Beckmann rearrangement of E,E-cinnamaldoxime on rare earth exchanged (Ce3+, La3+, and RE3+) HFAU-Y zeolites: An efficient green process for the synthesis of isoquinoline

In this paper, a novel application of solid acid catalysts in the Beckmann rearrangement of E,E-cinnamaldoxime in the synthesis of an important heterocyclic compound; isoquinoline is reported. E,E-Cinnamaldoxime under ambient reaction conditions on zeolite catalysts underwent Beckmann rearrangement to produce isoquinoline in yields of ca. 86–95%. Cinnamonitrile and cinnamaldehyde were formed as by-products. LaH-Y zeolite produces maximum amount of the desired product (yield 95.6%). However, the catalysts are susceptible for deactivation due to the basic nature of the reactants and products, which neutralize the active sites. H-Y zeolite is more susceptible (22% deactivation in 10 h) for deactivation compared to the cerium-exchanged counterpart (18% deactivation in 10 h). Thus, the optimal protocol allows isoquinoline to be synthesised in excellent yields through the Beckmann rearrangement of cinnamaldoxime. The reaction is simple, effective, does not involve any other additives, and environmentally benign.

Fabrication and characterisation of polymer optical fibers for smart sensing and optical amplification

The thesis presented the fabrication and characterisation of polymer optical fibers in their applications as optical amplifier and smart sensors.Optical polymers such as PMMA are found to be a very good host material due to their ability to incorporate very high concentration of optical gain media like fluorescent dyes and rare earth compounds. High power and high gain optical amplification in organic dye-doped polymer optical fibers is possible due to extremely large emission cross sections of oyes. Dye doped (Rhodamine 6G) optical fibers were fabricated by using indigenously developed polymer optical fiber drawing tower. Loss characterization of drawn dye doped fibers was carried out using side illumination technique. The advantage of the above technique is that it is a nondestructive method and can also be used for studying the uniformity in fiber diameter and doping. Sensitivity of the undoped polymer fibers to temperature and microbending were also studied in its application in smart sensors.Optical amplification studies using the dye doped polymer optical fibers were carried out and found that an amplification of l8dB could be achieved using a very short fiber of length lOcm. Studies were carried out in fibers with different dye concentrations and diameter and it was observed that gain stability was achieved at relatively high dye concentrations irrespective of the fiber diameter.Due to their large diameter, large numerical aperture, flexibility and geometrical versatility of polymer optical fibers it has a wide range of applications in the field of optical sensing. Just as in the case of conventional silica based fiber optic sensors, sensing techniques like evanescent wave, grating and other intensity modulation schemes can also be efficiently utilized in the case of POF based sensors. Since polymer optical fibers have very low Young's modulus when compared to glass fibers, it can be utilized for sensing mechanical stress and strain efficiently in comparison with its counterpart. Fiber optic sensors have proved themselves as efficient and reliable devices to sense various parameters like aging, crack formation, weathering in civil structures. A similar type of study was carried out to find the setting characteristics of cement paste used for constructing civil structures. It was found that the measurements made by using fiber optic sensors are far more superior than that carried out by conventional methods. More over,POF based sensors were found to have more sensitivity as well.

Spectral studies and crystal structures of some transition metal complexes of N4-substituted semicarbazones

The present work is concentrated on the studies of two novel semicarbazones, di-2-pyridyl ketone-N4-phenyl-3-semicarbazone (HL1) and quinoline-2-carboxaldehyde-N4-phenyl-3-semicarbazone (HL2). The compositions of these semicarbazones were determined by the CHN analyses. For the characterization of these compounds we have used IR, UV and NMR spectral studies. The molecular structure of quinoline-2-carboxaldehyde-N4-phenyl-3- semicarbazone (HL2) was obtained by single crystal X-ray diffraction studies. Also, we have synthesized Zn(II), Cd(II), Cu(II), Ni(II), Co(II) and Mn(II) complexes of these semicarbazones, HL1 and HL2. These complexes were characterized by various spectroscopic techniques, magnetic and conductivity studies. We could isolate single crystals of some Zn(II) and Cd(II) compounds suitable for X-ray diffraction studies. For other complexes we could not isolate single crystals of good quality for single crystal X-ray diffraction studies.

Transition metal and rare earth metal modified sol-gel titania: a versatile catalyst for organic transformations

Catalysis is a mature field with extensive practical applications in today's society.indeed,the catalysis of petroleum refining,fine chemical synthesis and emission control demands the production of catalysts in bulk quantities.Future improvement of these well established processes is likely to be incremental.On the other hand,the continuous demand for new products will require additional novel and innovative processes.The need for pollution abatement and prevention also imposes new demands on catalysis, and new processes are periodically advanced for the control of emission of gases as well as for remediation processes such as the cleaning of underground waters. The number of problems where catalysis can have a big impact is constantly growing.In general,science stimulated by the technology has enriched the field of catalysis in a way that has had broad and lasting value.The thesis"Transition metal and rare earth metal modified sol-gel titania: a versatile catalyst for organic transformations" accounts the preparation and characterization studies of both transition metals and rare earth metals modified sol-gel titania and its applications in industrially useful organic reactions.

Spectral studies of naphthalocyanine (Nc) and rare earth phthalocyanine (RePc) molecules in an inorganic glassy borate matrix

Optical absorption and emission spectral studies of free and metal naphthalocyanine doped borate glass matrix are reported for the first time. Absorption spectra recorded in the UV- VIS-NIR region show the characteristic absorption bands, namely, the B-band and Q-band of the naphthalocyanine (Nc) molecule. Some of the important spectral parameters, namely, the optical absorption coefficient (α), molar extinction coefficient (ε) and absorption cross section (σa) of the principal absorption transitions are determined. Optical band gap (Eg) of the materials evaluated from the functional dependence of absorption coefficient on photon energy lies in the range 1.6 eV≤Eg≤2.1 eV. All fluorescence spectra except that of EuNc consist of an intense band in the 765 nm region corresponding to the excitation of Q-band. In EuNc the maximum fluorescence intensity band is observed at 824 nm. The intensity of the principal fluorescence band is maximum in ZnNc, whereas it is minimum in H2Nc. Radiative parameters of the principal fluorescence transitions corresponding to the Q-band excitation are also reported for the naphthalocyanine and phthalocyanine based matrices.

Optical absorption studies of free (H2Pc) and rare earth (RePc) phthalocyanine doped borate glasses

Optical absorption studies of free base and rare earth incorporated phthalocyanine doped borate glass matrix are reported for the first lime. The absorption spectra recorded in the UV- VIS region show two well defined absorption bands of phthalocyanine (Pc) molecule, namely the Soret band (B) and the Q band. The Q band always shows its characteristic splitting in all the doped glass matrices and the intensities of these components are found to vary from one Pc to another. Some of the important optical parameters, namely optical absorption coefficient (a), molar extinction coefficient (ε), absorption cross section (σa), oscillator strength (f), electric dipole strength (q2), absorption half bandwidth (Δλ) of the principal optical transitions have also been evaluated. Moreover, the spectral dependence of refractive index (n) and thereby the optical dielectric constant (ε) on wavelength yielded values of carrier concentration to effective mass ratio (N/m*) of the phthalocyanine molecule in the present glassy systems. Optical band gap (Eg) and width of the band tail (Et) are computed and their variations among the prepared samples are also discussed.

Photoacoustic Thermal Characterization of Porous Rare-Earth Phosphate Ceramics

The laser induced non-destructive photoacoustic technique has been employed to measure the thermal diffusivity of lanthanum phosphate ceramics prepared by the sol–gel route. The thermal diffusivity value was evaluated by knowing the transition frequency between the thermally thin to thermally thick region from the log–log plot of photoacoustic amplitude versus chopping frequency. Analysis of the data was carried out on the basis of the one-dimensional model of Rosencwaig and Gersho. The present investigation reveals that the sintering temperature has great influence on the propagation of heat carriers and hence on the thermal diffusivity value. The results were interpreted in terms of variations in porosity with sintering temperature as well as with changes in grain size.

Photoluminescence studies on rare earth titanates prepared by self-propagating high temperature synthesis method

The laser-induced luminescence studies of the rare earth titanates (R2Ti2O7) (R = La, Nd and Gd) using 355 nm radiation from an Nd:YAG laser are presented. These samples with submicron or nanometer size are prepared by the self-propagating high temperature synthesis (SHS) method and there is no known fluorescence shown by these rare earths in the visible region. Hence, the luminescence transitions shown by the La2Ti2O7 near 610 nm and Gd2Ti2O7 near 767 nm are quite interesting. Though La3+ ions with no 4f electrons have no electronic energy levels that can induce excitation and luminescence processes in the visible region, the presence of the Ti3+ ions leads to luminescence in this region.

Optical-limiting response of rare-earth metallo-phthalocyanine-doped copolymer matrix

The nanosecond optical-limiting characteristics (at 532 nm) of some rare-earth metallo-phthalocyanines (Sm(Pc)2, Eu(Pc)2, and LaPc) doped in a copolymer matrix of poly(methyl methacrylate) and methyl-2-cyanoacrylate have been studied for the first time to our knowledge. The optical-limiting response is attributed to reverse saturable absorption due to excited-state absorption. The performance of LaPc in a copolymer host is studied at different linear transmissions. The laser damage thresholds of all the samples are also reported.

Applications of Fractal Based Structures in Radar Cross Section Reduction

This thesis presents the Radar Cross Section measurements of different geometric structures such as flat plate,cylinder, corner reflector and circular cone loaded with fractal based metallo dielectric structures.Use of different fractal geometris,metallizations of different shapes as well as the frequency tanability is investigated for TE and TM polarization of the incident electromagnetic field.Application of fractal based metallo-dielectric structures results in RCS reduction over a wide range of frequency bands.RCS enhancement of dihedral corner is observed at certain acute and obtuse corner angles.The experimental results are validated using electromagnetic simulation softwares.

Enhancement of Microwave Properties of Planar Filters and Antennas using Photonic Bandgap (PBG) Structures

In this thesis, we explore the design, computation, and experimental analysis of photonic crystals, with a special emphasis on structures and devices that make a connection with practically realizable systems. First, we analyze the propenies of photonic-crystal: periodic dielectric structures that have a band gap for propagation. The band gap of periodically loaded air column on a dielectric substrate is computed using Eigen solvers in a plane wave basis. Then this idea is extended to planar filters and antennas at microwave regime. The main objectives covered in this thesis are:• Computation of Band Gap origin in Photonic crystal with the abet of Maxwell's equation and Bloch-Floquet's theorem • Extension of Band Gap to Planar structures at microwave regime • Predict the dielectric constant - synthesized dieletric cmstant of the substrates when loaded with Photonic Band Gap (PBG) structures in a microstrip transmission line • Identify the resonant characteristic of the PBG cell and extract the equivalent circuit based on PBG cell and substrate parameters for microstrip transmission line • Miniaturize PBG as Defected Ground Structures (DGS) and use the property to be implemented in planar filters with microstrip transmission line • Extended the band stop effect of PBG / DGS to coplanar waveguide and asymmetric coplanar waveguide. • Formulate design equations for the PBG / DGS filters • Use these PBG / DGS ground plane as ground plane of microstrip antennas • Analysis of filters and antennas using FDID method

Scattering Behaviour of fractal based metallo-dielectric structures

The scattering behaviour of fractal based metallodielectric structures loaded over metallic targets of different shapes such as flat plate, cylinder and dihedral corner reflector are investigated for both TE and TM polarizations of the incident wave. Out of the various fractal structures studied,square Sierpinski carpet structure is found to give backscattering reduction for an appreciable range of frequencies. The frequency of minimum backscattering depends on the geometry of the structure as well as on the thickness of the substrate. This structure when loaded over a dihedral corner reflector is showing an enhancement in RCS for corner angles other than 90◦.

Radar cross-section enhancement of dihedral corner reflector using fractal-based metallo-dielectric structures

Effective use of fractal-based metallo-dielectric structures for enhancing the radar cross-section (RCS) of dihedral corner reflectors is reported. RCS enhancement of about 30 dBsm is obtained for corner reflectors with corner angles other than 90deg. This may find application in remote sensing and synthetic aperture radar.

Transition Metal Complexes with Ring Incorporated Thiosemicarbazones: Syntheses,Structures and Spectral Properties

In the present work,the chelating behaviour of thiosemicarbazones of a heterocyclic diketone, 2,6-diacetylpyridine is studied,with the aim of investigating the influence coordination exerts on their conformation and /or configuration, in connection with the nature of the metal and of the counter ion.The various possibilities like unsubstitution,ring incorporation at terminal nitrogen and condensation of one of the ketone group alone have been tried for ligand selection.Mainly first row transition metals like manganese,iron,nickel,copper,zinc and cadmium are studied.Metals like cobalt also were studied but could not result in fruitful isolation of the compound due to solubility problems.Different spectroscopic and characterization techniques have been utilized to reveal the nature of the metal and the ligands in coordinated metal complex.

Studies on development of novel rare earth doped (Bi,Pb)-2212 superconductors with enhanced properties

The objective of the present work is to study the effect of rare-earth (RE) doping on the superconducting properties of (Bi,Pb)-2212 system and to develop novel superconductors in the system with improved properties, especially, the self- and in-field critical current densities so as to use them for practical applications. This dissertation describes a range of findings in Bi-based superconductor using the cationic substitution of rare earth (RE) elements. Most of the experiments reported here take advantage of the difference in the valency and ionic radii of dopant and doping site.