9 resultados para Photochemistry reactor

em Cochin University of Science


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School of environmental studies, Cochin University of Science and Technology

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Invertase was immobilized on acid activated montmorillonite via two independent procedures, adsorption and covalent binding. The immobilized enzymes were characterized by XRD, NMR and N2 adsorption measurements and their activity was tested in a fixed bed reactor. XRD revealed that the enzyme was situated on the periphery of the clay and the side chains of different amino acid residues were involved in intercalation with the clay matrix. NMR demonstrated that tetrahedral Al was linked to the enzyme during adsorption and the octahedral Al was involved during covalent binding. Secondary interaction of the enzyme with Al was also observed. N2 adsorption studies showed that covalent binding of enzymes caused pore blockage since the highly polymeric species were located at the pore entrance. The fixed bed reactor proved to be efficient for the immobilized invertase. The optimum pH and pH stability improved upon immobilization. The kinetic parameters calculated also showed an enhanced efficiency of the immobilized systems. They could be used continuously for long period. Covalently bound invertase demonstrated greater operational stability.

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Glucoamylase from Aspergillus Niger was immobilized on montmorillonite clay (K-10) by two procedures, adsorption and covalent binding. The immobilized enzymes were characterized using XRD, surface area measurements and 27Al MAS NMR and the activity of the immobilized enzymes for starch hydrolysis was tested in a fixed bed reactor (FBR). XRD shows that enzyme intercalates into the inter-lamellar space of the clay matrix with a layer expansion up to 2.25 nm. Covalently bound glucoamylase demonstrates a sharp decrease in surface area and pore volume that suggests binding of the enzyme at the pore entrance. NMR studies reveal the involvement of octahedral and tetrahedral Al during immobilization. The performance characteristics in FBR were evaluated. Effectiveness factor (η) for FBR is greater than unity demonstrating that activity of enzyme is more than that of the free enzyme. The Michaelis constant (Km) for covalently bound glucoamylase was lower than that for free enzyme, i.e., the affinity for substrate improves upon immobilization. This shows that diffusional effects are completely eliminated in the FBR. Both immobilized systems showed almost 100% initial activity after 96 h of continuous operation. Covalent binding demonstrated better operational stability.

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Faculty of Engineering. Cochin University of Science and Technology

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National Centre for Aquatic Animal Health, Cochin University of Science and Technology

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The thesis entitled: ‘Synthesis and Photochemistry of a few Olefin appended Dibenzobarrelenes and Bisdibenzobarrelenes’ is divided into 5 chapters.In Chapter 1, the fundamental concepts of Diels-Alder reaction, di-r:methane rearrangement and energy transfer process in organic photochemistry is discussed.Chapter 2 presents the synthesis of 9-olefin appended anthracenes and bisanthracenes. The target of synthesising various bridgehead olefin appended dibenzobarrelenes and some novel bisdibenzobarrelenes, led us to the synthesis of the appropriate alkenylanthracenes and bisanthracenes as precursor molecules. Diels-Alder reaction was the synthetic tool for the preparation of the target olefin appended dibenzobarrelenes and bisdibenzobarrelenes. This chapter attempts to throw light on our endeavours in synthesising the various 9-alkenylanthracenes and bisanthracenes.Chapter 3 deals with the synthesis of olefin appended dibenzobarrelenes and bisdibenzobarrelenes. Ever since the discovery of di-It-methane rearrangement dibenzobarrelenes, tailored with dijferent substituents at various positions have always been a tool to photochemists in unravelling the mechanisms of light induced reactions. Our intention of analysing the role of a It-moiety at the bridgehead position of the dibenzobarrelene, was synthetically envisaged via the Diels-Alder reaction. Bisdibenzobarrelenes were synthesised through tandem Diels-Alder reaction. Various alkenylanthracenes and bisanthracenes were employed as dienes and the dienophiles used were dimethyl acetylenedicarboxylate and dibenzoylacetylene. In this chapter, we report our venture in synthesising the various olefin appended dibenzobarrelenes and bisdibenzobarrelenes. Chapter 4 describes the preliminary time-resolved fluorescence studies of some olefin appended dibenzobarrelenes and bisdibenzobarrelenes.To understand the primary and secondary physicochemical processes in a photochemical reaction it is necessary to characterise the excited states and the transient intermediates during their short lifetime. A number of methods developed on the basis of the physical properties of the transient species are available for their detection. Time-correlated single-photon counting technique has been utilised in the present study of the excited states of olefin appended dibenzobarrelenes and bisdibenzobarrelenes. To understand the primary and secondary physicochemical processes in a photochemical reaction it is necessary to characterise the excited states and the transient intermediates during their short lifetime. A number of methods developed on the basis of the physical properties of the transient species are available for their detection. Time-correlated single-photon counting technique has been utilised in the present study of the excited states of olefin appended dibenzobarrelenes and bisdibenzobarrelenes.Chapter 5 portrays the photochemistry of olefin appended dibenzobarrelenes and bisdibenzobarrelenes. Dibenzocyclooctatetraene and dibenzosemibullvalene are the photoproducts obtained respectively through the singlet excited state and the triplet excited state of dibenzobarrelenes. Chemical literature shows evidences of the photoreactivity of dibenzobarrelenes generating both the singlet and triplet mediated photoproducts, in a single photoreaction. Our research target in synthesising various bridgehead olefin appended dibenzobarrelenes and bisdibenzobarrelenes, was based on the perception that olefins are eflicient triplet quenchers, thereby quenching intramolecularly the triplet excited state of the barrelenes. A It-moiety at the bridgehead position of the dibenzobarrelene, creates a tetra tr-methane system, which similar to a 6li—7l' or tri-tr-methane systems, could be the fertile ground for interesting photochemical rearrangements. Our attempts in deciphering the photochemistry of the olefin appended dibenzobarrelenes and bisdibenzobarrelenes is the substance of this chapter.

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A marine Pseudomonas sp BTMS-51, immobilized by Ca-alginate gel entrapment was used for the production of extracellular Lglutaminase under repeated batch process and continuous process employing a packed bed reactor (PBR). Immobilized cells could produce an average of 25 U/ml of enzyme over 20 cycles of repeated batch operation and did not show any decline in production upon reuse. The enzyme yield correlated well with the biomass content in the beads. Continuous production of the enzyme in PBR was studied at different substrate concentrations and dilution rates. In general, the volumetric productivity increased with increased dilution rate and substrate concentrations and the substrate conversion efficiency declined. The PBR operated under conditions giving maximal substrate conversion efficiency gave an average yield of 21.07 U/ml and an average productivity of 13.49 U/ml/h. The system could be operated for 120 h without any decline in productivity

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L-Glutamine amidohydrolase (L-glutaminase, EC 3.5.1.2) is a therapeutically and industrially important enzyme. Because it is a potent antileukemic agent and a flavor-enhancing agent used in the food industry, many researchers have focused their attention on L-glutaminase. In this article, we report the continuous production of extracellular L-glutaminase by the marine fungus Beauveria bassiana BTMF S-10 in a packed-bed reactor. Parameters influencing bead production and performance under batch mode were optimized in the order-support (Na-alginate) concentration, concentration of CaCl2 for bead preparation, curing time of beads, spore inoculum concentration, activation time, initial pH of enzyme production medium, temperature of incubation, and retention time. Parameters optimized under batch mode for L-glutaminase production were incorporated into the continuous production studies. Beads with 12 × 108 spores/g of beads were activated in a solution of 1% glutamine in seawater for 15 h, and the activated beads were packed into a packed-bed reactor. Enzyme production medium (pH 9.0) was pumped through the bed, and the effluent was collected from the top of the column. The effect of flow rate of the medium, substrate concentration, aeration, and bed height on continuous production of L-glutaminase was studied. Production was monitored for 5 h in each case, and the volumetric productivity was calculated. Under the optimized conditions for continuous production, the reactor gave a volumetric productivity of 4.048 U/(mL·h), which indicates that continuous production of the enzyme by Ca-alginate-immobilizedspores is well suited for B. bassiana and results in a higher yield of enzyme within a shorter time. The results indicate the scope of utilizing immobilized B. bassiana for continuous commercial production of L-glutaminase