Electrochemical studies on Metal phthalocyanines

The primary aim of these investigations was to probe the elecnuchemical and material science aspects of some selected metal phthalocyanines(MPcs).Metal phthalocyanines are characterised by a unique planar molecular structure. As a single class of compounds they have been the subject of ever increasing number of physicochemical and technological investigations. During the last two decades the literature on these compounds was flooded by an outpour of original publications and patents. Almost every branch of materials science has benefited by their application-swface coating, printing, electrophotography, photoelectrochemistry, electronics and medicine to name a few.The present study was confined to the electrical and electrochemical properties of cobalt, nickel, zinc. iron and copper phthalocyanines. The use of soluble Pes as corrosion inhibitor for aluminium was also investigated.In the introductory section of the thesis, the work done so far on MPcs is reviewed. In this review emphasis is given to their general methods of synthesis and the physicochemical properties.In phthalocyanine chemistry one of the formidable tasks is the isolation of singular species. In the second chapter the methods of synthesis and purification are presented with necessary experimental details.The studies on plasma modified films of CoPe, FePc, ZnPc. NiPc and CuPc are also presented.Modification of electron transfer process by such films for reversible redox systems is taken as the criterion to establish enhanced electrocatalytic activity.Metal phthalocyanines are p- type semiconductors and the conductivity is enhanced by doping with iodine. The effect of doping on the activation energy of the conduction process is evaluated by measuring the temperature dependent variation of conductivity. Effect of thennal treatment on iodine doped CoPc is investigated by DSC,magnetic susceptibility, IR, ESR and electronic spectra. The elecnucatalytic activity of such doped materials was probed by cyclic voltammetry.The electron transfer mediation characteristics of MPc films depend on the film thickness. The influence of reducing the effective thickness of the MPc film by dispersing it into a conductive polymeric matrix was investigated. Tetrasulphonated cobalt phthalocyanine (CoTSP) was electrostatically immobilised into polyaniline and poly(o-toluidine) under varied conditions.The studies on corrosion inhibition of aluminium by CoTSP and CuTSP and By virtue of their anionic character they are soluble in water and are strongly adsorbed on aluminium. Hence they can act as corrosion inhibitors. CoTSP is also known to catalyze the reduction of dioxygen.This reaction can accelerate the anodic dissolution of metal as a complementary reaction. The influence of these conflicting properties of CoTSP on the corrosion of aluminium was studied and compared with those of CuTSP.In the course of these investigations a number of gadgets like cell for measuring the electrical conductivity of solids under non-isothermal conditions, low power rf oscillator and a rotating disc electrode were fabricated.

Fatty acids as Biomarkers in the Mangrove sediments of Cochin

The biogeochemistry of mangroves are the least understood ecological properties because of their sediment complexicity due to the tidal influx of allochthonous organic matter and the autochthonous inputs.In order to understand the relative importance of biogeochemical processes,it is necessary not only to characterise and qualify the organic matter but also to identify its major sources .The present study is a preliminary investigation to identify the sources of organic matter in three mangrove systems of Cochin Estuary using fatty acid biomarkers,δ13 C of total organic matter,elemental composition and biochemical composition.

Mangrove plant Ceriops tagal as a potential source of anti White Spot Syndrome Virus preparations for Penaeus monodon

White spot syndrome virus (WSSV) is the deadliest virus among crustaceans ever discovered having several unique and novel features. Recent developments in genomics and proteomics could elucidate the molecular process involved in the WSSV infection and the host pathogen interaction to some extent. Until now no fool proof treatment or prophylactic measure has been made available to control WSSV out breaks in culture system. Even though there are technologies like application of immunostimulants, vaccines, RNAi and several antiviral natural products none of them has been taken to the level of clinical trials. However, there are several management options such as application of bioremediation technologies to maintain the required environmental quality, maintenance of zero water exchange systems coupled with application of probiotics and vaccines which on adoption shall pave way for successful crops amidst the rapid spread of the virus. In this context the present work was undertaken to develop a drug from mangrove plants for protecting shrimp from WSSV.Mangroves belong to those ecosystems that are presently under the threat of destruction, diversion and blatant attack in the name of so called ‘developmental activities’. Mangrove plants have unique ecological features as it serves as an ecotone between marine and terrestrial ecosystem and hence possess diversity of metabolites with diverse activities. This prompted them being used as remedial measures for several ailments for ages. Among the mangrove plants Ceriops tagal, belonging to the family Rhizophororaceae was in attention for many years for isolating new metabolites such as triterpenes, phenolic compounds, etc. Even though there were attempts to study various plant extracts to develop anti-viral preparations their activity against WSSV was not investigated as yet.

Microalgal vegetation in the selected Mangrove Ecosystem of Kerala.

Department of Marine Biology, Cochin University of Science & Technology

Sterols in mangrove sediments of the cochin estuary

The thesis entitled “Sterols in Mangrove Sediments of the Cochin Estuary” is an attempt to characterize the sterol content of the mangrove sediments, their dietary status with respect to the natural flora and fauna present, their transfonnations in the sediment and assess contributions, if any to the nursery character of the mangrove eco system. Samplings were done from two sites at Mangalavanam and Vypin. Mangalavanam is a patchy mangrove area in the heart of the city of Cochin and serves as a small bird sanctuary. This is an almost closed system with a single narrow canal linking to the estuary. Vypin, the largest single stretch of mangroves in Kerala, is regularly inundated by a semi diurnal rhythm of Cochin bar mouth. Perhaps, this is the only site in Kerala where one can see mangroves right along the accreting seacoast. However a lot of developmental pressure is threatening the very existence of these mangroves. Post monsoon sediment samples from these areas were used for the present study, as it is the period of maximum faunal growth and activity

Seoimentology And Geochemistiiy Of Some Selected Mangrove Ecosystems Of Kerala, Southwest Coast Of India

As a result of the issues of care and conservation and sustainable utilisation, the proper management of mangrove forests have become more pressing than ever. Much recent ecological and toxicological debate has been centered around the question of validity of making predictions about the future of mangrove ecosystemas a result of the newly evolved environmental policy. Though muchinformation exist on the biodiversity, floristic composition and characteristics, geographical distribution and uses of mangroves, systematic documentation of the various sedimentological and geochemical phenomena in relation to the mangrove flora are scarce. Hazardous, persistent, man-made chemicals and waste produces are entering the mangrove ecosystem at from the adjacent watersheds which strengthened alarming rates the indispensible need for further researches on the environmental behaviours, fate and the effect of such products. Studies on the effect of heavy metals, pesticides and the other toxic signals through bioassay and toxicity tests on mangrove species as well as in sediments definitely will furnish ample clues to establish the actual operative mechanisms of these environments. A thorough review of literature made in this angle reveals that some attempts have already been initiated the world over the record the physico-chemical characteristics of major abiotic components such as sediments and water of many mangrove ecosystem, however, adequate information is lacking in the Indian Environmental Science scenario. The present investigation is an attempt to record the sedimentological, mineralogical and geochemical characteristics of sediments as well as the heavy metal enrichment in the various species ofmangrove flora of three important mangrove ecosystems of Kerala, located at Veli (SouthKerala), Kochi (Central Kerala) and Kannur (North Kerala). The results of the above investigation have been analysed statistically, discussed based on the available literature and presented in this thesis under seven chapters

Chemical Evaluation of Selected Organics and Trace Metals in the Mangrove Macroflora Of Cochin

Mangroves are considered to play a significant role in global carbon cycling. Themangrove forests would fix CO2 by photosynthesis into mangrove lumber and thus decrease the possibility of a catastrophic series of events - global warming by atmospheric CO2, melting of the polar ice caps, and inundation of the great coastal cities of the world. The leaf litter and roots are the main contributors to mangrove sediments, though algal production and allochthonous detritus can also be trapped (Kristensen et al, 2008) by mangroves due to their high organic matter content and reducing nature are excellent metal retainers. Environmental pollution due to metals is of major concern. This is due to the basic fact that metals are not biodegradable or perishable the way most organic pollutants are. While most organic toxicants can be destroyed by combustion and converted into compounds such as C0, C02, SOX, NOX, metals can't be destroyed. At the most the valance and physical form of metals may change. Concentration of metals present naturally in air, water and soil is very low. Metals released into the environment through anthropogenic activities such as burning of fossils fuels, discharge of industrial effluents, mining, dumping of sewage etc leads to the development of higher than tolerable or toxic levels of metals in the environment leading to metal pollution. Of course, a large number of heavy metals such as Fe, Mn, Cu, Ni, Zn, Co, Cr, Mo, and V are essential to plants and animals and deficiency of these metals may lead to diseases, but at higher levels, it would lead to metal toxicity. Almost all industrial processes and urban activities involve release of at least trace quantities of half a dozen metals in different forms. Heavy metal pollution in the environment can remain dormant for a long time and surface with a vengeance. Once an area gets toxified with metals, it is almost impossible to detoxify it. The symptoms of metal toxicity are often quite similar to the symptoms of other common diseases such as respiratory problems, digestive disorders, skin diseases, hypertension, diabetes, jaundice etc making it all the more difficult to diagnose metal poisoning. For example the Minamata disease caused by mercury pollution in addition to affecting the nervous system can disturb liver function and cause diabetes and hypertension. The damage caused by heavy metals does not end up with the affected person. The harmful effects can be transferred to the person's progenies. Ironically heavy metal pollution is a direct offshoot of our increasing ability to mass produce metals and use them in all spheres of existence. Along with conventional physico- chemical methods, biosystem approachment is also being constantly used for combating metal pollution

Physiology of the blood of cat fishes

The vast areas of derelict swamps covered by macrophyton and swarmed by insects scattered in different parts of India are at present either under total negligence or utilized as waste disposal dumps. Eventhough Indian subcontinent is ranked among the first ten fish producing countries in the world, the fish production is not at par with the increasing need of protein in the average Indian diet. So the water areas which become unusable for conventional human activities like the swamps could be used for fish culture which would increase the availability of protein in the form of fish flesh, thus providing new opportunities to the fishermen. But the conversion of swamps for fish culture would entail considerable expenditure. Hence the significance of a group of fresh water fishes which have made their favourable abode the muddy swamps of tropics depending partly on accessory _respiration to survive in the inimical environment. The homeostasis achieved in such a hostile, hypoxic medium make them excellent choices for culture in the derelict freshwater bodies of India. These air breathing fishes form an economically important group which are highly esteemed as food fishes in many parts of South Asia and Africa. Though their natural habitat seems to be the marshes, they have also conquered other freshwater bodies like ponds, tanks, rivers and flooded paddy fields. They can also tolerate slightly brackish waters. They are known for their nutritive, invigorating and therapeutic qualities and are recommended by physicians as diet during convalescence (Jhingran, 1982)

Studies on some aspects of mangrove ecosystem in a tropical estuary"

The situation in the backwaters of Kerala, which reportedly had about 70,000 ha of mangroves, is unique in the sense that there has been a total conversion to other uses such as paddy cultivation, coconut plantation, aquaculture, harbour development and urban development In order to save and restore what is left over national and international organisations are mounting pressure on scientists and policy makers to work out ways and means conserving and managing the mangrove ecosystems. In this context, it has been observed in recent years that mangrove vegetation has remained intact in isolated pockets of undisturbed areas in the Cochin estuarine system and also that there is resurgence of mangroves in areas of accretion and silting. The candidate took up the present study with a view to make an inventory of the existing mangrove locations, the areas of resurgence, species composition, zonation and other ecological parameters to understand their dynamism and to suggest a mangement plan for this important coastal ecosystem

A Novel Cache Resolution Technique For Cooperative Caching In Wireless Mobile Networks

Cooperative caching is used in mobile ad hoc networks to reduce the latency perceived by the mobile clients while retrieving data and to reduce the traffic load in the network. Caching also increases the availability of data due to server disconnections. The implementation of a cooperative caching technique essentially involves four major design considerations (i) cache placement and resolution, which decides where to place and how to locate the cached data (ii) Cache admission control which decides the data to be cached (iii) Cache replacement which makes the replacement decision when the cache is full and (iv) consistency maintenance, i.e. maintaining consistency between the data in server and cache. In this paper we propose an effective cache resolution technique, which reduces the number of messages flooded in to the network to find the requested data. The experimental results gives a promising result based on the metrics of studies.

A location aided cooperative caching protocol for mobile ad hoc networks

Cooperative caching is an attractive solution for reducing bandwidth demands and network latency in mobile ad hoc networks. Deploying caches in mobile nodes can reduce the overall traffic considerably. Cache hits eliminate the need to contact the data source frequently, which avoids additional network overhead. In this paper we propose a data discovery and cache management policy for cooperative caching, which reduces the caching overhead and delay by reducing the number of control messages flooded in to the network. A cache discovery process based on location of neighboring nodes is developed for this. The cache replacement policy we propose aims at increasing the cache hit ratio. The simulation results gives a promising result based on the metrics of studies

PEER TO PEER CACHE RESOLUTION MECHANISM FOR MOBILE AD HOC NETWORKS

In this paper we investigate the problem of cache resolution in a mobile peer to peer ad hoc network. In our vision cache resolution should satisfy the following requirements: (i) it should result in low message overhead and (ii) the information should be retrieved with minimum delay. In this paper, we show that these goals can be achieved by splitting the one hop neighbours in to two sets based on the transmission range. The proposed approach reduces the number of messages flooded in to the network to find the requested data. This scheme is fully distributed and comes at very low cost in terms of cache overhead. The experimental results gives a promising result based on the metrics of studies.

Energy Efficient Cache Discovery in Wireless Mobile Ad oc Networks

Data caching is an attractive solution for reducing bandwidth demands and network latency in mobile ad hoc networks. Deploying caches in mobile nodes can reduce the overall traf c considerably. Cache hits eliminate the need to contact the data source frequently, which avoids additional network overhead. In this paper we propose a data discovery and cache management policy for cooperative caching, which reduces the power usage, caching overhead and delay by reducing the number of control messages flooded into the network .A cache discovery process based on position cordinates of neighboring nodes is developed for this .The stimulstion results gives a promising result based on the metrics of the studies.

Predicted impact of the sea-level rise at VellareColeroon estuarine region of Tamil Nadu coast in India: Mainstreaming adaptation as a coastal zone management option

Low-lying coastal areas are more vulnerable to the impacts of climate change as they are highly prone for inundation to SLR (Sea-Level Rise). This study presents an appraisal of the impacts of SLR on the coastal natural resources and its dependent social communities in the low-lying area of VellareColeroon estuarine region of the Tamil Nadu coast, India. Digital Elevation Model (DEM) derived from SRTM 90M (Shuttle Radar Topographic Mission) data, along with GIS (Geographic Information System) techniques are used to identify an area of inundation in the study site. The vulnerability of coastal areas in Vellar-Coleroon estuarine region of Tamil Nadu coast to inundation was calculated based on the projected SLR scenarios of 0.5 m and 1 m. The results demonstrated that about 1570 ha of the LULC (Land use and Land cover) of the study area would be permanently inundated to 0.5 m and 2407 ha for 1 m SLR and has also resulted in the loss of three major coastal natural resources like coastal agriculture, mangroves and aquaculture. It has been identified that six hamlets of the social communities who depend on these resources are at high-risk and vulnerable to 0.5 m SLR and 12 hamlets for 1 m SLR. From the study, it has been emphasized that mainstreaming adaptation options to SLR should be embedded within a coastal zone management and planning effort, which includes all coastal natural resources (ecosystem-based adaptation), and its dependent social communities (community-based adaptation) involved through capacity building

Spatial Variability and Contamination of Heavy Metals in the Inter-tidal Systems of a Tropical Environment

Heavy metals in the surface sediments of the two coastal ecosystems of Cochin, southwest India were assessed. The study intends to evaluate the degree of anthropogenic influence on heavy metal concentration in the sediments of the mangrove and adjacent estuarine stations using enrichment factor and geoaccumulation index. The inverse relationship of Cd and Zn with texture in the mangrove sediments suggested the anthropogenic enrichment of these metals in the mangrove systems. In the estuarine sediments, the absence of any significant correlation of the heavy metals with other sedimentary parameters and their strong interdependence revealed the possibility that the input is not through the natural weathering processes. The analysis of enrichment factor indicated a minor enrichment for Pb and Zn in mangrove sediments. While, extremely severe enrichment for Cd, moderate enrichment for Zn and minor enrichment of Pb were observed in estuarine system. The geo accumulation index exhibited very low values for all metals except Zn, indicating the sediments of the mangrove ecosystem are unpolluted to moderately polluted by anthropogenic activities. However, very strongly polluted condition for Cd and a moderately polluted condition for Zn were evident in estuarine sediments