OFFLINE AND ONLINE SOLID PHASE EXTRACTION/PRECONCENTRATION OF INORGANICS

Solid phase extraction (SPE) is a powerful technique for preconcentration/removal or separation of trace and ultra trace amounts of toxic and nutrient elements. SPE effectively simplifies the labour intensive sample preparation, increase its reliability and eliminate the clean up step by using more selective extraction procedures. The synthesis of sorbents with a simplified procedure and diminution of the risks of errors shows the interest in the areas of environmental monitoring, geochemical exploration, food, agricultural, pharmaceutical, biochemical industry and high purity metal designing, etc. There is no universal SPE method because the sample pretreatment depends strongly on the analytical demand. But there is always an increasing demand for more sensitive, selective, rapid and reliable analytical procedures. Among the various materials, chelate modified naphthalene, activated carbon and chelate functionalized highly cross linked polymers are most important. In the biological and environmental field, large numbers of samples are to be analysed within a short span of time. Hence, online flow injection methods are preferred as they allow extraction, separation, identification and quantification of many numbers of analytes. The flow injection online preconcentration flame AAS procedure developed allows the determination of as low as 0.1 µg/l of nickel in soil and cobalt in human hair samples. The developed procedure is precise and rapid and allows the analysis of 30 samples per hour with a loading time of 60 s. The online FI manifold used in the present study permits high sampling, loading rates and thus resulting in higher preconcentration/enrichment factors of -725 and 600 for cobalt and nickel respectively with a 1 min preconcentration time compared to conventional FAAS signal. These enrichment factors are far superior to hitherto developed on line preconcentration procedures for inorganics. The instrumentation adopted in the present study allows much simpler equipment and low maintenance costs compared to costlier ICP-AES or ICP-MS instruments.

Raman spectra of polymethyl methacrylate optical fibres excited by a 532 nm diode pumped solid state laser

Polymethyl methacrylate (PMMA) optical fibres are fabricated by a preform drawing process. The Raman spectra of PMMA fibres are recorded using a diode pumped solid state laser emitting at 532 nm and a CCD-spectrograph in the 400–3800 cm−1 range. The variation of the Raman intensity with the length of the optical fibre is studied. Investigations are carried out on the variation of FWHM of the Raman peak at 2957 cm−1 with the length of the optical fibre and pump power. The differential scattering cross section and gain coefficient of the Raman peak at 2957 cm−1 in PMMA are calculated in relation to that of toluene.

Raman spectra of polymethyl methacrylate optical fibres excited by a 532 nm diode pumped solid state laser

Polymethyl methacrylate (PMMA) optical fibres are fabricated by a preform drawing process. The Raman spectra of PMMA fibres are recorded using a diode pumped solid state laser emitting at 532 nm and a CCD-spectrograph in the 400–3800 cm−1 range. The variation of the Raman intensity with the length of the optical fibre is studied. Investigations are carried out on the variation of FWHM of the Raman peak at 2957 cm−1 with the length of the optical fibre and pump power. The differential scattering cross section and gain coefficient of the Raman peak at 2957 cm−1 in PMMA are calculated in relation to that of toluene

Characterization and Imaging Diagnostics of Laser Induced Plasma from Solid Targets

Laser induced plasma (LIP) emissions from some metal oxide targets were studied with corresponding metal targets of pure quality as a reference. Atomic emissions in the visible region were used in the spectroscopic procedures of LIP characterization. The studies were meant to throw light into LIP dynamics and they provided many experimental results which improved the general awareness of plasma state.When target materials were photo-ablated with an energetically suitable laser pulse, they developed electric charges in them.An electrical signal which was delivered from the target served as an alternative probe signal for the diagnostics of LIP and to track different charged states in the plasma. The signal showed a double peak distribution with positive polarity and a modified time of flight with various voltage levels of a given polarity.The expansion dynamics of LIP in magnetic field were also investigated by monitoring the voltage transients generated at the target.

Solid acid-catalyzed dehydration/Beckmann rearrangement of aldoximes: towards high atom efficiency green processes

Rare earth metal ion exchanged (La3+, Ce3+, RE3+) KFAU-Y zeolites were prepared by simple ion-exchange methods and have been characterized using different physico-chemical techniques. In this paper a novel application of solid acid catalysts in the dehydration/ Beckmann rearrangement of aldoximes; benzaldoxime and 4-methoxybenzaldoxime is reported. Dehydration/Beckmann rearrangement reactions of benzaldoxime and 4-methoxybenzaldoxime is carried out in a continuous down flow reactor at 473K. 4-Methoxybenzaldoxime gave both Beckmann rearrangement product (4-methoxyphenylformamide) and dehydration product (4-methoxybenzonitrile) in high overall yields. The difference in behavior of the aldoximes is explained in terms of electronic effects. The production of benzonitrile was near quantitative under heterogeneous reaction conditions. The optimal protocol allows nitriles to be synthesized in good yields through the dehydration of aldoximes. Time on stream studies show a fast decline in the activity of the catalyst due to neutralization of acid sites by the basic reactant and product molecules.

Synthesis of dimethyl acetal of ketones: design of solid acid catalysts for one-pot acetalization reaction

The synthesis of dimethyl acetals of carbonyl compounds such as cyclohexanone, acetophenone, and benzophenone has successfully been carried out by the reaction between ketones and methanol using different solid acid catalysts. The strong influence of the textural properties of the catalysts such as acid amount and adsorption properties (surface area and pore volume) determine the catalytic activity. The molecular size of the reactants and products determine the acetalization ability of a particular ketone. The hydrophobicity of the various rare earth exchanged Mg–Y zeolites, K-10 montmorillonite clay, and cerium exchanged montmorillonite (which shows maximum activity) is more determinant than the number of active sites present on the catalyst. The optimum number of acidic sites as well as dehydrating ability of Ce3+-montmorillonite and K-10 montmorillonite clays and various rare earth exchanged Mg–Y zeolites seem to work well in shifting the equilibrium to the product side.

Sulfated titania mediated regioselective nitration of phenol in solid state

Titania, sulfated titania and chromium loaded sulfated titania were prepared by sol–gel method and characterized using different technique. Phenol is nitrated regioselectively by nitric acid using chromium loaded sulfated titania catalysts. A remarkable ortho selectivity is observed in solid state nitration to yield exclusively ortho-nitrophenol. Compared to the conventional process, phenol nitration over solid acid catalyst is a clean and environment friendly process. Catalytic activity well correlates with the Brönsted acid sites of these catalysts.

Production of Alkaline Protease by Free and Immobilised Cells of VIBRIO sp. Under Different Fermentation Systems and Its Application on Deproteinisation of Prawn Shell Waste for Chitin Recovery

This thesis presents a detailed account of a cost - effective approach towards enhanced production of alkaline protease at profitable levels using different fermentation designs employing cheap agro-industrial residues. It involves the optimisation of process parameters for the production of a thermostable alkaline protease by Vibrio sp. V26 under solid state, submerged and biphasic fermentations, production of the enzyme using cell immobilisation technology and the application of the crude enzyme on the deproteinisation of crustacean waste.The present investigation suggests an economic move towards Improved production of alkaline protease at gainful altitudes employing different fermentation designs utilising inexpensive agro-industrial residues. Moreover, the use of agro-industrial and other solid waste substrates for fermentation helps to provide a substitute in conserving the already dwindling global energy resources. Another alternative for accomplishing economically feasible production is by the use of immobilisation technique. This method avoids the wasteful expense of continually growing microorganisms. The high protease producing potential of the organism under study ascertains their exploitation in the utilisation and management of wastes. However, strain improvement studies for the production of high yielding variants using mutagens or by gene transfer are required before recommending them to Industries.Industries, all over the world, have made several attempts to exploit the microbial diversity of this planet. For sustainable development, it is essential to discover, develop and defend this natural prosperity. The Industrial development of any country is critically dependent on the intellectual and financial investment in this area. The need of the hour is to harness the beneficial uses of microbes for maximum utilisation of natural resources and technological yields. Owing to the multitude of applications in a variety of industrial sectors, there has always been an increasing demand for novel producers and resources of alkaline proteases as well as for innovative methods of production at a commercial altitude. This investigation forms a humble endeavour towards this perspective and bequeaths hope and inspiration for inventions to follow.

Structural tuning of Montmorillonite clays by pillaring: Designing of shape selective solid acid catalysts and PANI - Montmorillonite nanocomposites

Green chemistry boots eco-friendly,natural clays as catalysts in the chemical as well as in the pharmaceutical industry.Industry demands thermal stability,mechanical strength etc for the catalyst and there the modification methods becomes important.Pillaring tunes clays as efficient catalytic templates for shape selective organic synthesis.Here pillared clays are used as promising alternatives for the environmentally hazardous homogeneous catalysts in some industrially important Friedel-Crafts alkylation reactions of arenes with lower alchohols and higher olefins.The layer structure is enhanced upon pillaring and allows the nanocomposite formation with polyaniline to develop today’s nanoscale diameter devices.Present work gives an entry of pillared clays to the world of conducting composite nanofibers.

Application of Imaging to Study the Evolution and Dynamics of Laser Produced Plasma from Solid and Thin Film Li Targets

The present thesis report the results obtained from the studies carried out on the laser blow off plasma (LBO) from LiF-C (Lithium Fluoride with Carbon) thin film target, which is of particular importance in Tokamak plasma diagnostics. Keeping in view of its significance, plasma generated by the irradiation of thin film target by nanosecond laser pulses from an Nd:YAG laser over the thin film target has been characterized by fast photography using intensified CCD. In comparison to other diagnostic techniques, imaging studies provide better understanding of plasma geometry (size, shape, divergence etc) and structural formations inside the plume during different stages of expansion.