solar Radiometer (MWR) during January 2005-December 2006 (a total of 404 clear-sky observations) using the Langley technique. In this paper, we highlighted the studies on monthly, seasonal and spectral variations of aerosol optical depth and their implications. The results showed seasonal variation with higher values during pre-monsoon (March-May) and lower in the monsoon (June-November) season at all wavelengths. The pre-monsoon increase is found to be due to the high wind speed producing larger amounts of wind-driven dust particles. The post-monsoon (December-February) AOD values decrease more at higher wavelengths, indicating a general reduction in the number of bigger particles. Also during the post-monsoon, direction of winds in association with high or low pressure weather systems and the air brings more aerosol content to the region which is surrounded by a number of cement plants, lime kilns, slab polishing and brick making units. The quantity of AOD values in pre-monsoon is higher (low during post-monsoon) for wavelength, such as shortwave infrared (SWIR) or near infrared (NIR), which shows that coarse particles contribute more compare with the sub-micron particles. The composite aerosols near the surface follow suit with the share of the accumulation mode to the total mass concentration decreasing from approximately 70% to 30% from post-monsoon to pre-monsoon. Coarse mode particle loading observed to be high during pre-monsoon and accumulation mode particles observed to be high during post-monsoon. The backward trajectories at three representative altitudes with source point at the observing site indicate a possible transport from the outflow regions into Bay of Bengal, southern peninsular India and Arabian Sea. The temporal variations of AOD, Angstrom wavelength exponent and precipitable water content over Anantapur have also been compared with those reported from selected locations in India.

Mycobacterium tuberculosis WhiB3 responds to O2 and nitric oxide via its [4Fe-4S] cluster and is essential for nutrient starvation survival.

A fundamental challenge in the redox biology of Mycobacterium tuberculosis (Mtb) is to understand the mechanisms involved in sensing redox signals such as oxygen (O2), nitric oxide (NO), and nutrient depletion, which are thought to play a crucial role in persistence. Here we show that Mtb WhiB3 responds to the dormancy signals NO and O2 through its iron-sulfur (Fe-S) cluster. To functionally assemble the WhiB3 Fe-S cluster, we identified and characterized the Mtb cysteine desulfurase (IscS; Rv3025c) and developed a native enzymatic reconstitution system for assembling Fe-S clusters in Mtb. EPR and UV-visible spectroscopy analysis of reduced WhiB3 is consistent with a one-electron reduction of EPR silent [4Fe-4S]2+ to EPR visible [4Fe-4S]+. Atmospheric O2 gradually degrades the WhiB3 [4Fe-4S]2+ cluster to generate a [3Fe-4S]+ intermediate. Furthermore, EPR analysis demonstrates that NO forms a protein-bound dinitrosyl-iron-dithiol complex with the Fe-S cluster, indicating that NO specifically targets the WhiB3 Fe-S cluster. Our data suggest that the mechanism of WhiB3 4Fe-4S cluster degradation is similar to that of fumarate nitrate regulator. Importantly, Mtb DeltawhiB3 shows enhanced growth on acetate medium, but a growth defect on media containing glucose, pyruvate, succinate, or fumarate as the sole carbon source. Our results implicate WhiB3 in metabolic switching and in sensing the physiologically relevant host signaling molecules NO and O2 through its [4Fe-4S] cluster. Taken together, our results suggest that WhiB3 is an intracellular redox sensor that integrates environmental redox signals with core intermediary metabolism.

Phenanthroline-polyoxometalate hybrid compounds and the observation of intramolecular charge transfer.

A phenanthroline ligand has been covalently modified at the 2 and 9 positions by an aminophenylhexamolybdate substituent. The 1H NMR spectrum indicated a strong electron-withdrawing effect of the hexamolybdate (Mo6O19(2-)) moiety on the phenanthroline ligand. UV-vis and cyclic voltammetry showed extended conjugation of the hybrid phenanthroline-polyoxometalate compound and the possibility of easy oxidation of the extended phenanathroline ligand. Further EPR experiments provided strong evidence for an intramolecular charge-transfer process with the formation of a phenanthroline cation radical and a reduced hexamolybdate.

EPR, optical and infrared absorption studies of Mn2+ ions doped in zinc malate trihydrate single crystal.

Electron paramagnetic resonance (EPR) studies have been carried out on Mn2+ ions doped in zinc malate trihydrate single crystals in the temperature range 123-413 K on X-band frequency. The EPR spectrum at room temperature exhibits a group of five fine structure transitions each splits into six hyperfine components. Angular variation studies reveal that Mn2+ ions enter the lattice substitutionally. From the observed EPR spectrum, the spin-Hamiltonian parameters have been evaluated. The variation of zero-field splitting parameter (D) with temperature is measured. From the optical absorption spectrum, the crystal field splitting parameter Dq and the Racah interelectronic repulsion parameters B and C have been evaluated. The infrared spectrum exhibits bands characteristic of the carboxylic acid salts.

EPR and optical absorption studies on Cr3+ ions doped in KZnClSO4 x 3H2O single crystals.

EPR and optical absorption spectra of Cr3+ ions doped in KZnClSO4 x 3H2O single crystals have been studied at room temperature. The EPR spectrum exhibits a group of three fine structure transitions characteristic of Cr3+ ions. From the observed EPR spectra, the spin-Hamiltonian parameters have been determined. The optical absorption spectrum exhibits two broad bands characteristic of Cr3+ ions in an octahedral symmetry. From the observed band positions, the crystal field parameters have been evaluated.

Structural studies of the biomineralized species of calcified pancreatic stones in patients suffering from chronic pancreatitis.

The pancreatic stones (Pancreatic calculi) collected from patients suffering from chronic calcific pancreatitis were studied in a view to explore the constituents involved in the calcification. The calcified stones were characterized by XRD, EPR and IR spectroscopic techniques. The detailed studies indicate that these stones consist of calcium carbonate as a major component, besides phosphates and other protein content. The presence of aragonite phases in the biomineralized stones is also discussed. The EPR spectra gave an evidence of the presence of traces of manganese in different oxidation states, which is used as one of the EPR probes in the present work. The samples were sintered at different temperatures to remove all the organic matter, and their EPR spectra have been studied to obtain detailed information regarding the changes in the symmetry of these stone samples. The X-irradiated sample was also characterized by EPR and the resonance signals are attributed to freely rotating CO(2)(-) radicals. The infrared spectrum reveals the presence of many organic bands corresponding to the protein amides.

EPR, optical, infrared and Raman spectral studies of Actinolite mineral.

Electron paramagnetic resonance (EPR), optical, infrared and Raman spectral studies have been performed on a natural Actinolite mineral. The room temperature EPR spectrum reveals the presence of Mn(2+) and Fe(3+) ions giving rise to two resonance signals at g = 2.0 and 4.3, respectively. The resonance signal at g = 2.0 exhibits a six line hyperfine structure characteristic of Mn(2+) ions. EPR spectra have been studied at different temperatures from 123 to 433 K. The number of spins (N) participating in the resonance at g = 2.0 has been calculated at different temperatures. A linear relationship is observed between log N and 1/T in accordance with Boltzmann law and the activation energy was calculated. The paramagnetic susceptibility (chi) has been calculated at different temperatures and is found to be increasing with decreasing temperature as expected from Curie's law. From the graph of 1/chi versus T, the Curie constant and Curie temperature have been evaluated. The optical absorption spectrum exhibits bands characteristic of Fe(2+) and Fe(3+) ions. The crystal field parameter Dq and the Racah parameters B and C have been evaluated from the optical absorption spectrum. The infrared spectral studies reveal the formation of Fe(3+)--OH complexes due to the presence of higher amount of iron in this mineral. The Raman spectrum exhibits bands characteristic of Si--O--Si stretching and Mg?OH translation modes.

The microstructures of biomineralized surfaces: a spectroscopic study on the exoskeletons of fresh water (Apple) snail, Pila globosa.

In view of the importance in understanding biomineralization processes in different molluskan species, the common fresh water apple snail Pila globosa in Indian origin was taken to explore its mineralized exoskeleton structures. The detailed structural studies of the exoskeletons of P. globosa have been undertaken. The isolated layers present in these shells were studied by electron paramagnetic resonance (EPR), optical absorption, and infrared spectral techniques. The EPR spectra of the organic protein layer periostracum show the characteristic signals corresponding to Fe(3+) ions at g = 4.1 and 2.0. The EPR spectra of the ostracum (middle) layer at room temperature gives a complicated spectrum consisting of a number of Mn(2+) signals of at least three sets due to the aragonite nature of the material. The results indicate the presence of the multivalent manganese ions, which undergo the redox mechanisms. The thermal variation of the EPR spectra show marked effect on these samples both in g-values and the basic spectral pattern.

Structural studies of marine exoskeletons: redox mechanisms observed in the Cu-supported CaCO3 surfaces tudied by EPR.

Electron Paramagnetic Resonance (EPR), optical and infrared (IR) spectral studies have been performed on the pure and Cu-adsorbed exoskeletons of marine environment. The EPR spectrum of exoskeletons at room temperature exhibits a sharp signal at g approximately 1.9970. The possible redox mechanisms have been noticed on heating these exoskeletons in which the low spin Mn(3+) reduces to Mn(2+). The optical absorption spectra also give the evidence of the presence of Mn(3+) ions. The effects of thermal sintering on the EPR spectra have been studied and discussed in detail. The Cu-adsorbed samples clearly showed the adsorption of the Cu(2+) ions over CaCO(3) and the redox mechanism in these samples have been monitored by EPR.

EPR and IR spectral studies of the sea water mussel Mytilus conradinus shells.

The electron paramagnetic resonance (EPR) and infrared (IR) spectral studies have been employed on the periostracum, the prismatic layer and the nacre of the shell of the marine bivalve molluscan Mytilus conradinus of the South Indian origin. All the layers of this shell show Fe3+ ion spin resonance signals in common. The inner layer namely nacre at room temperature shows EPR signals of Fe3+ ions and the heated one exhibits a sextet hyperfine pattern characteristic of Mn2+ ions. The prismatic layer of the shell also exhibits a similar spectrum, but of distinct pattern. The spin-Hamiltonian parameters have been evaluated for the prismatic and nacreous layers of this shell. Infrared spectra of the two main layers of the shell namely prismatic and the nacre exhibit the characteristic bands of CO3(2-) molecular ion in different symmetries of CaCO3.