Liquid phase benzoylation of arenes over iron promoted sulphated zirconia

The present work undertakes the preparation and physico-chemical characterisation of iron promoted sulphated zirconia (SZ) with different amounts of iron loading and their application to Friedel–Crafts benzoylation of benzene, toluene and xylene under different experimental conditions. XRD and laser Raman techniques reveal the stabilisation of the tetragonal phase of zirconia and the existence of iron in highly dispersed form as Fe₂O₃ on the catalyst surface. The surface acidic properties were determined by ammonia temperature programmed desorption (TPD) and perylene adsorption. The results were supported by the TGA studies after adsorption of pyridine and 2,6-dimethylpyridine (2,6-DMP). Strong Lewis acid sites on the surface, which are evident from TPD and perylene adsorption studies, explain the high catalytic activity of the systems towards benzoylation. The experimental results provide evidence for the truly heterogeneous nature of the reaction. The studies also establish the resistance to deactivation in the metal incorporated sulphated systems.     

On the Mechanisms Governing Aluminum-Mediated Solid-Phase Epitaxy of Silicon

Mechanisms governing the aluminum-mediated solid-phase epitaxy of Si on patterned crystalline Si substrates have been identified by studying the deposited material as a function of growth conditions when varying parameters such as temperature, growth time, and layer-stack properties. Early growth stages can be discerned as first formation of “free” Si at the Al/α-Si interface, then diffusion of Si along the Al grain boundaries, nucleation at the Si substrate surface, nuclei rearrangement, and finally crystal growth. The acquired understanding is applied to control the selectivity and completeness of single-crystal growth in various sizes of contact windows to the Si substrate.     

Optimization of preparation conditions on the dielectric properties of polyaniline

The dielectric response in the microwave field of polyaniline prepared at different temperatures and using different inorganic and organic dopants was studied. Chemical oxidative polymerization of aniline was done at low temperature (0–5°C), at room temperature, and at high (60°C) temperature using different inorganic dopants like HCl, HNO₃, H₂SO₄, HClO₄, etc. Polyaniline was also prepared with different organic dopants like camphor sulfonic acid, Toluene sulfonic acid, and Naphthalene sulfonic acid. All polymers formed were characterized using IR, TGA, DSC, and SEM, etc. The dielectric responses of all polymers are studied using cavity perturbation technique in the microwave field. The studies indicates that the polyaniline prepared with perchloric acid at room temperature shows higher conductivity and absorption coefficient compared with all other samples. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Relative importance of the lift force on heavy particles due to turbulence driven secondary flows

Saffman lift forces on dense particles due to gradients in both streamwise and cross-stream velocities in a downward, fully developed turbulent square duct flow at Re_τ = 360 are studied using large eddy simulations. Volume fraction of the dispersed phase is low enough (≤ 10^− 5) that the one-way coupling approach is reasonable, i.e., two-way coupling and particle-particle collisions are not considered. Eulerian and Lagrangian approaches are used to treat the continuous and dispersed phases, respectively. Subgrid stresses are modeled with the dynamic subgrid kinetic energy model of Kim and Menon [W.W. Kim and S. Menon. Application of the localized dynamic subgrid-scale model to turbulent wall-bounded flows, AIAA 97-0210, 1997.]. The particle equation of motion includes drag, lift forces due to both the streamwise and cross-stream velocity gradients, gravity, and is integrated using the fourth-order accurate Runge-Kutta scheme. Dependence of particle drag and lift forces on duct cross-sectional location and particle response time is demonstrated using the mean value contours and probability density functions (PDFs) of particle forces. It is shown that the streamwise component of the mean drag force experienced by particles of all response times is a deceleration force, i.e. on average, fluid streamwise velocity lags the particle streamwise velocity. Secondly, the two wall-normal (or lateral) components of the mean drag force are oriented such that the particles experience a net mean force toward the duct corners. PDFs of particle drag force components show that smaller response time particles experience a wider range of drag force about the mean value, as compared to the more inertial particles. Contours of mean wall-normal lift forces due to streamwise velocity gradients show that this force predominantly acts toward the duct walls and that the maximum lift force occurs close to the walls. PDFs of lift force due to streamwise velocity gradients show that the range of fluctuations increases with particle response time, but the dependence on particle response time is weaker compared to drag force. Lift forces due to cross-stream velocity gradients are at least an order of magnitude smaller than lift forces due to streamwise velocity gradients and are found to decrease in their range of fluctuations with particle response time. It is demonstrated that lift forces due to secondary flow velocity gradients are not as important as those due to streamwise velocity gradients in a square duct flow.     

Essential Oil of <Emphasis Type="Italic">Artemisia scoparia</Emphasis> Inhibits Plant Growth by Generating Reactive Oxygen Species and Causing Oxidative Damage

We investigated the chemical composition and phytotoxicity of the essential oil extracted from leaves of Artemisia scoparia Waldst. et Kit. (red stem wormwood, Asteraceae). GC/GC-MS analyses revealed 33 chemical constituents representing 99.83% of the oil. The oil, in general, was rich in monoterpenes that constitute 71.6%, with β-myrcene (29.27%) as the major constituent followed by (+)-limonene (13.3%), (Z)-β-ocimene (13.37%), and γ-terpinene (9.51%). The oil and β-myrcene were evaluated in a dose–response bioassay under laboratory conditions for phytotoxicity against three weeds—Avena fatua, Cyperus rotundus, and Phalaris minor. A significant reduction in germination, seedling growth, and dry matter accumulation was observed in the test weeds. At the lowest treatment of 0.07 mg/ml Artemisia oil, germination was reduced by 39%, 19%, and 10.6% in C. rotundus, P. minor, and A. fatua, respectively. However, the inhibitory effect of β-myrcene was less. In general, a dose-dependent effect was observed and the growth declined with increasing concentration. Among the three weeds, the inhibitory effect was greatest on C. rotundus, so it was selected for further studies. We explored the explanation for observed growth inhibition in terms of reactive oxygen species (ROS: lipid peroxidation, membrane integrity, and amounts of conjugated dienes and hydrogen peroxide)-induced oxidative stress. Exposure of C. rotundus to Artemisia oil or β-myrcene enhanced solute leakage, indicating membrane disintegration. There were increased levels of malondialdehyde and hydrogen peroxide, indicating lipid peroxidation and induction of oxidative stress. We conclude that Artemisia oil inhibits plant root growth through generation of ROS-induced oxidative damage.     

Evaluation of oxidative stress biomarkers in hepatocytes of grey mullet inhabiting natural and polluted estuaries

The aim of the study was to evaluate the impact of environmental contaminants on oxidative stress biomarkers in hepatocytes of Indian estuarine water grey mullet, Mugil cephalus collected from unpolluted Kovalam and polluted Ennore estuaries. Initially, a comparison was made between the general water chemistry and environmental pollutants like heavy metals to identify the ecotype of the estuaries. Biomarker responses and bioaccumulation of metals were determined along with histological studies of fish hepatocytes to assess contamination impact. Water chemistry data with higher temperature, salinity, pH, biochemical oxygen demand, chemical oxygen demand and low dissolved oxygen and environmental pollutants with higher metal concentration (p < 0.05) were observed at Ennore than Kovalam indicating its polluted environment. A significant increase (p < 0.05) in lipid and protein oxidation markers, decrease (p < 0.05) in thiol status and antioxidant enzyme activities were observed in the Ennore fish hepatocytes compared to Kovalam counterpart. Bioaccumulation of heavy metals was significantly higher (p < 0.05) in fish from Ennore. Hepatocytes from Ennore also featured extensive lipid-type vacuolation, increased size and membrane disruption. All the findings highlighted the value of oxidative stress biomarkers and membrane disruption as the sensitive parameters of environmental pollutant contamination and their importance in biomonitoring of aquatic ecosystems. This is also the first such attempt reported at the cellular level from South India stressing the importance of biomarkers in biomonitoring programmes using fish hepatocytes as the model system.     

Defluoridation of groundwater using brick powder as an adsorbent

Defluoridation of groundwater using brick powder as an adsorbent was studied in batch process. Different parameters of adsorption, viz. effect of pH, effect of dose and contact time were selected and optimized for the study. Feasible optimum conditions were applied to two groundwater samples of high fluoride concentration to study the suitability of adsorbent in field conditions. Comparison of adsorption by brick powder was made with adsorption by commercially available activated charcoal. In the optimum condition of pH and dose of adsorbents, the percentage defluoridation from synthetic sample, increased from 29.8 to 54.4% for brick powder and from 47.6 to 80.4% for commercially available activated charcoal with increasing the contact time starting from 15 to 120 min. Fluoride removal was found to be 48.73 and 56.4% from groundwater samples having 3.14 and 1.21 mg l(-1) fluoride, respectively, under the optimized conditions. Presence of other ions in samples did not significantly affect the deflouridation efficiency of brick powder. The optimum pH range for brick powder was found to be 6.0-8.0 and adsorption equilibrium was found to be 60 min. These conditions make it very suitable for use in drinking water treatment. Deflouridation capacity of brick powder can be explained on the basis of the chemical interaction of fluoride with the metal oxides under suitable pH conditions. The adsorption process was found to follow first order rate mechanism as well as Freundlich isotherm.     

Heavy metal accumulation in vegetables irrigated with water from different sources

The present study was carried out to assess levels of different heavy metals like iron, manganese, copper and zinc, in vegetables irrigated with water from different sources. The results indicated a substantial build-up of heavy metals in vegetables irrigated with wastewater. The range of various metals in wastewater-irrigated plants was 116–378, 12–69, 5.2–16.8 and 22–46 mg/kg for iron (Fe), manganese (Mn), copper (Cu) and zinc (Zn), respectively. The highest mean levels of Fe and Mn were detected in mint and spinach, whereas the levels of Cu and Zn were highest in carrot. The present study highlights that both adults and children consuming vegetables grown in wastewater-irrigated soils ingest significant amount of these metals. However, the values of these metals were below the recommended maximum tolerable levels proposed by the [Joint FAO/WHO Expert Committee on Food Additives (1999). Summary and conclusions. In 53rd Meeting, Rome, June 1–10, 1999]. However, the regular monitoring of levels of these metals from effluents and sewage, in vegetables and in other food materials is essential to prevent excessive build-up of these metals in the food chain.