Performance of correlation functionals in ab initio chemisorption cluster-model calculations: Alkali metals on Si(111)

The performance of different correlation functionals has been tested for alkali metals, Li to Cs, interacting with cluster models simulating different active sites of the Si(111) surface. In all cases, the ab initio Hartree-Fock density has been obtained and used as a starting point. The electronic correlation energy is then introduced as an a posteriori correction to the Hartree-Fock energy using different correlation functionals. By making use of the ionic nature of the interaction and of different dissociation limits we have been able to prove that all functionals tested introduce the right correlation energy, although to a different extent. Hence, correlation functionals appear as an effective and easy way to introduce electronic correlation in the ab initio Hartree-Fock description of the chemisorption bond in complex systems where conventional configuration interaction techniques cannot be used. However, the calculated energies may differ by some tens of eV. Therefore, these methods can be employed to get a qualitative idea of how important correlation effects are, but they have some limitations if accurate binding energies are to be obtained.

Adsorption energy and spin state of first-row transition metals adsorbed on MgO(100)

Slab and cluster model spin-polarized calculations have been carried out to study various properties of isolated first-row transition metal atoms adsorbed on the anionic sites of the regular MgO(100) surface. The calculated adsorption energies follow the trend of the metal cohesive energies, indicating that the changes in the metal-support and metal-metal interactions along the series are dominated by atomic properties. In all cases, except for Ni at the generalized gradient approximation level, the number of unpaired electron is maintained as in the isolated metal atom. The energy required to change the atomic state from high to low spin has been computed using the PW91 and B3LYP density-functional-theory-based methods. PW91 fails to predict the proper ground state of V and Ni, but the results for the isolated and adsorbed atom are consistent within the method. B3LYP properly predicts the ground state of all first-row transition atom the high- to low-spin transition considered is comparable to experiment. In all cases, the interaction with the surface results in a reduced high- to low-spin transition energy.

Physiological Effects Of Some Heavy Metals On Perna Viridis (Linnaeus)

No serious attempt has so far been made in India to make use of the ‘Mussel watch’ concept as a useful tool for pollution monitoring of the marine and estuarine environment. The recently conducted 'National seminar on mussel watch’ by the Cochin University of Science and Technology (13-14 Feb, 1986) discussed the technical aspects related to mussel watch programme and the application of sentinel organism concept to the coastal areas of India. It is well known that the biological and physiological characteristics of the organism inhabiting tropical waters such as those prevailing in India, and the ecological as well as the environmental characteristics of temperate areas, where mussel watch programmes are already in existence differ greatly. So it is essential to adopt the techniques and standards developed for temperate species to the situations and conditions in India. In this context it is a prerequisite to collect information on physiology and other biological indices of stress of possible sentinel organisms like P.viridis. In consideration of the above, P. viridis which is a potential sentinel organism, is selected for the present study

Studies on the effects of selected trace metals on Matapenaeus Dobsoni (MIERS)

This thesis is an attempt by the author to assess the suitability of Metapenaeus dobsoni (Miers), an economically important crustacean species as a sentinel organism of trace metal pollution. The results of detailed investigations on seasonal variation, bioassay, accumulation and depuration of three metals viz., mercury, copper and zinc are presented and discussed. The importance of trace metals in the aquatic environment and their present status in the study area - Cochin backwaters, the significance of crustacean fisheries, the species M. dobsoni and the objectives of the present studies are described in Chapter 1. The methodology adopted during the investigation is given in Chapter 2. Chapter 3 delineates the seasonal variation of Hg, Cu and Zn in the edible and non-edible parts of M. dobsoni collected from Cochin backwaters for a period of one year (June 1984-May 1985). The results of bioassay experiments are given in Chapter 4. Kinetics of accumulation ,retention and depuration of trace metals, their biological half-life, the influence of size group and environmental factors are given in Chapter 5. The effect of these metals on the physiological response of M. dobsoni viz. oxygen consumption is included in Chapter 6. A summary and list of references are also appended.

Studies on Catalysis by Nano Titania Modified with Metals and Nonmetals

Semiconductor photocatalysis has received much attention during last three decades as a promising solution for both energy generation and environmental problems. Heterogeneous photocatalytic oxidation allows the degradation of organic compounds into carbon dioxide and water in the presence of a semiconductor catalyst and UV light source. The •OH radicals formed during the photocatalytic processes are powerful oxidizing agents and can mineralise a number of organic contaminants. Titanium dioxide (TiO2), due to its chemical stability, non-toxicity and low cost represents one of the most efficient photocatalyst. However, only the ultraviolet fraction of the solar radiation is active in the photoexcitation processes using pure TiO2 and although, TiO2 can treat a wide range of organic pollutants the effectiveness of the process for pollution abatement is still low. A more effective and efficient catalyst therefore must be formulated. Doping of TiO2 was considered with the aim of improving photocatalytic properties. In this study TiO2 catalyst was prepared using the sol-gel method. Metal and nonmetal doped TiO2 catalysts were prepared. The photoactivity of the catalyst was evaluated by the photodegradation of different dyes and pesticides in aqueous solution. High photocatalytic degradation of all the pollutants was observed with doped TiO2. Structural and optical properties of the catalysts were characterized using XRD, BET surface area, UV-Vis. DRS, CHNS analysis, SEM, EDX, TEM, XPS, FTIR and TG. All the catalysts showed the anatase phase. The presence of dopants shifts the absorption of TiO2 into the visible region indicating the possibility of using visible light for photocatalytic processes.

‘Biochemical Responses to Heavy Metals in Oreochromis mossambicus with special reference to Metal Detoxifying Mechanism

The present work is focused on the organelle and biochemical responses to heavy metal exposure in the fish Oreochromis mossambicus giving particular importance to the metal detoxifying machinery of the organism. The thesis is an outcome of the effort aimed at developing practicable monitoring techniques to deliver guidelines for biological effect monitoring and the need for specific biochemical methods to detect biological effects of heavy metals that can be interpreted in terms of the health status of the individual organism and eventually alterations in vital processes as growth and reproduction. The efficiency of the metal detoxifying metallothioneins which is an attractive tool for biological monitoring, their role as scavengers of trace metal ions and thus in relieving the biological machinery from their toxicity effects are important themes of this study. Efforts have also been made to test the reliability of the spill over hypothesis of the action of metallothioneins (Winge et a1.,1973) and their use as a biological barometer of heavy metal stress.

Studies on the toxic effects of selected heavy metals in the freshwater mussel lamellidens corrianus (lea)

Industrialisation affects air, water, and soil. Industrial effluents which enter the aquatic environment either by direct disposal or through run off, affect living organisms at morphological and physiological levels. In any living tissue toxic materials exert their effects first at molecular and biochemical levels (Robbins and Angell, 1976). Most of the industrial effluents contain elevated concentrations of organic and inorganic chemicals capable of eliciting stimulatory or inhibitory effects on the metabolism of aquatic organisms. Heavy metals form an important group of environmental pollutants. Effects of pollution on the aquatic environment by heavy metals have received considerable attention in recent years due to their toxicity even at very low levels, persistence in the environment, and chances of getting biomagnified. A pollutant that does not affect a particular process under normal unstressed condition may affect the ability of the animal to adjust to changing environmental conditions which ultimately decrease its chances of survival (Thurberg et al., 1973

“Assessment of Heavy Metals in the Environmental Compartments of the Central and Northern Coast of Kerala, India”

The nearshore marine ecosystem is a dynamic environment impacted by many activities, especially the coastal waters and sediments contiguous to major urban areas. Although heavy metals are natural constituents of the marine environment, inputs are considered to be conservative pollutants and are potentially toxic, accumulate in the sediment, are bioconcentrated by organisms and may cause health problems to humans via the food chain. A variety of metals in trace amounts are essential for biological processes in all organisms, but excessive levels can be detrimental by acting as enzyme inhibitors. Discharge of industrial wastewater, agriculture runoff and untreated sewage pose a particularly serious threat to the coastal environment of Kerala, but there is a dearth of studies in documenting the contaminant metals. This study aimed principally to assess such contamination by examining the results of heavy metal (Cu, Pb, Cr, Ni, Zn, Cd and Hg) analysis in seawater, sediment and benthic biota from a survey of five transects along the central and northern coast of Kerala in 2008 covering a 10.0 km stretch of near shore environment in each transect. Trophic transfer of metal contaminants from aquatic invertebrates to its predators was also assessed, by employing a suitable benthic food chain model in order to understand which all metals are undergoing biotransference (transfer of metals from a food source to consumer).The study of present contamination levels will be useful for potential environmental remediation and ecosystem restoration at contaminated sites and provides a scientific basis for standards and protective measures for the coastal waters and sediments. The usefulness of biomonitor proposed in this study would allow identification of different bioavailable metals as well as provide an assessment of the magnitude of metal contamination in the coastal marine milieu. The increments in concentration of certain metals between the predator and prey discerned through benthic food chain can be interpreted as evidence of biotransference.

"Effects of some heavy metals copper. zinc and lead on certain tissues of £153 Qarsia (Hamilton and Buchanan) in different environments

The research investigations on pollution, particularly in coastal/ estuarine environments are recent ones and started only in 1970s. Hence the informations available are fragmentary and scattered. They throw some light only on either the concentration of heavy metals in water or in sediment or in organisms. No concerted efforts have been made to consolidate and correlate the results between the environment and biota. Literature on the level of concentration of heavy metals in different tissues of organisms with regard to their availability in the living media, their ratio, their inter—relationship, tolerance limit of organisms, etc. are very few or rather nil. in view of the importance enumerated above, the candidate has selected the topic "Effects of some heavy metals copper, zinc and lead on certain tissues of E E (Hamilton and Buchanan) in different environments" for detailed studies and to understand systematically (i) the source of effluents and wastes, (ii) the concentration of heavy metals copper, zinc and lead in water, in sediments and in tissues of the test animal, (iii) their effects, (iv) capacity of tolerance and accumulation in different tissues of the animal, and (V) the "Bioaccumulation Factor", etc.

“Catalysis by Nanocrystalline Ceria Modified with Transition Metals”

The objective of the present work is to improve the textural and structural properties of cerium oxide by the incorporation of transition metals as well as sulphate ions. We have incorporated tungsten, molybdenum and chromium oxide into pure as well as sulphated cerium oxide and the catalytic systems thus prepared were characterised using various techniques. lndustrially important reactions such as acetalization and deacetalization, oxidative dehydrogenation of ethylbenzene, MTBE synthesis and Beckmann rearrangement of cinnamaldoxime and salicylaldoxime have been selected for the measurement of the catalytic activity of the systems. The work is presented in eight chapters

"Catalysis by pillared montmorillonites exchanged with transition metals"

The present work is oriented to obtain a comparative evaluation of the physicochemical properties and catalytic activities of iron, aluminium and iron aluminium mixed pillared montmorillonites and their transition metal exchanged analogues. Reactions of industrial importance like Friedel Crafts alkylations, catalytic wet peroxide oxidation of phenol and MTBE synthesis have been selected for the present study. The thesis is structured into seven chapters. First chapter deals with a brief introduction and literature survey on pillared clays. Second chapter explains the materials and methods employed in the work. Results and discussions on the characterisation techniques are described in the third chapter. The subsequent three chapters describe the catalytic activities of pillared clays in the industrially important reactions. Last chapter comprises the summary of the investigations and the conclusions drawn from the earlier chapters

‘‘catalysis by nano sulfated titania modified by transition metals"

in the present study, we have prepared and evaluated the physical and chemical properties and catalytic activities of transition metal loaded sulfated titania via the sol-gel route. Sol-gel method is widely used for preparing porous materials having controlled properties and leads to the formation of oxide particles in nano range, which are spherical or interconnected to each other. Characterization using various physico-chemical techniques and a detailed study of acidic properties are also carried out. Some reactions of industrial importance such as Friedel-Crafts reaction, fen-butylation of phenol,Beckmann rearrangement of cyclohexanone oxime, nitration of phenol and photochemical degradation of methylene blue have been selected for catalytic activity study in the present venture. The work is organized into eight chapters

Application of primary haemocyte culture of Penaeus monodon in the assessment of cytotoxicity and genotoxicity of heavy metals and pesticides

Lack of shrimp cell lines has hindered the study of pollutants which adversely affects shrimp health and its export value. In this context a primary haemocyte culture developed from Penaeus monodon was employed for assessing the cytotoxicity and genotoxicity of two heavy metal compounds, cadmium chloride and mercuric chloride and two organophosphate insecticides, malathion and monocrotophos. Using MTT assay 12 h IC50 values calculated were 31.09 16.27 mM and 5.52 1.16 mM for cadmium chloride and mercuric chloride and 59.94 52.30 mg l 1 and 186.76 77.00 mg l 1 for malathion and monocrotophos respectively. Employing Comet assay, DNA damage inflicted by these pollutants on haemocytes were evaluated and the pollutants induced DNA damage in >60% of the cells. The study suggested that haemocyte culture could be used as a tool for quantifying cytotoxicity and genotoxicity of aquaculture drugs, management chemicals and pollutants

An Encoded Infrared Sheet Of Light Navigational Beacon System For Precise Localization Of Indoor Mobile Robot Vehicles

A new localization approach to increase the navigational capabilities and object manipulation of autonomous mobile robots, based on an encoded infrared sheet of light beacon system, which provides position errors smaller than 0.02m is presented in this paper. To achieve this minimal position error, a resolution enhancement technique has been developed by utilising an inbuilt odometric/optical flow sensor information. This system respects strong low cost constraints by using an innovative assembly for the digitally encoded infrared transmitter. For better guidance of mobile robot vehicles, an online traffic signalling capability is also incorporated. Other added features are its less computational complexity and online localization capability all these without any estimation uncertainty. The constructional details, experimental results and computational methodologies of the system are also described