Spectral, Structural And Biological Studies Of Some Metal Complexes Of ‘Nsubstituted 2-Benzoylpyridine Thiosemicarbazones

Aqua complex ions of metals must have existed since the appearance of water on the earth, and the subsequent appearance of life depended on, and may even have resulted from the interaction of metal ions with organic molecules. Studies on the coordinating ability of metal ions with other molecules and anions culminated in the theories of/\lfred Werner. Thereon the progress in the studies of metal complex chemistry was rapid. Many factors, like the utility and economic importance of metal chemistry, the intrinsic interest _in many of the compounds and the intellectual challenge of the structural problems to be solved, have contributed to this rapid progress. X—ray diffraction studies further accelerated the progress. The work cited in this thesis was carried out by the author in the Department of Applied Chemistry during 2001-2004. The primary aim of these investigations was to synthesise and characterize some transition metal complexes of 2-benzoylpyridine N(4)-substituted thiosemicarbazones and to study the antimicrobial activities of the ligands and their metal complexes. The work is divided into eight chapters

Bioremediation of Zinc Using Bacillus sp. Isolated from Metal- Contaminated Industrial Zone

The production of heavy metals has increased quickly since the industrial revolution. Heavy metals frequently form compounds that can be toxic, carcinogenic, or mutagenic, even in very small concentrations. The usual techniques of removing metals from wastewaters are in general expensive and have many restrictions. Alternative methods of metal removal and recovery based on biological materials have been measured. Among various agents, the use of microbes for the removal of metals from industrial and municipal wastewater has been proposed as a promising alternative to conventional heavy metal management strategies in past decades. Thus, the present study aims to isolate and characterize bacteria from soil, sediment, and waters of metal-contaminated industrial area to study the zinc resistance patterns and the zinc bioaccumulation potential of the selected microorganism. Zinc analysis of the samples revealed that concentrations varying from 39.832 m g/L to 310.24 m g/L in water, 12.81 m g/g to 407.53 m g/g in soil, and 81.06 m g/g to 829.54 m g/g in sediment are present. Bacterial zinc resistance study showed that tolerance to Zn was relatively low (<500 m g/ml). Ten bacterial genera were represented in soil and 11 from water, while only 5 bacterial genera were recorded from sediment samples. Bacillus, Pseudomonas , and Enterobacter were found in soil, sediment, and water samples. Highly zincresistant Bacillus sp. was selected for zinc removal experiment. Zinc removal studies revealed that at pH 5 about 40% reduction occurs; at pH 7, 25% occurs; and at pH 9, 50% occurs. Relatively an increased removal of Zinc was observed in the fi rst day of the experiment by Bacillus sp. The metal bioaccumulative potential of the selected isolates may have possible applications in the removal and recovery of zinc from industrial ef fluents.

Characterization of low dielectric constant polyaniline thin film synthesized by ac plasma polymerization technique

Polyaniline thin films were prepared by ac plasma polymerization technique. Capacitance, dielectric loss, dielectric constant and ac conductivity of these films were investigated in the frequency range from 100 Hz to 1MHz and in the temperature range from 300 to 373 K. Capacitance and dielectric loss decreased with frequency and increased with temperature. This type of behaviour was found to be in good agreement with an existing model. The ac conductivity σ(ω) was found to vary as ωs with the index s 1. Annealing of polyaniline thin films in high vacuum at 373K for 1 h was found to reduce the dielectric loss. FTIR studies reveal that the aromatic ring is retained in the polyaniline thin films, which enhances the thermal stability of the polymer films

ToxicMetals Enrichment in the Surficial Sediments of a Eutrophic Tropical Estuary (Cochin Backwaters, Southwest Coast of India)

Concentrations and distributions of trace metals (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) in surficial sediments of the Cochin backwaters were studied during both monsoon and pre-monsoon periods. Spatial variations were in accordance with textural charaterstics and organic matter content. A principal component analysis distinguished three zones with different metal accumulation capacity: (i) highest levels in north estuary, (ii) moderate levels in central zone, and (iii) lowest levels in southern part. Trace metal enrichments are mainly due to anthropogenic contribution of industrial, domestic, and agricultural effluents, whose effect is enhanced by settling of metals due to organic flocculation and inorganic precipitation associated with salinity changes. Enrichments factors using Fe as a normalizer showed that metal contamination was the product of anthropogenic activities. An assessment of degree of pollution-categorized sediments as moderately polluted with Cu and Pb, moderately-to-heavily polluted with Zn, and heavily-to-extremely polluted with Cd. Concentrations at many sites largely exceed NOAA ERL (e.g., Cu, Cr, and Pb) or ERM (e.g., Cd, Ni, and Zn). This means that adverse effects for benthic organisms are possible or even highly probable.

Toxic Metal Distribution in the Core Sediment of Cochin Estuarine System (CES)

This article present the result from a study of two sediment cores collected from the environmentally distinct zones of CES. Accumulation status of five toxic metals: Cadmium (Cd), Chromium (Cr), Cobalt (Co), Copper (Cu) and Lead (Pb) were analyzed. Besides texture and CHNS were determined to understand the composition of the sediment. Enrichment Factor (EF) and Anthropogenic Factor (AF) were used to differentiate the typical metal sources. Metal enrichment in the cores revealed heavy load at the northern (NS1 ) region compared with the southern zone (SS1). Elevation of metal content in core NS1 showed the industrial input. Statistical analyses were employed to understand the origin of metals in the sediment samples. Principal Component Analysis (PCA) distinguishes the two zones with different metal accumulation capacity: highest at NS1 and lowest at SS1. Correlation analysis revealed positive significant relation only in core NS1, adhering to the exposition of the intensified industrial pollution

Dezincification of Epoxy Coated Brass in Cochin Estuary, India

Inhibited α brasses are largely immune to dezincification in most water, but the effect of tin and arsenic addition to α/β brasses is not so reliable or predictable in controlling the problem. There have been many cases of dezincification in duplex brasses in both fresh water and seawater. There is no reliable method of inhibiting the dezincification of two-phase brass despite there are some protection methods such as inhibitors, electro deposition and electro polymerization. Organic coatings are effectively used for the protection of metals due to their capacity to act as a physical barrier between the metal surface and corrosive environment. Hence, epoxy coating on brass was applied and effect of this against dezincification in Cochin estuarine water over a period of one year was studied and reported in this paper

Synthesis, Characterization and Applications of Modified TiO2 Systems

This thesis is divided in to 9 chapters and deals with the modification of TiO2 for various applications include photocatalysis, thermal reaction, photovoltaics and non-linear optics. Chapter 1 involves a brief introduction of the topic of study. An introduction to the applications of modified titania systems in various fields are discussed concisely. Scope and objectives of the present work are also discussed in this chapter. Chapter 2 explains the strategy adopted for the synthesis of metal, nonmetal co-doped TiO2 systems. Hydrothermal technique was employed for the preparation of the co-doped TiO2 system, where Ti[OCH(CH3)2]4, urea and metal nitrates were used as the sources for TiO2, N and metals respectively. In all the co-doped systems, urea to Ti[OCH(CH3)2]4 was taken in a 1:1 molar ratio and varied the concentration of metals. Five different co-doped catalytic systems and for each catalysts, three versions were prepared by varying the concentration of metals. A brief explanation of physico-chemical techniques used for the characterization of the material was also presented in this chapter. This includes X-ray Diffraction (XRD), Raman Spectroscopy, FTIR analysis, Thermo Gravimetric Analysis, Energy Dispersive X-ray Analysis (EDX), Scanning Electron Microscopy(SEM), UV-Visible Diffuse Reflectance Spectroscopy (UV-Vis DRS), Transmission Electron Microscopy (TEM), BET Surface Area Measurements and X-ray Photoelectron Spectroscopy (XPS). Chapter 3 contains the results and discussion of characterization techniques used for analyzing the prepared systems. Characterization is an inevitable part of materials research. Determination of physico-chemical properties of the prepared materials using suitable characterization techniques is very crucial to find its exact field of application. It is clear from the XRD pattern that photocatalytically active anatase phase dominates in the calcined samples with peaks at 2θ values around 25.4°, 38°, 48.1°, 55.2° and 62.7° corresponding to (101), (004), (200), (211) and (204) crystal planes (JCPDS 21-1272) respectively. But in the case of Pr-N-Ti sample, a new peak was observed at 2θ = 30.8° corresponding to the (121) plane of the polymorph brookite. There are no visible peaks corresponding to dopants, which may be due to their low concentration or it is an indication of the better dispersion of impurities in the TiO2. Crystallite size of the sample was calculated from Scherrer equation byusing full width at half maximum (FWHM) of the (101) peak of the anatase phase. Crystallite size of all the co-doped TiO2 was found to be lower than that of bare TiO2 which indicates that the doping of metal ions having higher ionic radius into the lattice of TiO2 causes some lattice distortion which suppress the growth of TiO2 nanoparticles. The structural identity of the prepared system obtained from XRD pattern is further confirmed by Raman spectra measurements. Anatase has six Raman active modes. Band gap of the co-doped system was calculated using Kubelka-Munk equation and that was found to be lower than pure TiO2. Stability of the prepared systems was understood from thermo gravimetric analysis. FT-IR was performed to understand the functional groups as well as to study the surface changes occurred during modification. EDX was used to determine the impurities present in the system. The EDX spectra of all the co-doped samples show signals directly related to the dopants. Spectra of all the co-doped systems contain O and Ti as the main components with low concentrations of doped elements. Morphologies of the prepared systems were obtained from SEM and TEM analysis. Average particle size of the systems was drawn from histogram data. Electronic structures of the samples were identified perfectly from XPS measurements. Chapter 4 describes the photocatalytic degradation of herbicides Atrazine and Metolachlor using metal, non-metal co-doped titania systems. The percentage of degradation was analyzed by HPLC technique. Parameters such as effect of different catalysts, effect of time, effect of catalysts amount and reusability studies were discussed. Chapter 5 deals with the photo-oxidation of some anthracene derivatives by co-doped catalytic systems. These anthracene derivatives come underthe category of polycyclic aromatic hydrocarbons (PAH). Due to the presence of stable benzene rings, most of the PAH show strong inhibition towards biological degradation and the common methods employed for their removal. According to environmental protection agency, most of the PAH are highly toxic in nature. TiO2 photochemistry has been extensively investigated as a method for the catalytic conversion of such organic compounds, highlighting the potential of thereof in the green chemistry. There are actually two methods for the removal of pollutants from the ecosystem. Complete mineralization is the one way to remove pollutants. Conversion of toxic compounds to another compound having toxicity less than the initial starting compound is the second way. Here in this chapter, we are concentrating on the second aspect. The catalysts used were Gd(1wt%)-N-Ti, Pd(1wt%)-N-Ti and Ag(1wt%)-N-Ti. Here we were very successfully converted all the PAH to anthraquinone, a compound having diverse applications in industrial as well as medical fields. Substitution of 10th position of desired PAH by phenyl ring reduces the feasibility of photo reaction and produced 9-hydroxy 9-phenyl anthrone (9H9PA) as an intermediate species. The products were separated and purified by column chromatography using 70:30 hexane/DCM mixtures as the mobile phase and the resultant products were characterized thoroughly by 1H NMR, IR spectroscopy and GCMS analysis. Chapter 6 elucidates the heterogeneous Suzuki coupling reaction by Cu/Pd bimetallic supported on TiO2. Sol-Gel followed by impregnation method was adopted for the synthesis of Cu/Pd-TiO2. The prepared system was characterized by XRD, TG-DTG, SEM, EDX, BET Surface area and XPS. The product was separated and purified by column chromatography using hexane as the mobile phase. Maximum isolated yield of biphenyl of around72% was obtained in DMF using Cu(2wt%)-Pd(4wt%)-Ti as the catalyst. In this reaction, effective solvent, base and catalyst were found to be DMF, K2CO3 and Cu(2wt%)-Pd(4wt%)-Ti respectively. Chapter 7 gives an idea about the photovoltaic (PV) applications of TiO2 based thin films. Due to energy crisis, the whole world is looking for a new sustainable energy source. Harnessing solar energy is one of the most promising ways to tackle this issue. The present dominant photovoltaic (PV) technologies are based on inorganic materials. But the high material, low power conversion efficiency and manufacturing cost limits its popularization. A lot of research has been conducted towards the development of low-cost PV technologies, of which organic photovoltaic (OPV) devices are one of the promising. Here two TiO2 thin films having different thickness were prepared by spin coating technique. The prepared films were characterized by XRD, AFM and conductivity measurements. The thickness of the films was measured by Stylus Profiler. This chapter mainly concentrated on the fabrication of an inverted hetero junction solar cell using conducting polymer MEH-PPV as photo active layer. Here TiO2 was used as the electron transport layer. Thin films of MEH-PPV were also prepared using spin coating technique. Two fullerene derivatives such as PCBM and ICBA were introduced into the device in order to improve the power conversion efficiency. Effective charge transfer between the conducting polymer and ICBA were understood from fluorescence quenching studies. The fabricated Inverted hetero junction exhibited maximum power conversion efficiency of 0.22% with ICBA as the acceptor molecule. Chapter 8 narrates the third order order nonlinear optical properties of bare and noble metal modified TiO2 thin films. Thin films were fabricatedby spray pyrolysis technique. Sol-Gel derived Ti[OCH(CH3)2]4 in CH3CH2OH/CH3COOH was used as the precursor for TiO2. The precursors used for Au, Ag and Pd were the aqueous solutions of HAuCl4, AgNO3 and Pd(NO3)2 respectively. The prepared films were characterized by XRD, SEM and EDX. The nonlinear optical properties of the prepared materials were investigated by Z-Scan technique comprising of Nd-YAG laser (532 nm,7 ns and10 Hz). The non-linear coefficients were obtained by fitting the experimental Z-Scan plot with the theoretical plots. Nonlinear absorption is a phenomenon defined as a nonlinear change (increase or decrease) in absorption with increasing of intensity. This can be mainly divided into two types: saturable absorption (SA) and reverse saturable absorption (RSA). Depending on the pump intensity and on the absorption cross- section at the excitation wavelength, most molecules show non- linear absorption. With increasing intensity, if the excited states show saturation owing to their long lifetimes, the transmission will show SA characteristics. Here absorption decreases with increase of intensity. If, however, the excited state has strong absorption compared with that of the ground state, the transmission will show RSA characteristics. Here in our work most of the materials show SA behavior and some materials exhibited RSA behavior. Both these properties purely depend on the nature of the materials and alignment of energy states within them. Both these SA and RSA have got immense applications in electronic devices. The important results obtained from various studies are presented in chapter 9.

Studies on Chemical Bath Deposited Semiconducting Copper Selenide and Iron Sulfide Thin Films Useful For Photovoltaic Applications

Chemical bath deposition (CBD)is one of the simplest, very convient and probably the cheapest method for thin film preparation. Photovoltaic is the cleanest and the most efficient mode of conversion of energy to electrical power. Silicon is the most popular material in this field. The present study on chemical bath deposited semiconducting copper selenide and iron sulfide thin films useful for photovoltaic applications. Semiconducting thin films prepared by chemical deposition find applications as photo detectors, solar control coatings and solar cells. Copper selenide is a p-type semiconductor that finds application in photovolitics. Several heterojunction systems such as Cu2-xSe/ZnSe (for injection electro luminescence), Cu2Se/AgInSe2 and Cu2Se/Si (for photodiodes), Cu2-xSe/CdS, Cu2-xSe/CdSe, CuxSe/InP and Cu2-xSe/Si for solar cells are reported. A maximum efficiency of 8.3% was achieved for the Cu2-xSe/Si cell, various preparation techniques are used for copper selenide like vacuum evaporation, direct reaction, electrodeposition and CBD. Instability of the as-prepared films was investigation and is accounted as mainly due to deviation from stoichiometry and the formation of iron oxide impurity. A sulphur annealing chamber was designed and fabricated for this work. These samples wee also analysed using optical absorption technique, XPS (X-ray Photoelectron Spectroscopy) and XRD.(X-Ray Diffraction).The pyrite films obtained by CBD technique showed amorphous nature and the electrical studies carried out showed the films to be of high resistive nature. Future work possible in the material of iron pyrite includes sulphur annealing of the non-stochiometric iron pyrite CBD thin films in the absence of atmospheric oxygen

Studies on Catalysis by Titania

Scientists throughout the world are in search of a better methodology to reduce the use of environmentally hazardous chemicals common in industries .A significant contribution in this field is given by different redox catalysts in oxidation reactions. The oxidation of organic substrates represents one of the most important industrial chemical reactions, explaining the significant efforts invested in the research and development of new heterogeneous catalysts with increased activities and selectivities in these type reactions[l-4|. Hence liquid phase reactions like epoxidation of cylcohexene and hydroxylation of phenol were carried out with a new outlook in the challenge using CeO2/TiO;; and CuO/TiO2 catalysts denoted as TiO2-Ce as TiO2-Cu respectively in this work. Also different wt% of metals incorporated titania catalysts like 3, 6, 9 wt% CeO2/TiO; and CuO/TiO;were subjected to the present study .The interaction between metal oxides and the oxide supports have attracted much attention because of the wide applications of supported metal oxide systems[7,8]. It is well known that supported oxides of transition metals are widely used as catalysts for various reactions. Titania as well its metal modified catalysts systems afford high activity and selectivity in the liquid phase epoxidation of cyclohexene[9]. Cyclohexene epoxide is obtained as the major product during the reaction with small amounts of allylic substitution products.This chapter gives an idea about the liquid phase oxidation reactions like epoxidation of cylcohexene and hydroxylation of phenol in which many industrially important products are formed. Here discusses about the redox properties of the ceria and copper incorporated titania catalysts.The epoxidation of cyclohcxene is carried out efficiently over the prepared systems with the selective formation of cyclohexane epoxide. This reaction hints that it might be possible to create cleaner nylon chemistry. The total acidity of the prepared systems plays an important role in determining the catalytic activity in the dehydrogenation of cyclohexane and cyclohexene. The total acidity of the prepared systems plays an important role in determining the catalytic activity in the dehydrogenation of cyclohexane and cyclohexene.

Swift Heavy Ion Irradiation and Thermal Annealing Induced Modification of Structural, Topographical and Magnetic Properties in Monolayer and Bilayer Films Based on FeNiMoB and Zinc Ferrite

Magnetism and magnetic materials have been playing a lead role in the day to day life of human beings. The human kind owes its gratitude to the ‘lodestone’ meaning ‘leading stone’ which lead to the discovery of nations and the onset of modern civilizations. If it was William Gilbert, who first stated that ‘earth was a giant magnet’, then it was the turn of Faraday who correlated electricity and magnetism. Magnetic materials find innumerable applications in the form of inductors, read and write heads, motors, storage devices, magnetic resonance imaging and fusion reactors. Now the industry of magnetic materials has almost surpassed the semiconductor industry and this speaks volumes about its importance. Extensive research is being carried out by scientists and engineers to remove obsolescence and invent new devices. Though magnetism can be categorized based on the response of an applied magnetic field in to diamagnetic, paramagnetic, ferromagnetic, ferrimagnetic and antiferromagnetic; it is ferrimagnetic, ferromagnetic and antiferromagnetic materials which have potential applications. The present thesis focusses on these materials, their composite structures and different ways and means to modify their properties for useful applications. In the past, metals like Fe, Ni and Co were sought after for various applications though iron was in the forefront because of its cost effectiveness and abundance. Later, alloys based on Fe and Ni were increasingly employed. They were used in magnetic heads and in inductors. Ferrites entered the arena and subsequently most of the newer applications were based on ferrites, a ferrimagnetic material, whose composition can be tuned to tailor the magnetic properties. In the late 1950s a new class of magnetic material emerged on the magnetic horizon and they were fondly known as metallic glasses. They are well known for their soft magnetic properties. They were synthesized in the form of melt spun ribbons and are amorphous in nature and they are projected to replace the crystalline counterparts.

Dynamics And Speciation Of The Heavy Metals In The Lower Reaches Of Chithrapuzha- A Tropical Tidal River

The proposed study is an attempt to quantify and study the seasonal and spatial variations in the distribution of Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb among the various geochemical phases in the surficial sediments of Chitrapuzha river. The study also estimates the concentration of heavy metals in dissolved, particulate and sediments and their variation in seasonal and spatial distribution. Chitrapuzha River originates as a small stream from the upper reaches of high ranges in the eastern boundary of Kerala, passes through the valley and finally joints in the Cochin backwaters. Numerous industrial units located along the banks of the river discharge treated and untreated effluents into the water. These are long standing local complaints about water pollution causing fish mortality and serious damage to agricultural crops resulting in extensive unemployment in the area. The river is thus of considerable social and economic importance.

Phase Transitions of Trace Metals in the Aquatic Environment of Kuttanad, Kerala

This thesis is a modest attempt in assessing the trace metal levels and their behavior in the aquatic environment of Kuttanad, an aquatic system that is severely affected by man’s intervention on natural processes, by study seriously evaluating the levels of trace metals in dissolved and particulate phases and also in the different chemical fractions of the sediments. Understanding of the distributions, variations and transfer processes of trace metals in different environmental phases in the backwaters of Kuttanad is vital for the assessment of the water pollution problems and study the ecology of the area which contributes 20% of the rice production in the State of Kerala. Kuttand is a low-lying, shallow bay formed as a result of geological uplift. The major economic activity is agriculture involving 40% of the population. About 1.5% of the people are engaged in aquaculture. The trace metal distribution in the Kuttand backwaters is considerably influenced by the tropical features of the location and by human activities including agricultural activities and construction of salinity barrier. In this study an attempt is made to differentiate the metals in the sediment into exchangeable, reducible and resistant fractions in the sediments.

Geochemistry of Rare Erath Elements and Trace Metals along the Western Continental Shelf of India

Rare earth elements have occupied an important role in marine geochemical research, particularly as used in the format of REE abundance patterns to describe the geochemical pathways in marine sedimentation and authigenesis. This study concentrates on the distribution pattern of Rare earth elements in the sediments, behavior of Eu and Ce with respect to their occurrence in multiple oxidation states. It also concentrate the depth wise variation of sediment REEs from near shore areas (30m) to deeper depths 200m) in the Arabian Sea. It includes the downcore variation of REEs and other trace elements in the sediment cores and a comparison between the REE distributions of Arabian Sea sediment with the sediments of Andaman Sea. The study gives a general introduction regarding the importance of RRE studies, its occurrence and abundance, electronic configuration, lanthanide contraction, oxidations states and REE supply to the ocean, seawater and sediments.

Polycyclic aromatic hydrocarbons and toxic trace metals in seawater and sediments from the west coast of India and their bioaccumulation in some selected species of fishes

Polycyclic Aromatic Hydrocarbons and other toxic compounds from industrial effluents are noted for their high potency for skin, lung, bladder and gastrointestinal cancers. Increased industrialization, and population growth led to greater production of wastes, Pesticides and PAHs have received attention due to their carcinogenic effects. The main objectives of the study were; to collect base line data on the concentration of PAHs in seawater and sediment from the west coast of India, the concentration of PAHs in certain species of fishes, the comparative levels of PAHs in fish, the influence of sediment characteristics on the concentration of PAH in sediment, changes in PAH concentration in water, sediment and fish, to provide a base line concentration of trace metals in water, sediment and fish, the seasonal changes in content of selected trace metals in water, sediment and fish from the west coast of India. The present study revealed that a predominance of silt and clay at all stations in the off Cochin area. The study has provided comprehensive information available to date for PAHs in seawater, sediment and fishes from the west cost of India especially from the Quilon to Mangalore region.

Tailored Ion Imprinted Polymer Materials for the Preconcentrative Separation of Noble Metals

Tailored ion imprinted polymer materials for the preconcentrative separation of noble metals. This study deals with the synthesis, separation,characterization and analytical application of the noble metals especially palladium and platinum. Platinum group metals(PGM) are currently receiving world wide attention. This group include Palladium(Pt),rhodium(Rh), ruthenium(Ru), iridium(Ir) and osmium(Os).PGM are used as catalysts for a wide variety of hydrogenation, oxidation, isomerization,cyclization,dehydrogenation and dehalogenation reactions.The corrosion resistance of PGM enables them to use in jewellery,electrical and glass industries,extrusion of synthetic fibres,manufacture of laboratory utensils,dental and medical devices. This study clearly establishes selective recovery of platinum from other noble and transition elements.