Novel1, 3-Dipolar Cycloaddition Reactions of Acyclic Carbonyl Ylides and Related Chemistry

The thesis entitled novel 1,3-dipolar cycloaddition reactions of acyclic carbonyl ylides and related chemistry embodies the results of the investigations carried out to explore the reactivity of acyclic carbonyl ylides,generated by the reaction of dicarbomethoxy carbine and aldehydes towards dipolarophiles such as activated styrenes,1,2-and 1,4-quinones. In conclusion ,we have explored the reactivity pattern of acyclic carbonyl ylides derived from dicarbomethoxycarbene and aldehyde towards activated styrenes with a view to develop a stereoselective synthesis of highly substituted tetrahydrofuran derivatives. It was also found that the ylide could be trapped by various 1,2-and 1,4-diones to form dioxolane derivatives. It is noteworthy that the cycloaddition is highly region- and stereoselective. With isatins the ylide preferentially adds to the more electrone deficient carbonyl group making it regiospecific. Hetrocyclic compounds are of pivotal importance in organic chemistry, and enormous efforts have been devoted to develop new methodologies for their synthesis. It is noteworthy in this context that, 1,3-dipolar cycloaddition reaction,otherwise called Huisgen reaction, constitutes one of the most efficient methods for the synthesis of five membered heterocycles. Among the various dipoles, carbonyl ylides have received substiancial attention in recent years largely due to their utility in the synthesis of a wide range of oxygen hetrocycles, which are often found as structural subunits of many bioactive natural products.

Use of an open photoacoustic cell for the thermal characterisation of liquid crystals

In this paper, we describe the use of an open cell photoacoustic configuration for the evaluation of the thermal effusivity of liquid crystals. The feasibility, precision and reliability of the method are initially established by measuring the thermal effusivities of water and glycerol, for which the effusivity values are known accurately. In order to demonstrate the use of the present method in the thermal characterization of liquid crystals, we have measured the thermal effusivity values in various mesophases of 4-cyano-4 - octyloxybiphenyl (8OCB) and 4-cyano-4 -heptyloxybiphenyl (7OCB) liquid crystals using a variable temperature open photoacoustic cell. A comparison of the measured values for the two liquid crystals shows that the thermal effusivities of 7OCB in the nematic and isotropic phases are slightly less than those of 8OCB in the corresponding phases

Use of an open photoacoustic cell for the thermal characterisation of liquid crystals

In this paper, we describe the use of an open cell photoacoustic configuration for the evaluation of the thermal effusivity of liquid crystals. The feasibility, precision and reliability of the method are initially established by measuring the thermal effusivities of water and glycerol, for which the effusivity values are known accurately. In order to demonstrate the use of the present method in the thermal characterization of liquid crystals, we have measured the thermal effusivity values in various mesophases of 4-cyano-4 - octyloxybiphenyl (8OCB) and 4-cyano-4 -heptyloxybiphenyl (7OCB) liquid crystals using a variable temperature open photoacoustic cell. A comparison of the measured values for the two liquid crystals shows that the thermal effusivities of 7OCB in the nematic and isotropic phases are slightly less than those of 8OCB in the corresponding phases

Use of an open photoacoustic cell for the thermal characterisation of liquid crystals

In this paper, we describe the use of an open cell photoacoustic configuration for the evaluation of the thermal effusivity of liquid crystals. The feasibility, precision and reliability of the method are initially established by measuring the thermal effusivities of water and glycerol, for which the effusivity values are known accurately. In order to demonstrate the use of the present method in the thermal characterization of liquid crystals, we have measured the thermal effusivity values in various mesophases of 4-cyano-4 - octyloxybiphenyl (8OCB) and 4-cyano-4 -heptyloxybiphenyl (7OCB) liquid crystals using a variable temperature open photoacoustic cell. A comparison of the measured values for the two liquid crystals shows that the thermal effusivities of 7OCB in the nematic and isotropic phases are slightly less than those of 8OCB in the corresponding phases

Optimization of carbon and nitrogen sources and growth factors for the production of an aquaculture probiotic (Pseudomonas MCCB 103) using response surface methodology

Aim: To develop a new medium for enhanced production of biomass of an aquaculture probiotic Pseudomonas MCCB 103 and its antagonistic phenazine compound, pyocyanin. Methods and Results: Carbon and nitrogen sources and growth factors, such as amino acids and vitamins, were screened initially in a mineral medium for the biomass and antagonistic compound of Pseudomonas MCCB 103. The selected ingredients were further optimized using a full-factorial central composite design of the response surface methodology. The medium optimized as per the model for biomass contained mannitol (20 g l)1), glycerol (20 g l)1), sodium chloride (5 g l)1), urea (3Æ3 g l)1) and mineral salts solution (20 ml l)1), and the one optimized for the antagonistic compound contained mannitol (2 g l)1), glycerol (20 g l)1), sodium chloride (5Æ1 g l)1), urea (3Æ6 g l)1) and mineral salts solution (20 ml l)1). Subsequently, the model was validated experimentally with a biomass increase by 19% and fivefold increase of the antagonistic compound. Conclusion: Significant increase in the biomass and antagonistic compound production could be obtained in the new media. Significance and Impact of the Study: Media formulation and optimization are the primary steps involved in bioprocess technology, an attempt not made so far in the production of aquaculture probiotics.

Open-cell photoacoustic investigation of the thermal effusivity of liquid crystals

We report the use of an open photoacoustic cell configuration for the evaluation of thermal effusivity of liquid crystals. Initially, the method is calibrated using water and glycerol as transparent liquid samples, and the role of thermal conductivity of these liquids on the photoacoustic signal amplitude is discussed. To demonstrate the application of the present method for the evaluation of thermal effusivity of liquid crystals, we have used certain multicomponent nematic liquid crystal mixtures, namely BL001, BL002, BL032, and BL035. Each of these liquid crystal mixtures contains four to nine components and are primarily based on the cyanobiphenyl structure. The measured values of thermal effusivity of BL001 and BL002 were found to be almost the same, but differ from those of BL032 and BL035, which implies a difference in composition of the latter two from the former two mixtures.

Organic Synthesis Mediated by Heterogeneous Catalysts

Catalysis is a technologically important field which determines the quality of life in future. Catalyst research in pharmaceutical industry,fine chemical synthesis and emission control demands supported catalysts in bulk quantities.In the present work it was observed that clay supported catalysts mentioned in various chapters could also be used for the synthesis of similar molecules. The K10Ti catalyst can be used for the synthesis similar substituted imidazole derivatives under solvent free conditions and synthetically important Mannich bases of substrates containing various substitutes.Al-pillared saponite can be used for acetalation of other polyhydroxy compounds like glycerol,mannitol etc.Cu-Pd KSF catalyst has found application in C-C bond forming reactions which can be applied to other reactions and similar methods can be adopted for the synthesis of other catalyst by changing the transition metals. Montmorillonite K10 catalysed synthesis of triarylpyridines can be extended to the synthesis tetrasubstuted pyroles.K10Ti can also be utilized for the synthesis of similar heterocycles.

Threading dislocation lines in two-sided flux-array decorations

Two-sided flux decoration experiments indicate that threading dislocation lines (TDLs), which cross the entire film, are sometimes trapped in metastable states. We calculate the elastic energy associated with the meanderings of a TDL. The TDL behaves as an anisotropic and dispersive string with thermal fluctuations largely along its Burgers vector. These fluctuations also modify the structure factor of the vortex solid. Both effects can, in principle, be used to estimate the elastic moduli of the material.

“Studies on short polyester fiber - polyurethane elastomer composite with different interfacial bonding agents”

The work presented in this thesis is regarding the development and evaluation of new bonding agents for short polyester fiber - polyurethane elastomer composites. The conventional bonding system based on hexamethylenetetramine, resorcinol and hydrated silica was not effective as a bonding agent for the composite, as the water eliminated during the formation of the RF resin hydrolysed the urethane linkages. Four bonding agents based on MDI/'I‘DI and polypropyleneglycol, propyleneglycol and glycerol were prepared and the composite recipe was optimised with respect to the cure characteristics and mechanical properties. The flow properties, stress relaxation pattern and the thermal degradation characteristics of the composites containing different bonding agents were then studied in detail to evaluate the new bonding systems. The optimum loading of resin was 5 phr and the ratio of the -01 to isocyanate was 1:1. The cure characteristics showed that the optimum combination of cure rate and processability was given by the composite with the resin based on polypropyleneglycol/ glycerol/ 4,4’diphenylmethanediisocynate (PPG/GL/MDI). From the rheological studies of the composites with and without bonding agents it was observed that all the composites showed pseudoplastic nature and the activation energy of flow of the composite was not altered by the presence of bonding agents. Mechanical properties such as tensile strength, modulus, tear resistance and abrasion resistance were improved in the presence of bonding agents and the effect was more pronounced in the case of abrasion resistance. The composites based on MDI/GL showed better initial properties while composites with resins based on MDI/PPG showed better aging resistance. Stress relaxation showed a multistage relaxation behaviour for the composite. Within the-strain levels studied, the initial rate of relaxation was higher and the cross over time was lesser for the composite containing bonding agents. The bonding agent based on MDI/PPG/GL was found to be a better choice for improving stress relaxation characteristics with better interfacial bonding. Thennogravimetirc analysis showed that the presence of fiber and bonding agents improved the thennal stability of the polyurethane elastomer marginally and it was maximum in the case of MDI / GL based bonding agents. The kinetics of degradation was not altered by the presence of bonding agents

Distribution and bioactive potential of soil actinomycetes from different ecological habitats

Emergence of drug resistance among pathogenic bacteria to currently available antibiotics has intensified the search for novel bioactive compounds from unexplored habitats. In the present study actinomycetes were isolated from two relatively unexplored and widely differing habitats such as mountain and wetlands and their ability to produce antibacterial substances were analyzed. Pure cultures of actinomycetes were identified by morphological and biochemical tests. Various genera of actinomycetes encountered included Nocardia, Pseudonocardia, Streptomyces, Nocardiopsis, Streptosporangium, Micromonospora, Rhodococcus, Actinosynnema, Nocardiodes, Kitasatosporia, Gordona, Intrasporangium and Streptoalloteichus. The frequency of occurrence of each genus was found to vary with sample. About 47% of wetland isolates and 33% of mountain isolates were identified as various species of Nocardia. The isolated strains differed among themselves in their ability to decompose proteins and amino acids and also in enzyme production potential. Antibiotic activities of these actinomycetes were evaluated against 12 test pathogenic bacteria by well diffusion method using agar wells in glycerol-yeast extract agar. About 95% of actinomycete isolates from wetland ecosystem and 75% of highland isolates suppressed in different degrees the growth of test pathogens. Relatively high antibacterial activity among these isolates underlined their potential as a source of novel antibiotics.

Optimization of carbon and nitrogen sources and growth factors for the production of an aquaculture probiotic (Pseudomonas MCCB 103) using response surface methodology

Aim: To develop a new medium for enhanced production of biomass of an aquaculture probiotic Pseudomonas MCCB 103 and its antagonistic phenazine compound, pyocyanin. Methods and Results: Carbon and nitrogen sources and growth factors, such as amino acids and vitamins, were screened initially in a mineral medium for the biomass and antagonistic compound of Pseudomonas MCCB 103. The selected ingredients were further optimized using a full-factorial central composite design of the response surface methodology. The medium optimized as per the model for biomass contained mannitol (20 g l)1), glycerol (20 g l)1), sodium chloride (5 g l)1), urea (3Æ3 g l)1) and mineral salts solution (20 ml l)1), and the one optimized for the antagonistic compound contained mannitol (2 g l)1), glycerol (20 g l)1), sodium chloride (5Æ1 g l)1), urea (3Æ6 g l)1) and mineral salts solution (20 ml l)1). Subsequently, the model was validated experimentally with a biomass increase by 19% and fivefold increase of the antagonistic compound. Conclusion: Significant increase in the biomass and antagonistic compound production could be obtained in the new media. Significance and Impact of the Study: Media formulation and optimization are the primary steps involved in bioprocess technology, an attempt not made so far in the production of aquaculture probiotics

A new inexpensive method for the preparation of acicular precursors for magnetic recording media

Magnetic materials meant for audio/video recording applications necessitate that polycrystalline materials be in acicular shape. So preparation of acicular precursors for magnetic storage materials assumes significance. The employment of aqueous solutions do not produce needle shape crystallites. Glycerol is one of the complexing media used for the precipitation of ferrous oxalate dihydrate. An inexpensive method using starch for preparation of acicular particles is described. The influence of an additive namely Gd on acicularity is also investigated

Synthesis and characterization of γ-Fe2O3—a magnetic tape material

Acicular FeC~O4-2H20 was precipitated from glycerol and starch media. Thermal decomposition of this oxalate in dry and moist nitrogen yielded primarily FeO and Fe 3Oa respectively. Characterization was attempted through DTA, TG, x-ray diffraction, TEM and magnetization studies. It was found that the oxalate can be completely decomposed to FeaO~ in moist nitrogen (PH~o ,"-" 35 torr) at 775 K and then oxidised by dry air to acicular "/-Fe~Oa at 575 K. The resulting material has saturation magnetization (,-,., 70 emu/g), coercive field (N300 Oe) and squareness ratio ( ,~, 0-60-0-65), which values art comparable with those of the commercial samples

Characterization of Lipid Droplets and Functional Analysis of Lipid Droplet-Associated Proteins in Dictyostelium discoideum

Lipid droplets (LDs) are the universal storage form of fat as a reservoir of metabolic energy in animals, plants, bacteria and single celled eukaryotes. Dictyostelium LD formation was investigated in response to the addition of different nutrients to the growth medium. LDs were induced by adding exogenous cholesterol, palmitic acid (PA) as well as growth in bacterial suspension, while glucose addition fails to form LDs. Among these nutrients, PA addition is most effective to stimulate LD formation, and depletion of PA from the medium caused LD degradation. The neutral lipids incorporated into the LD-core are composed of triacylglycerol (TAG), steryl esters, and an unknown neutral lipid (UKL) species when the cells were loaded simultaneously with cholesterol and PA. In order to avoid the contamination with other cellular organelles, the LD-purification method was modified. The isolated LD fraction was analysed by mass spectrometry and 100 proteins were identified. Nineteen of these appear to be directly involved in lipid metabolism or function in regulating LD morphology. Together with a previous study, a total of 13 proteins from the LD-proteome were confirmed to localize to LDs after the induction with PA. Among the identified LD-proteins, the localization of Ldp (lipid droplet membrane protein), GPAT3 (glycerol-3-phosphate acyltransferase 3) and AGPAT3 (1-acylglycerol-3-phosphate-acyltransferase 3) were further verified by GFP-tagging at the N-termini or C-termini of the respective proteins. Fluorescence microscopy demonstrated that PA-treatment stimulated the translocation of the three proteins from the ER to LDs. In order to clarify DGAT (diacylglycerol acyltransferase) function in Dictyostelium, the localization of DGAT1, that is not present in LD-proteome, was also investigated. GFP-tagged DGAT1 localized to the ER both, in the presence and absence of PA, which is different from the previously observed localization of GFP-tagged DGAT2, which almost exclusively binds to LDs. The investigation of the cellular neutral lipid level helps to elucidate the mechanism responsible for LD-formation in Dictyostelium cells. Ldp and two short-chain dehydrogenases, ADH (alcohol dehydrogenase) and Ali (ADH-like protein), are not involved in neutral lipid biosynthesis. GPAT, AGPAT and DGAT are three transferases responsible for the three acylation steps of de novo TAG synthesis. Knock-out (KO) of AGPAT3 and DGAT2 did not affect storage-fat formation significantly, whereas cells lacking GPAT3 or DGAT1 decreased TAG and LD accumulation dramatically. Furthermore, DGAT1 is responsible for the accumulation of the unknown lipid UKL. Overexpression of DGAT2 can rescue the reduced TAG content of the DGAT1-KO mutant, but fails to restore UKL content in these cells, indicating that of DGAT1 and DGAT2 have overlapping functions in TAG synthesis, but the role in UKL formation is unique to DGAT1. Both GPAT3 and DGAT1 affect phagocytic activity. Mutation of GPAT3 increases it but a DGAT1-KO decreases phagocytosis. The double knockout of DGAT1 and 2 also impairs the ability to grow on a bacterial lawn, which again can be rescued by overexpression of DGAT2. These and other results are incorporated into a new model, which proposes that up-regulation of phagocytosis serves to replenish precursor molecules of membrane lipid synthesis, whereas phagocytosis is down-regulated when excess fatty acids are used for storage-fat formation.