Investigations on the Structural, Spectral and Magnetic Interactions of Transition Metal Complexes of Multidentate Ligands from Di-2-pyridyl ketone and N(4)-substituted Thiosemicarbazides

The present work deals with the investigations on sthe structural spectral and magnetic interactions of transition metal complexes of multidentate ligands from D1-2-pyridyl ketone and N(4)-Substituted thiosemicarbazides.Thiosemicarbazones are thiourea derivatives with the general formula R2N— C(S)—NH—N=CR2. In the solution state, the thiosemicarbazones exhibit the thionethiol tautomerism similar to the keto-enol tautomerism, and in solution state the thiol form predominates and a deprotonation at the thiolate group in alcoholic medium enhances the coordination abilities ofthe thiosemicarbazones.The magnetochemistry of metal complexes of di-2-pyridyl ketone is a current hot subject of research, which mainly owes to the excellent structural diversity of the complexes ranging from cubanes to clusters, with promising ferromagnetic outputs.Only few efforts were aimed at the magnetochemistry of metal complexes of thiosemicarbazones, and that too were concerned with the complexes of bisttltioscinicarbazones). However, as far as the monothiosemicarbazones are concerned, the magnetochemistry of transition metal complexes of di-2-pyridyl ketone thiosemicarbazones turned up quite unexplored. Consequently, an investigation into it appeared novel and promising to us and that prompted this study, which can be regarded as the initial step towards exploring the magnetochemistry of thiosemicarbazone complexes, especially of di-2-pyridyl ketone derivatives.We could successfully isolate single crystals suitable for X-ray diffraction for the first three ligands. To conclude, we have synthesized some new thiosemicarbazones and their transition metal complexes and studied their structural, spectral and magnetic attributes. Some ofthe complexes revealed interesting stereochemistries and possible bridging characteristics with spectroscopic evidences. Unfortunately, single crystal Xray diffraction studies could not be carried out for many of these interesting compounds due to the lack of availability of suitable quality single crystals. However, the magnetic studies provided support for the proposed stereochemistry giving evidences for their magnetically concentrated nature. The magnetic susceptibilities measured at six different temperatures in the 80-298 K range are fitted into different magnetic equations, which provided an idea about the magnetic behavior of the compounds under study. Some of the copper, oxovanadium, nickel and cobalt complexes are found to possess anomalous magnetic moments, i.e., they revealed no regular gradation with temperature. However, some other copper complexes are observed to be antiferromagnetic, due to super-exchange pathways. The manganese complexes and one of the cobalt complexes are also observed to be antiferromagnetic in nature. However, some nickel complexes have turned up to be ferromagnetic. Accordingly, the versatile stereoehemistry and magnetic behavior of the complexes studied, prompt us to conclude that the transition metal complexes of di-2-pyridyl ketone thiosemicarbazones are promising systems for potential magnetic applications.

Studies on the structural, electrical and magnetic properties of composites based on spinel ferrites

This thesis mainly deals with the preparation and studies on magnetic composites based on spinel ferrites prepared both chemically and mechanically. Rubber ferrite composites (RFC) are chosen because of their mouldability and flexibility and the ease with which the dielectric and magnetic properties can be manipulated to make them as useful devices. Natural rubber is chosen as the Matrix because of its local availability and possible value addition. Moreover, NR represents a typical unsaturated nonpolar matrix. The work can be thought of as two parts. Part l concentrates on the preparation and characterization of nanocomposites based on y-Fe203. Part 2 deals with the preparation and characterization of RFCs containing Nickel zinc ferrit In the present study magnetic nanocomposites have been prepared by ionexchange method and the preparation conditions have been optimized. The insitu incorporation of the magnetic component is carried out chemically. This method is selected as it is the easiest and simplest method for preparation of nanocomposite. Nanocomposite samples thus prepared were studied using VSM, Mossbauer spectroscopy, Iron content estimation, and ESR spectroscopy. For the preparation of RFCs, the filler material namely nickel zinc ferrite having the general formula Ni)_xZnxFez04, where x varies from 0 to 1 in steps of 0.2 have been prepared by the conventional ceramic techniques. The system of Nil_xZn"Fe204 is chosen because of their excellent high frequency characteristics. After characterization they are incorporated into the polymer matrix of natural rubber by mechanical method. The incorporation is done according to a specific recipe and for various Loadings of magnetic fillers and also for all compositions. The cure characteristics, magnetic properties and dielectric properties of these composites are evaluated. The ac electrical conductivity of both ceramic nickel zinc ferrites and rubber ferrite composites are also calculated using a simple relation. The results are correlated.

Studies on magnetic monopole solutions of non-abelian gauge theories and related problems

In 1931 Dirac studied the motion of an electron in the field of a magnetic monopole and found that the quantization of electric charge can be explained by postulating the mere existence of a magnetic monopole. Since 1974 there has been a resurgence of interest in magnetic monopole due to the work of ‘t’ Hooft and Polyakov who independently observed that monopoles can exist as finite energy topologically stable solutions to certain spontaneously broken gauge theories. The thesis, “Studies on Magnetic Monopole Solutions of Non-abelian Gauge Theories and Related Problems”, reports a systematic investigation of classical solutions of non-abelian gauge theories with special emphasis on magnetic monopoles and dyons which possess both electric and magnetic charges. The formation of bound states of a dyon with fermions and bosons is also studied in detail. The thesis opens with an account of a new derivation of a relationship between the magnetic charge of a dyon and the topology of the gauge fields associated with it. Although this formula has been reported earlier in the literature, the present method has two distinct advantages. In the first place, it does not depend either on the mechanism of symmetry breaking or on the nature of the residual symmetry group. Secondly, the results can be generalized to finite temperature monopoles.

Circulation in the indian ocean in relation to the monsoon circulation of the atmosphere

The present thesis is an attempt by the researcher to Investigate the surface circulation of the Indian Ocean, north of 2095 in relation to the atmospheric circulation over the ocean. The aim is achieved by working out the circu1ation pattern and correlating it with the computed wind stress and its vorticity. The month wise surface circulation is arrived by drawing the streamlines, using freshand method with superimposed isotache. The zonal ad meridional componance of the wind stress and the curl of the wind stress are computed for each month over 2° latitude longitude quadrangle from the bulk aerodynamic formula, using a computer program. The data for drawing the surface circu1ation and for computing the wind stress and its curl have come from the Dutch Atlas.

Length-weight relationship, relative condition factor (Kn) and morphometry of Arius subrostratus (Valenciennes, 1840) from a coastal wetland in Kerala

The length – weight relationship and relative condition factor of the shovel nose catfish, Arius subrostratus (Valenciennes, 1840) from Champakkara backwater were studied by examination of 392 specimens collected during June to September 2008. These fishes ranged from 6 to 29 cm in total length and 5.6 to 218 g in weight. The relation between the total length and weight of Arius subrostratus is described as Log W = -1.530+2.6224 log L for males, Log W = - 2.131 + 3.0914 log L for females and Log W = - 1.742 + 2.8067 log L for sexes combined. The mean relative condition factor (Kn) values ranged from 0.75 to 1.07 for males, 0.944 to 1.407 for females and 0.96 to 1.196 for combined sexes. The length-weight relationship and relative condition factor showed that the well-being of A. subrostratus is good. The morphometric measurements of various body parts and meristic counts were recorded. The morphometric measurements were found to be non-linear and there is no significant difference observed between the two sexes. From the present investigation, the fin formula can be written as D: I, 7; P: I, 12; A: 17 – 20; C: 26 – 32. There is no change in meristic counts with the increase in body length.

Simple approach to determine resonant frequencies of microstrip antennas

A simple approach for accurate determination of the resonant frequencies of microstrip antennas of regular geometries is developed and presented. In this approach, a generalised empirical formula for the computation of effective dielectric permittivity is given which takes into account the ratio of the fringing area to the area of the patch. A correction to the equivalent side length of an equilateral triangular patch, previously published, is modified and a new formula is given. A correction to the effective dimensions of an elliptical microstrip antenna is also carried out. Numerical results obtained for the resonant frequencies of elliptical, circular, rectangular and equilateral-triangular microstrip antennas are in good agreement with the available theoretical and experimental results reported by others. The present approach is more efficient, simpler and more accurate

Deep-sea shrimp fishery off Kerala coast with emphasis on biology and population characteristics of Plesionika quasigrandis Chace, 1985

The present study is the first attempt to understand population characteristics of the deep-sea pandalid shrimp, P. quasigrandis and to assess the status of these resources off Kerala coast.Total mortality coefficient (Z) of P. quasigrandis estimated by various methods.Natural mortality coefficient (M) calculated was 0.65 and 1.02 by Pauly‟sempirical formula and Srinaths‟s formula respectively The deep-sea shrimp P. quasigrandis exploited from the present fishing ground and their monetary return has started showing a declining trend. By observing the current yield and economic return, there is no further scope for increasing the catch from the present fishing ground. The study indicated that majority of the deep-sea shrimp trawlers, especially targeted for pandalid shrimps still concentrated off Kollam area (Quilon Bank). Even though researchers had located several potential deep-sea fishing grounds based on exploratory surveys in Indian EEZ , fishermen are unaware of these fishing grounds located and hence sharing the information about new potential deep-sea fishing grounds could avert the possible stock decline due to the intensive targeted deep-sea shrimp fishery in the Quilon Bank. Hence, the present study recommended that part of the effort from existing fishing grounds may be shifted to newly located deep-sea fishing grounds which will help in a sustainableexploitation of deep-sea resources off Kerala coast.

Synthesis and Photoluminescence Properties of Novel Red Phosphors for White Light Emitting Diode Applications

Several series of Eu3+ based red emitting phosphor materials were synthesized using solid state reaction route and their properties were characterized. The present studies primarily investigated the photoluminescence properties of Eu3+ in a family of closely related host structure with a general formula Ln3MO7. The results presented in the previous chapters throws light to a basic understanding of the structure, phase formation and the photoluminescence properties of these compounds and their co-relations. The variation in the Eu3+ luminescence properties with different M cations was studied in Gd3-xMO7 (M = Nb, Sb, Ta) system.More ordering in the host lattice and more uniform distribution of Eu3+ ions resulting in the increased emission properties were observed in tantalate system.Influence of various lanthanide ion (Lu, Y, Gd, La) substitutions on the Eu3+ photoluminescence properties in Ln3MO7 host structures was also studied. The difference in emission profiles with different Ln ions demonstrated the influence of long range ordering, coordination of cations and ligand polarizability in the emission probabilities, intensity and quantum efficiency of these phosphor materials. Better luminescence of almost equally competing intensities from all the 4f transitions of Eu3+ was noticed for La3TaO7 system. Photoluminescence properties were further improved in La3TaO7 : Eu3+ phosphors by the incorporation of Ba2+ ions in La3+ site. New red phosphor materials Gd2-xGaTaO7 : xEu3+ exhibiting intense red emissions under UV excitation were prepared. Optimum doping level of Eu3+ in these different host lattices were experimentally determined. Some of the prepared samples exhibited higher emission intensities than the standard Y2O3 : Eu3+ red phosphors. In the present studies, Eu3+ acts as a structural probe determining the coordination and symmetry of the atoms in the host lattice. Results from the photoluminescence studies combined with the powder XRD and Raman spectroscopy investigations helped in the determination of the correct crystal structures and phase formation of the prepared compounds. Thus the controversy regarding the space groups of these compounds could be solved to a great extent. The variation in the space groups with different cation substitutions were discussed. There was only limited understanding regarding the various influential parameters of the photoluminescence properties of phosphor materials. From the given studies, the dependence of photoluminescence properties on the crystal structure and ordering of the host lattice, site symmetries, polarizability of the ions, distortions around the activator ion, uniformity in the activator distribution, concentration of the activator ion etc. were explained. Although the presented work does not directly evidence any application, the materials developed in the studies can be used for lighting applications together with other components for LED lighting. All the prepared samples were well excitable under near UV radiation. La3TaO7 : 0.15Eu3+ phosphor with high efficiency and intense orange red emissions can be used as a potential red component for the realization of white light with better color rendering properties. Gd2GaTaO7 : Eu3+, Bi2+ red phosphors give good color purity matching to NTSC standards of red. Some of these compounds exhibited higher emission intensities than the standard Y2O3 : Eu3+ red phosphors. However thermal stability and electrical output using these compounds should be studied further before applications. Based on the studies in the closely related Ln3MO7 structures, some ideas on selecting better host lattice for improved luminescence properties could be drawn. Analyzing the CTB position and the number of emission splits, a general understanding on the doping sites can be obtained. These results could be helpful for phosphor designs in other host systems also, for enhanced emission intensity and efficiency.