A comparative study on the anisole methylation activity of lanthanum-promoted Sn02 catalyst and its sulfate-doped analogue

A comparative study on the anisole methylation with methanol over lanthanum-promoted Sn02 catalyst and its sulfate-doped analogue is presented. A maximum 2.6-xylenol selectivity of 82% was achieved at 400 degreeC under optimized conditions at an anisole conversion of 65% over lanthanum-promoted Sn02 catalyst. The sulfate modification resulted in the dealkylation of anisole to phenol followed by several unselective side reactions due to the creation of strong acid sites. The activity of lanthanum-modified tin oxide catalysts in the selective formation of 2.6-xylenol is ascribed to the presence of weak Lewis acid sites and comparatively stronger basic sites.

Dynamic and Thermodynamic Structure of the Monsoon Boundary Layer over India

The objective of the study is to examine the dynamic and thermodynamic structure and the variations that occur in the surface layer during the pre-monsoon, onset and post-monsoon periods over the Indian region. The variations caused during the occurrence of micro and mesoscale systems, structure and variation in the marine boundary layer over the Indian region is also investigated. The drag coefficient computed indirectly also shows variation during various seasons. The thermodynamic structure of the atmosphere shows variation during the various seasons. The onset monsoon causes lowering of the Lifting Condensation Levels. The outcome of the study is expected to provide a better understanding of the structure and variations in the boundary layer over India, which is useful for many applications especially for numerical modeling studies.

Synthesis, characterization, and structure of a new cobalt(II) Schiff-base complex with quinoxaline- 2-carboxalidine-2-amino-5-methylphenol

The mononuclear cobalt(II) complex [CoL2] H2O (where HL is quinoxaline-2-carboxalidine- 2-amino-5-methylphenol) has been prepared and characterized by elemental analysis, conductivity measurement, IR, UV-Vis spectroscopy, TG-DTA, and X-ray structure determination. The crystallographic study shows that cobalt(II) is distorted octahedral with each tridentate NNO Schiff base in a cis arrangement. The crystal exhibits a 2-D polymeric structure parallel to [010] plane, formed by O-H...N and O-H... O intermolecular hydrogen bonds and pye stacking interactions, as a racemic mixture of optical enantiomers. The ligand is a Schiff base derived from quinoxaline-2-carboxaldehyde

Synthesis and crystal structure of cobalt(III) complex with a Schiff base and azide

The cobalt(III) complex, [Co(L)2(N3)2]2(ClO4)2, L being a Schiff base N-[phenyl(pyridin-2-yl)methylene]aniline has been synthesized and the crystal structure determined using X-ray crystallography. The complex crystallizes in triclinic system, space group P-1 with unit cell parameters a=10.9367(9) , b=18.0817(17) , c=20.1629(16) , α=111.341(2), β=91.622(2), γ=107.5030(10), V=3499.1(5) 3 and Z=2. It crystallizes with two independent molecules in the asymmetric unit. The two cobalt atoms are hexa-coordinate and have a distorted octahedral geometry, satisfied by four nitrogen atoms from two molecules of the Schiff base and two nitrogen atoms from the monodentate azide group. The perchlorate ions are non-coordinating.

Chelating behavior of acylhydrazones towards transition metals:Spectral and structural aspects

The current work deals with the synthesis and characterization of metal complexes derived from some substituted acylhydrazones. The hydrazones under investigation were characterized by IR, UV, NMR spectral studies and the molecular structure of one of the hydrazones was solved by single crystal XRD studies. In the present work dioxovanadium(V), manganese(II), cobalt(II/III), nickel(II), copper(II), zinc(II) and cadmium(II) complexes were synthesized and characterized by various spectroscopic techniques, molar conductance measurements, magnetic susceptibility measurements and cyclic voltammetry. Single crystals of some of the complexes were isolated and characterized by single crystal X-ray diffraction.The thesis is divided into eight chapters. Chapter 1 gives an introduction on hydrazones, diversity in their chelating behavior and their application in various fields. This chapter also describes different analytical techniques employed for the characterization of hydrazones and their metal complexes. Chapter 2 includes the synthesis and characterization of two substituted acylhydrazones. This chapter also discusses how the coordination behavior of hydrazones under investigation is interesting. Chapters 3-8 discuss the synthesis and characterization of some transition metal complexes derived from the acylhydrazones under study.The hydrazones synthesized were found to exist in the amido form. Various characterization techniques were carried out to explore the structure of the synthesized complexes. The results indicate that both the hydrazones coordinate through the pyridyl and azomethine nitrogens and amide oxygen either in enolate or neutral form. Out of synthesized complexes V(V), Zn/Cd(II) and one of the cobalt complex was found to diamagnetic. We could isolate single crystals of some of the complexes and most of the complexes crystallized were found to have a distorted octahedral geometry. Thus X-ray crystallographic study which was used as major tool in the structure determination revealed that the hydrazones undergo a rotation about the azomethine bond on complexation. We hope the work presented in the thesis would be helpful for those who are working in the field of metal complexes and can further they can be utilized for various applications.

Photopyroelectric study of thermal properties and phase transitions in selected solids

This thesis presents in detail. the theoretical developments and calculations which are used for the simultaneous determination of thermal parameters, namely thermal diffusivity (a). thermal effusivity (e), thermal conductivity (K) and heat capacity (cr ) employing photopyroelectric technique. In our calculations. we have assumed that the pyroelectric detector is supported on a copper backing. so that there will be sufficient heat exchange between the heated pyroelectric detector and the backing so that the signal fluctuations are reduced to a minimum. Since the PPE signal depends on the properties of the detector that are also temperature dependent. a careful temperature calibration of the system need to be carried out. APPE cell has been fabricated for the measurements that can be used to measure the thermal properties of solid samples from ~ 90 K to ~ 350 K. The cell has been calibrated using standard samples and the accuracy of the technique is found to be of the order of± 1%.In this thesis, we have taken up work n photopyroelectric investigation of thermal parameters of ferroelectric crystals such as Glycine phosphite (NH3CH2COOH3P03), Triglycine sulfate and Thiourea as well as mixed valence perovskites samples such as Lead doped Lanthanum Manganate (Lal_xPb~Mn03) Calcium doped (Lal_xCaxMnOJ) and Nickel doped Lanthanum Stroncium Cobaltate (Lao~Sro5Ni,Col_x03).The three ferroelectric crystals are prepared by the slow evaporation technique and the mixed valence perovskites by solid state reaction technique.Mixed valence perovskites, with the general formula RI_xA~Mn03 (R = La. Nd or Pr and A = Ba, Ca, Sr or Pb) have been materials of intense experimental and theoretical studies over the past few years. These materials show . colossal magneloresis/ance' (CMR) in samples with 0.2 < x < 0.5 in such a doping region, resistivity exhibits a peak at T = T p' the metal - insulator transition temperature. The system exhibits metallic characteristics with d %T > Oabove Tp (wherep is the resistivity) and insulating characteristics with d % T < 0 above T p. Despite intensive investigations on the CMR phenomena and associated electrical properties. not much work has been done on the variation of thermal properties of these samples. We have been quite successful in finding out the nature of anomaly associated with thermal properties when the sample undergoes M-I transition.The ferroelectric crystal showing para-ferroelectric phase transitions - Glycine phosphite. Thiourea and Triglycine sulfate - are studied in detail in order to see how well the PPE technique enables one to measure the thermal parameters during phase transitions. It is seen that the phase transition gets clearly reflected in the variation of thermal parameters. The anisotropy in thermal transport along different crystallographic directions are explained in terms of the elastic anisotropy and lattice contribution to the thermal conductivity. Interesting new results have been obtained on the above samples and are presented in three different chapters of the thesis.In summary. we have carried investigations of the variations of the thermal parameters during phase transitions employing photopyroelectric technique. The results obtained on different systems are important not only in understanding the physics behind the transitions but also in establishing the potentiality of the PPE tool. The full potential of PPE technique for the investigation of optical and thermal properties of materials still remains to be taken advantage of by workers in this field.

Development and Analysis of Compact AMicrostrip Antennas

The practical applications of microstrip antennas for mobile systems are in portable or pocket-size equipment and in vehicles. Antennas for VHFIUHF handheld portable equipment, such as pagers, portable telephones and transceivers, must naturally be small in size, light in weight and compact in structure. There is a growing tendency for portable equipment to be made smaller and smaller as the demand for personal communication rapidly increases, and the development of very compact hand-held units has become urgent.In this thesis work, main aim is to develop a more and more reduced sized microstrip patch antenna. It is well known that the smaller the antenna size, the lower the antenna efficiency. During the period of work, three different compact circular sided microstrip patches are developed and analysed, which have a significant size reduction compared to standard circular disk antenna (the most compact one of the basic microstrip patch configurations), without much deterioration of its properties like gain, bandwidth and efficiency. In addition to this the interesting results, dual port operation and circular polarization are also observed for some typical designs of these patches. These make the patches suitable for satellite and mobile communication systems.The theoretical investigations are carried out on these compact patches. The empirical relations are developed by modifying the standard equations of rectangular and circular disk microstrip patches, which helps to predict the resonant frequencies easily.

Studies on Thermal structure in the seas around in India

The thesis entitled Studies on Thermal Structure in the Seas Around India. An attempt is made in this study to document the observed variability of thermal structure, both on seasonal and short-term scales, in the eastern Arabian Sea and southwestern Bay of Bengal, from the spatial and time series data sets from a reasonably strong data base. The present study has certain limitations. The mean temperatures are based on an uneven distribution of data in space and time. Some of the areas, although having a ‘full annual coverage, do not have adequate data for some months. Some portions in the area under study are having data gaps. The consistency and the coherence in the internal wave characteristics could not be examined due to non-availability of adequate data sets. The influence of generating mechanisms; other than winds and tides on the observed internal wave fields could not be ascertained due to lack of data. However, a comprehensive and intensive data collection can overcome these limitations. The deployment of moored buoys with arrays of sensors at different depths at some important locations for about 5 to 10 years can provide intensive and extensive data sets. This strong data base can afford to address the short-term and seasonal variability of thermal field and understand in detail the individual and collective influences of various physical and dynamical mechanisms responsible for such variability.

Mesozooplankton of the Arabian Sea and the Bay of Bengal with special reference to planktonic ostracods

The Arabian Sea and the Bay of Bengal are both highly dynamic ecosystems, due to the seasonally reversing monsoon winds, but the processes affecting the mesozooplankton community remain poorly understood. These are important basins exhibiting enhanced biological production as a result of upwelling, winter cooling and other episodic events such as eddies and gyres. Zooplankters are primarily the prey for almost all fish larvae. Seasonal changes in the biogeochemical processes can strongly affect zooplankton density and distribution, which in turn, strongly affect the larval growth, and consequently, the pelagic fish recruitment. It is clear that plankton biomass and biogeochemical fluxes are not in steady state. Acoustic data on mesozooplankton abundance suggests that they also exist in the mesopelagic zone. Earlier studies were confined only to the upper 200 m and hence the structure of mesozooplankton community in the deeper layers was not well known. Copepods are the dominant mesoplankton group, and therefore the majority of the studies were focused on them. The planktonic ostracods are the second major crustacean group and at times, their swarms can outnumber all other planktonic groups. The understanding of the community structure of the ostracods is essential to establish their role in the marine food web. Mesozooplankton is responsible for the vertical flux of organic matter produced by phytoplankton and is assumed to be equivalent to new production (Eppley & Peterson, 1979). Since the fate of newly produced organic matter depends upon their consumers, the zooplankton biomass must be estimated in size fractions or taxonomic components to understand the vertical flux of organic carbon. It is thus important to update our knowledge on different groups of zooplankton on the basis of seasonal and temporal distribution. The distribution in space and time is essential for modeling the carbon cycling that structure the marine ecosystems

Investigations On The Preparation And Properties Of Reactively Evaporated Lead Sulphide And Tin Telluride Thin Films

The work reported in this thesis is the preparation, and the structural, electrical and optical properties of reactively evaporated lead sulphide and tin telluride thin films. The three temperature method had been used for the preparation of these semiconductor thin films. In this preparation technique constituent elements are evaporated from separate sources with the substrate kept at a particular temperature. when one of the constituent element is a gas near room temperature, the method is often called reactive evaporation. It has been found for many materials that a stoichiometric interval exists with a limited range of flux and substrate temperature. Usually this technique is used for the preparation of thin films of high melting point compounds or of materials which decompose during evaporation. Tin telluride and lead sulphide are neither high melting point materials nor do they decompose on melting. But even than reactive evaporation offers the possibility of changing the ratios of the flux of the constituent elements within a wide range and studying its effect on the properties of the films

An investigation on the preparation and properties of some transparent conducting oxides and lead selenide thin films”

The investigation of physical properties of matter has progressed so much during the last hundred years. Today physics is divided in to a large distinct group of special branches. These branches are distinguished by the particular area studied, method of investigation and so on. An independent and important branch that has developed is the physics ofthin films.Any object in solid or liquid form with one of its dimensions very much smaller than that of the other two may be called a thin film. It is having only one common property, namely, one of their dimensions is very small, though all their physical properties may be different. Thin layers of oil, floating on the surface of water, with their fascinating colours, have attracted men’s curiosity from time immemorial. The earliest application of thin films was the protective coatings in the form of paints. A thin layer of tin has been used from ancient times to protect copper utensils from corrosion. Indium thin films are used in certain applications on account of their good lubricating property. Relay contacts are coated with thin films of rare earth metals in order to prevent burning due to arcing. Hard coatings are also available using diamond like carbon (i-carbon). The basic properties of thin films are of considerable interest because of their potential applications in various fields of science and technology

Genetic divergence in lobsters (Crustacea: Palinuridae and Scyllaridae) from the Indian EEZ

The management of exploited species requires the identification of demographically isolated populations that can be considered as independent management units (MUs), failuring in which can lead to over -fishing and depletion of less productive stocks. By characterizing the distribution of genetic variation, population sub structuring can be detected and the degree of connectivity among populations can be estimated. The genetic variation can be observed using identified molecular markers of both nuclear and mitochondrial origin. Hence, the present work was undertaken to study the genetic diversity and population/stock structure in P. homarus homarus and T. unimaculatus from different landing centres along the Indian coast using nuclear (RAPD) and mitochondrial DNA marker tools which will help towards developing management strategies for management and conservation of these declining resources.To make consistent conservation and fisheries management decisions, accurate species identifications are needed. It is also suggested that it is not always desirable to rely on a single sequence for taxonomic identification. Thus, the feasibility of using partial sequences of additional mitochondrial genes like 16SrRNA, 12SrRNA and nuclear 18SrRNA has also been explored in our study. Phylogenies provide a sound foundation for establishing taxonomy. The present work also attempts to reconstruct the phylogeny of eleven species of commercially important lobsters from the Indian EEZ using molecular markers

Characterization and Pathogenicity of Vibrio cholerae and Vibrio vulnificus from Marine environments

The genus Vibrioof the family Vibrionaceae are Gram negative, oxidasepositive, rod- or curved- rodshaped facultative anaerobes, widespread in marine and estuarine environments. Vibrio species are opportunistic human pathogens responsible for diarrhoeal disease, gastroenteritis, septicaemia and wound infections and are also pathogens of aquatic organisms, causing infections to crustaceans, bivalves and fishes. In the present study, marine environmental samples like seafood and water and sediment samples from aquafarms and mangroves were screened for the presence of Vibrio species. Of the134 isolates obtained from the various samples, 45 were segregated to the genus Vibrio on the basis of phenotypic characterization.like Gram staining, oxidase test, MoF test and salinity tolerance. Partial 16S rDNA sequence analysis was utilized for species level identification of the isolates and the strains were identified as V. cholerae(N=21), V. vulnificus(N=18), V. parahaemolyticus(N=3), V. alginolyticus (N=2) and V. azureus (N=1). The genetic relatedness and variations among the 45 Vibrio isolates were elucidated based on 16S rDNA sequences. Phenotypic characterization of the isolates was based on their response to 12 biochemical tests namely Voges-Proskauers’s (VP test), arginine dihydrolase , tolerance to 3% NaCl test, ONPG test that detects β-galactosidase activity, and tests for utilization of citrate, ornithine, mannitol, arabinose, sucrose, glucose, salicin and cellobiose. The isolates exhibited diverse biochemical patterns, some specific for the species and others indicative of their environmental source.Antibiogram for the isolates was determined subsequent to testing their susceptibility to 12 antibiotics by the disc diffusion method. Varying degrees of resistance to gentamycin (2.22%), ampicillin(62.22%), nalidixic acid (4.44%), vancomycin (86.66), cefixime (17.77%), rifampicin (20%), tetracycline (42.22%) and chloramphenicol (2.22%) was exhibited. All the isolates were susceptible to streptomycin, co-trimoxazole, trimethoprim and azithromycin. Isolates from all the three marine environments exhibited multiple antibiotic resistance, with high MAR index value. The molecular typing methods such as ERIC PCR and BOX PCR revealed intraspecies relatedness and genetic heterogeneity within the environmental isolatesof V. cholerae and V. vulnificus. The 21 strains of V. choleraewere serogroupedas non O1/ non O139 by screening for the presence O1rfb and O139 rfb marker genes by PCR. The virulence/virulence associated genes namely ctxA, ctxB, ace, VPI, hlyA, ompU, rtxA, toxR, zot, nagst, tcpA, nin and nanwere screened in V. cholerae and V. vulnificusstrains.The V. vulnificusstrains were also screened for three species specific genes viz., cps, vvhand viu. In V. cholerae strains, the virulence associated genes like VPI, hlyA, rtxA, ompU and toxR were confirmed by PCR. All the isolates, except for strain BTOS6, harbored at least one or a combination of the tested genes and V. choleraestrain BTPR5 isolated from prawn hosted the highest number of virulence associated genes. Among the V. vulnificusstrains, only 3 virulence genes, VPI, toxR and cps, were confirmed out of the 16 tested and only 7 of the isolates had these genes in one or more combinations. Strain BTPS6 from aquafarm and strain BTVE4 from mangrove samples yielded positive amplification for the three genes. The toxRgene from 9 strains of V. choleraeand 3 strains of V. vulnificus were cloned and sequenced for phylogenetic analysis based on nucleotide and the amino acid sequences. Multiple sequence alignment of the nucleotide sequences and amino acid sequences of the environmental strains of V. choleraerevealed that the toxRgene in the environmental strains are 100% homologous to themselves and to the V. choleraetoxR gene sequence available in the Genbank database. The 3 strains of V. vulnificus displayed high nucleotide and amino acid sequence similarity among themselves and to the sequences of V. cholerae and V. harveyi obtained from the GenBank database, but exhibited only 72% homology to the sequences of its close relative V. vulnificus. Structure prediction of the ToxR protein of Vibrio cholerae strain BTMA5 was by PHYRE2 software. The deduced amino acid sequence showed maximum resemblance with the structure of DNA-binding domain of response regulator2 from Escherichia coli k-12 Template based homology modelling in PHYRE2 successfully modelled the predicted protein and its secondary structure based on protein data bank (PDB) template c3zq7A. The pathogenicity studies were performed using the nematode Caenorhabditiselegansas a model system. The assessment of pathogenicity of environmental strain of V. choleraewas conducted with E. coli strain OP50 as the food source in control plates, environmental V. cholerae strain BTOS6, negative for all tested virulence genes, to check for the suitability of Vibrio sp. as a food source for the nematode;V. cholerae Co 366 ElTor, a clinical pathogenic strain and V. cholerae strain BTPR5 from seafood (Prawn) and positive for the tested virulence genes like VPI, hlyA, ompU,rtxA and toxR. It was found that V. cholerae strain BTOS6 could serve as a food source in place of E. coli strain OP50 but behavioral aberrations like sluggish movement and lawn avoidance and morphological abnormalities like pharyngeal and intestinal distensions and bagging were exhibited by the worms fed on V. cholerae Co 366 ElTor strain and environmental BTPR5 indicating their pathogenicity to the nematode. Assessment of pathogenicity of the environmental strains of V. vulnificus was performed with V. vulnificus strain BTPS6 which tested positive for 3 virulence genes, namely, cps, toxRand VPI, and V. vulnificus strain BTMM7 that did not possess any of the tested virulence genes. A reduction was observed in the life span of worms fed on environmental strain of V. vulnificusBTMM7 rather than on the ordinary laboratory food source, E. coli OP50. Behavioral abnormalities like sluggish movement, lawn avoidance and bagging were also observed in the worms fed with strain BTPS6, but the pharynx and the intestine were intact. The presence of multi drug resistant environmental Vibrio strainsthat constitute a major reservoir of diverse virulence genes are to be dealt with caution as they play a decisive role in pathogenicity and horizontal gene transfer in the marine environments.