Photocatalytic degradation of dimethoate using LbL fabricated TiO2/polymer hybrid films

Degradation of dimethoate under UV irradiation using TiO2/polymer films prepared by the layer-by-layer (LbL) method was investigated. The thin films were fabricated on glass slides and the surface morphology and roughness of the thin films were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The effect of lamp intensity, catalyst loading in the layers, number of bilayers, pH and initial dimethoate concentration on the degradation of dimethoate was systematically studied. The degradation was monitored using high performance liquid chromatography (HPLC) analysis and total organic carbon (TOC) measurements as a function of irradiation time, to see the change in concentration of dimethoate and mineralization, respectively. Complete degradation of dimethoate was achieved under TiO2 optimum loading of 4 g/L at an UV irradiation time of 180 min. Increase in the lamp intensity, catalyst loading and number of bilayers increased the rate of degradation. At a pH of 4.62, complete degradation of dimethoate was observed. The degradation efficiency decreased with increase in initial dimethoate concentration. The degradation byproducts were analyzed and confirmed by gas chromatography-mass spectra (GC-MS). Toxicity of the irradiated samples was measured using the luminescence of bacteria Vibrio fischeri after 30 min of incubation and the results showed more toxicity than the parent compound. Catalyst reusability studies revealed that the fabricated thin films could be repeatedly used for up to ten times without affecting the photocatalytic activity of the films. The findings of the present study are very useful for the treatment of wastewaters contaminated with pesticides. (C) 2011 Elsevier B.V. All rights reserved.

Carbon nanotube mat as substrate for ZnO nanotip field emitters

We have reported the synthesis of ZnO nanotips on a multi walled carbon nanotube (MWCNT) mat by a vapour transport process. This combination of ZnO nanotips and a MWCNT mat exhibit ideal field emission behaviour. The turn on field and threshold field is found to be 0.34 and 1.5 V mu m(-1), respectively. The low threshold field is due to the good adherence of the ZnO nanotips on the MWCNT mat. The field enhancement factor is found to be 5 x 10(2) which is in agreement with the intrinsic field emission factor of ZnO nanotips. The emission current is found to be highly stable even at moderate vacuum.

Lipopeptides from the Banyan Endophyte, Bacillus subtilis K1: Mass Spectrometric Characterization of a Library of Fengycins

Mass spectrometric analysis of a banyan endophyte, Bacillus subtilis K1, extract showing broad spectrum antifungal activity revealed a complex mixture of lipopeptides, iturins, surfactins, and fengycins. Fractionation by reversed-phase high performance liquid chromatography (HPLC) facilitated a detailed analysis of fengycin microheterogeneity. Matrix assisted laser desorption ionization (MALDI) and electrospray ionization (ESI) mass spectrometric studies permitted the identification of several new fengycin variants. Four major sites of heterogeneity are identified: (1) N-terminus beta-hydroxy fatty acid moiety, where chain length variation and the presence of unsaturation occur, (2) position 6 (Ala/Val/Ile/Leu), (3) position 10 (Val/Ile) within the macrocyclic ring, and (4) Gln to Glu replacement at position 8, resulting in fengycin variants that differ in mass by 1 Da. Diagnostic fragment ions provide a quick method for localizing the sites of variation in the macrocycle or the linear segment. Subsequent establishment of the sequences is achieved by MS/MS analysis of linear fengycin species produced by hydrolysis of the macrocyclic lactone. Unsaturation in the fatty acid chain and the presence of linear precursors in the B. subtilis K1 extract are also established by mass spectrometry. The anomalous distribution of intensities within isotopic multiplets is a diagnostic for Gln/Glu replacements. High resolution mass spectrometry facilitates the identification of fengycin species differing by 1 Da by localizing the variable position (Gln(8)/Glu(8)) in the fengycin variants.

Uninterrupted and reusable source for the controlled growth of nanowires

Generally, the length of the oxide nanowires grown by vapor phase transport is limited by the degradation of the source materials. Furthermore, the source material is used once for the nanowires growth. By exploiting the Si-Zn phase diagram, we have developed a simple methodology for the non-catalytic growth of ultralong ZnO nanowires in large area with controllable aspect ratio and branched structures. The insolubility of Zn in Si and the use of a Si cap on the Zn source to prevent local source oxidation of Zn (i.e. prevents the degradation of the source) are the keys to grow longer nanowires without limitations. It has been shown that the aspect ratio can be controlled by thermodynamically (temperature) and more importantly by kinetically (vapor flux). One of the interesting findings is that the same source material can be used for several depositions of oxide nanostructured materials.

Doping by diffusion of dopants from the substrate: synthesis of doped ZnO nanowires

We report on the substrate assisted doping of ZnO nanowires grown by a vapor transport technique. The nanowires were grown non-catalytically on multiwalled carbon nanotubes (MWCNTs) and soda lime glass (SLG). Carbon from MWCNTs and sodium from SLG diffuse into ZnO during the growth and are distributed uniformly and provide doping. An advantage associated with the technique is that no conventional external dopant source is required to obtain doped ZnO nanowires. The diameter, length and hence the aspect ratio can easily be varied by changing the growth conditions. The transport studies on both carbon and sodium doped ZnO support the p-type nature of ZnO. The p-type nature of carbon doped ZnO is stable for at least eight months.

Annihilation of vortex dipoles in an oblate Bose-Einstein condensate

We theoretically explore the annihilation of vortex dipoles, generated when an obstacle moves through an oblate Bose-Einstein condensate, and examine the energetics of the annihilation event. We show that the grey soliton, which results from the vortex dipole annihilation, is lower in energy than the vortex dipole. We also investigate the annihilation events numerically and observe that annihilation occurs only when the vortex dipole overtakes the obstacle and comes closer than the coherence length. Furthermore, we find that noise reduces the probability of annihilation events. This may explain the lack of annihilation events in experimental realizations.

Carbon nanotube-ZnO nanowire hybrid architectures as multifunctional devices

We report on multifunctional devices based on CNT arrays-ZnO nanowires hybrid architectures. The hybrid structure exhibit excellent high current Schottky like behavior with ZnO as p-type and an ideality factor close to the ideal value. Further the CNT-ZnO hybrid structures can be used as high current p-type field effect transistors that can deliver currents of the order of milliamperes and also can be used as ultraviolet detectors with controllable current on-off ratio and response time. The p-type nature of ZnO and possible mechanism for the rectifying characteristics of CNT-ZnO has been presented.

Ultralong ZnO nanowires: problems and prospects

ZnO is a unique material with numerous applications. There has been great interest in the synthesis of long nanowires to explore new technology coupled with length. But the quest to enhance the length is limited by various experimental shortcomings such as catalytic poisoning, degradation of the precursors and growth in all possible directions. This review article focuses on the growth of ultralong ZnO nanowires along with possible methodologies to overcome these limitations.

Polyvinylidene fluoride film based nasal sensor to monitor human respiration pattern: An initial clinical study

Design and development of a piezoelectric polyvinylidene fluoride (PVDF) thin film based nasal sensor to monitor human respiration pattern (RP) from each nostril simultaneously is presented in this paper. Thin film based PVDF nasal sensor is designed in a cantilever beam configuration. Two cantilevers are mounted on a spectacle frame in such a way that the air flow from each nostril impinges on this sensor causing bending of the cantilever beams. Voltage signal produced due to air flow induced dynamic piezoelectric effect produce a respective RP. A group of 23 healthy awake human subjects are studied. The RP in terms of respiratory rate (RR) and Respiratory air-flow changes/alterations obtained from the developed PVDF nasal sensor are compared with RP obtained from respiratory inductance plethysmograph (RIP) device. The mean RR of the developed nasal sensor (19.65 +/- A 4.1) and the RIP (19.57 +/- A 4.1) are found to be almost same (difference not significant, p > 0.05) with the correlation coefficient 0.96, p < 0.0001. It was observed that any change/alterations in the pattern of RIP is followed by same amount of change/alterations in the pattern of PVDF nasal sensor with k = 0.815 indicating strong agreement between the PVDF nasal sensor and RIP respiratory air-flow pattern. The developed sensor is simple in design, non-invasive, patient friendly and hence shows promising routine clinical usage. The preliminary result shows that this new method can have various applications in respiratory monitoring and diagnosis.

Analysis of 20alpha-hydroxysteroid dehydrogenase expression in the corpus luteum of the buffalo cow: effect of prostaglandin F2-alpha treatment on circulating 20alpha-hydroxyprogesterone levels

Background: During female reproductive cycles, a rapid fall in circulating progesterone (P4) levels is one of the earliest events that occur during induced luteolysis in mammals. In rodents, it is well recognized that during luteolysis, P4 is catabolized to its inactive metabolite, 20alpha-hydroxyprogesterone (20alpha-OHP) by the action of 20alpha-hydroxysteroid dehydrogenase (20alpha-HSD) enzyme and involves transcription factor, Nur77. Studies have been carried out to examine expression of 20alpha-HSD and its activity in the corpus luteum (CL) of buffalo cow. Methods: The expression of 20alpha-HSD across different bovine tissues along with CL was examined by qPCR analysis. Circulating P4 levels were monitored before and during PGF2alpha treatment. Expression of 20alpha-HSD and Nur77 mRNA was determined in CL at different time points post PGF2alpha treatment in buffalo cows. The chromatographic separation of P4 and its metabolite, 20alpha-OHP, in rat and buffalo cow serum samples were performed on reverse phase HPLC system. To further support the findings, 20alpha-HSD enzyme activity was quantitated in cytosolic fraction of CL of both rat and buffalo cow. Results: Circulating P4 concentration declined rapidly in response to PGF2alpha treatment. HPLC analysis of serum samples did not reveal changes in circulating 20alpha-OHP levels in buffalo cows but serum from pseudo pregnant rats receiving PGF2alpha treatment showed an increased 20alpha-OHP level at 24 h post treatment with accompanying decrease in P4 concentration. qPCR expression of 20alpha-HSD in CL from control and PGF2alpha-treated buffalo cows showed higher expression at 3 and 18 h post treatment, but its specific activity was not altered at different time points post PGF2alpha treatment. The Nur77 expression increased several fold 3 h post PGF2alpha treatment similar to the increased expression observed in the PGF2alpha-treated pseudo pregnant rats which perhaps suggest initiation of activation of apoptotic pathways in response to PGF2alpha treatment. Conclusions: The results taken together suggest that synthesis of P4 appears to be primarily affected by PGF2alpha treatment in buffalo cows in contrast to increased metabolism of P4 in rodents.

Rapid determination of main constituents of packed juices by reverse phase-high performance liquid chromatography: an insight in to commercial fruit drinks

The present work reports the compositional analysis of thirteen different packed fruit juices using high performance liquid chromatography (HPLC). Vitamin C, organic acids (citric and malic) and sugars (fructose, glucose and sucrose) were separated, analyzed and quantified using different reverse phase methods. A new rapid reverse phase HPLC method was developed for routine analysis of vitamin C in fruit juices. The precision results of the methods showed that the relative standard deviations of the repeatability and reproducibility were < 0.05 and < 0.1 respectively. Correlation coefficient of the calibration models developed was found to be higher than 0.99 in each case. It has been found that the content of Vitamin C was less variable amongst different varieties involved in the study. It is also observed that in comparison to fresh juices, the packed juices contain lesser amounts of vitamin C. Citric acid was found as the major organic acids present in packed juices while maximum portion of sugars was of sucrose. Comparison of the amount of vitamin C, organic acids and sugars in same fruit juice of different commercial brands is also reported.

Multistage effect in enhancing the field emission behaviour of ZnO branched nanostructures

We report the synthesis of branched ZnO nanostructures by vapour phase transport and their multistage effect in enhancing the field emission behaviour. First, the ZnO nanowires (first generation) are grown and second generation nanowires are grown on first one and so on to obtain the branched structures. The number of branches increases and the diameter of the branches decreases till the third generation nanowires. Fourth generation onwards, dense branched structures are obtained eventually yielding nanoforest-like morphology. The field emission behaviour is found to improve till the third generation and is assigned to smaller diameter of the branches. (C) 2014 AIP Publishing LLC.

Local spatial structure of forest biomass and its consequences for remote sensing of carbon stocks

Advances in forest carbon mapping have the potential to greatly reduce uncertainties in the global carbon budget and to facilitate effective emissions mitigation strategies such as REDD+ (Reducing Emissions from Deforestation and Forest Degradation). Though broad-scale mapping is based primarily on remote sensing data, the accuracy of resulting forest carbon stock estimates depends critically on the quality of field measurements and calibration procedures. The mismatch in spatial scales between field inventory plots and larger pixels of current and planned remote sensing products for forest biomass mapping is of particular concern, as it has the potential to introduce errors, especially if forest biomass shows strong local spatial variation. Here, we used 30 large (8-50 ha) globally distributed permanent forest plots to quantify the spatial variability in aboveground biomass density (AGBD in Mgha(-1)) at spatial scales ranging from 5 to 250m (0.025-6.25 ha), and to evaluate the implications of this variability for calibrating remote sensing products using simulated remote sensing footprints. We found that local spatial variability in AGBD is large for standard plot sizes, averaging 46.3% for replicate 0.1 ha subplots within a single large plot, and 16.6% for 1 ha subplots. AGBD showed weak spatial autocorrelation at distances of 20-400 m, with autocorrelation higher in sites with higher topographic variability and statistically significant in half of the sites. We further show that when field calibration plots are smaller than the remote sensing pixels, the high local spatial variability in AGBD leads to a substantial ``dilution'' bias in calibration parameters, a bias that cannot be removed with standard statistical methods. Our results suggest that topography should be explicitly accounted for in future sampling strategies and that much care must be taken in designing calibration schemes if remote sensing of forest carbon is to achieve its promise.

Anticancer Effects of Brominated Indole Alkaloid Eudistomin H from Marine Ascidian Eudistoma viride Against Cervical Cancer Cells (HeLa)

Marine invertebrates called ascidians are prolific producers of bioactive substances. The ascidian Eudistoma viride, distributed along the Southeast coast of India, was investigated for its in vitro cytotoxic activity against human cervical carcinoma (HeLa) cells by the MTT assay. The crude methanolic extract of E. viride, with an IC50 of 53 mu g/ml, was dose-dependently cytotoxic. It was more potent at 100 mu g/ml than cyclohexamide (1 mu g/ml), reducing cell viability to 9.2%. Among nine fractions separated by chromatography, ECF-8 exhibited prominent cytoxic activity at 10 mu g/ml. The HPLC fraction EHF-21 of ECF-8 was remarkably dose- and time-dependently cytotoxic, with 39.8% viable cells at 1 mu g/ml compared to 51% in cyclohexamide-treated cells at the same concentration; the IC50 was 0.49,mu g/ml. Hoechst staining of HeLa cells treated with EHF-2I at 0.5 mu g/ml revealed apoptotic events such an cell shrinkage, membrane blebbing, chromatin condensation and formation of apoptotic bodies. Cell size and granularity study showed changes in light scatter, indicating the characteristic feature of cells dying by apoptosis. The cell-cycle analysis of HeLa cells treated with fraction EHF-21 at 1 mu g/ml showed the marked arrest of cells in G(0)/G(1), S and G(2)/M phases and an increase in the sub G(0)/G(1) population indicated an increase in the apoptotic cell population. The statistical analysis of the sub-G(1) region showed a dose-dependent induction of apoptosis. DNA fragmentation was also observed in HeLa cells treated with EHF-21. The active EHF-2I fraction, a brominated indole alkaloid Eudistomin H, led to apoptotic death of HeLa cells.

Cryogenian magmatism and crustal reworking in the Southern Granulite Terrane, India

Understanding Neoproterozoic crustal evolution is fundamental to reconstructing the Gondwana supercontinent, which was assembled at this time. Here we report evidence of Cryogenian crustal reworking in the Madurai Block of the Southern Granulite Terrane of India. The study focuses on a garnet-bearing granite-charnockite suite, where the granite shows in situ dehydration into patches and veins of incipient charnockite along the contact with charnockite. The granite also carries dismembered layers of Mg-Al-rich granulite. Micro-textural evidence for dehydration of granite in the presence of CO2-rich fluids includes the formation of orthopyroxene by the breakdown of biotite, neoblastic zircon growth in the dehydration zone, at around 870 degrees C and 8kbar. The zircon U-Pb ages suggest formation of the granite, charnockite, and incipient charnockite at 836 +/- 73, 831 +/- 31, and 772 +/- 49Ma, respectively. Negative zircon epsilon Hf (t) (-5 to -20) values suggest that these rocks were derived from a reworked Palaeoproterozoic crustal source. Zircon grains in the Mg-Al-rich granulite record a spectrum of ages from ca. 2300 to ca. 500Ma, suggesting multiple provenances ranging from Palaeoproterozoic to mid-Neoproterozoic, with neoblastic zircon growth during high-temperature metamorphism in the Cambrian. We propose that the garnet-bearing granite and charnockite reflect the crustal reworking of aluminous crustal material indicated by the presence of biotite+quartz+aluminosilicate inclusions in the garnet within the granite. This crustal source can be the Mg-Al-rich layers carried by the granite itself, which later experienced high-temperature regional metamorphism at ca. 550Ma. Our model also envisages that the CO2 which dehydrated the garnet-bearing granite generating incipient charnockite was sourced from the proximal massive charnockite through advection. These Cryogenian crustal reworking events are related to prolonged tectonic activities prior to the final assembly of the Gondwana supercontinent.