Synergic Reactions in the Estuarine Environment leading to Modulation of Aluminium metal during Transport Processes (in Cochin Estuary)

The research work which was carried out to Synergic Reactions in the Estuarine Environment leading to Modulation of Aluminium metal during Transport Processes (in Cochin Estuary)Estuaries are considered as sink or source for terrestrial and various anthropogenically generated materials. These include naturally occurring elements Al, Si, Fe or trace inorganics or industrial pollutants of different types. There have been reports on both positive and negative impacts by the introduction of above materials into the ecosystem.This thesis deals with the trace metal Aluminium (Al) whose average concentration (about 8%) in the earths crust is surpassed only by that of Oxygen and Silicon. There can be no doubt that most of the land derived materials reaches the ocean through rivers via estuaries. An important aspect noticed here is that the concentration of dissolved Al is much lower in sea water than in river water.On critically analysing Cochin estuary, for the entire cycles, covering monsoon, postmonsoon and premonsoon, the following salient features are documented as hereunder. Dissolved Al exhibits high and variable trends in Cochin estuary, the influencing parameters being salinity, SPM, pH and dissolved Si. A general profile showed removal in upper/mid estuary followed by regeneration in the mid/lower estuary and further decrease seawards in the southern/northem arms.Distribution appears to be a function of freshwater input, the monsoon season exhibiting very high concentrations throughout the estuary. As the river discharge decreased with the progress of seasons, dissolved Al concentration also decreased, the metal limiting itself to the upper and mid estuary.

Synthesis and reactions of flavazoles

The study deals with the production of l-phenylflavazoles with chloro, amino, hydroxy, chloromethyl, carboxamido, trichloromethyl, N-pyrrolidyl and N-pyrrolidylmethyl groups substituted at position 3. The interconversions of 3-amino, 3-hydroxy and 3-chlorol- phenylflavazoles were also investigated. Further, an unusual phenylation reaction was found to take place if stored or air-oxidised phenylhydrazine was used as the condensing agent for the formation of flavazoles from quinoxaline-2-carboxaldehyde phenylhydrazones. By this phenylation reaction 1,3-diphenyl, l-p-tolyl-3-phenyl, l-p-chlorophenyl-3-phenyl, l-p-bromophenyl- 3-phenyl and l-phenyl-3-p-tolylflavazoles were prepared. In addition to establishing the structure of the phenylation products, the reaction was shown to take place by a free radical mechanism involving phenyl radicals formed from oxidised phenylhydrazine. Also the oxidation, reduction and bromination reactions of l-phenylflavazole were investigated. The product obtained when a mixture of l-phenylflavazole and sodium borohydride in isopropanol was heated under reflux was shown to be 2-anilinoquinoxaline-3-carboxamide which when refluxed with concentrated hydrochloric acid gave the known 2-anilinoquinoxaline. New procedures were worked out for the oxidative cyclisation reactions of quinoxaline-2carboxaldehyde phenylhydrazones to l-phenylflavazoles in excellent yields using azobenzene as a dehydrogenating agent. These cyclisations were also shown to take place, though in low Yield, if the quinoxaline2- carboxaldehyde phenylhydrazones were heated above their melting points in an atmosphere containing oxygen.

Palladium Catalyzed Carbon-Carbon/Carbonheteroatom Bond Formation Reactions Utilizing Pentafulvene Derived Bicyclic Hydrazines

The reactions involving fulvenes and its derivatives have received a great deal of attention over the years in synthetic organic chemistry. Functionalizations of fulvenes provide versatile and powerful approaches to various polycyclic systems and natural products. They serve as versatile intermediates in the construction of various ring systems through inter- as well as intramolecular cycloadditions. Compared to the rich literature on the cycloaddition reactions of pentafulvenes, much less attention has been paid to the synthetic utilization of their cycloadducts. Tactical manipulations on the chosen adduct offer the prospects for designing a variety of useful molecular skeletons. Addition of heterodienophiles to fulvenes offers an efficient strategy towards the synthesis of azabicyclic olefins. However, there have been no serious attempts to study the synthetic utility of these substrates. In this context and with the intention of utilizing pentafulvenes towards synthetically important molecules, author decided to explore the reactivity of pentafulvene derived azabicyclic olefins. Our attention was focused on the synthetic potential associated with the ring opening of fulvene derived bicyclic hydrazines under palladium catalysis. It was envisioned that the desymmetrization of these adducts using various soft nucleophiles will provide a novel access to synthetically and biologically important alkylidene cyclopentenes. The investigations along this line form the focal theme of this thesis entitled “PALLADIUM CATALYZED CARBONCARBON/ CARBON-HETEROATOM BOND FORMATION REACTIONS UTILIZING PENTAFULVENE DERIVED BICYCLIC HYDRAZINES

Synthesis And Reactions Of Pyrazoldouinoxalines

The present work reports the synthesis of 2-ary1—3—oxo-3—pyrazolino[3,4-b]quinoxalines for the first time. These compounds have been prepared by the reaction of ethyl 2-chloroquinoxaline—3—carboxylate with different phenylhydrazines. 2-Aryl—3-oxo—3—pyrazolino[3,4—b]quinoxalines are generally light yellow in either neutral or acid solutions but changed the colour to deep violet or green in basic media. The change in colour appears to be sharp and therefore these compounds may be used as acid base indicators. Their UV absorption maxima under acidic and basic media are also very different. However, the actual conditions under which these compounds may be used as indicators have not been worked out. The synthesis and reactions of a new heterocyclic system, lH—l,5—benzodiazepino[2,3—b]quinoxaline is also reported here. This novel nitrogen heterocycke was prepared by the condensation of ethyl 2-chloroquinoxaline-3—carboxylate with o-phenylene diamine and subsequent manipulationsa to give the parent compound. Several derivatives which are expected tx> have valuable biological properties have also beenlreported. The structures of all new compounds have been established by elemental analysis and also by analysing their spectral data smch as ultraviolet, infrared, nuclear magnetic resonance and mass spectrometry. Compounds obtained from this work will be submitted for screening their biological properties.

Enzyme reactions as index of freshness of Fish and Shellfish

An attempt has been made in this study to screen some fish muscle enzymes to assess their potential worth in testing the degree of freshness of fish. A problem with routine enzyme activity determinations is the complexity of the method of enzyme assay. Hence, in the present study as far as possible simple assay techniques were adopted. Several species were screened to assess the possibility of employing this procedure on a large scale. It is hoped that findings of this study will lead to the development of meaningful criteria in testing the freshness of fish. This thesis has been divided into five chapters

Kinetics and mechanism of urea - formaldehyde and related reactions

Urea-formaldehyde resins find numerous applications in adhesive, textile finishing and moulded plastic industries. Kinetic investigations of the reactions of urea and its related compounds with formaldehyde in aqueous acid, alkaline and neutral media have been carried out. A thin—layer chromatographic method was developed for the separation and estimation of the products of these reactions. Using this technique the various initial steps in the reactions were analysed and the rate constants have been determined.

“A comparative study of medium and large pore zeolites in alkylation reactions”

Zeolites have established themselves as industrial catalysts for over two decades for a variety of hydrocarbon processing reactions where acidity and shape selectivity are important factors. As solid catalysts, zeolites may be advantageous and superior compared to their homogenous counterparts due to their characteristic properties. It is only in recent years that the utility of zeolites for organic synthesis is recognized for producing specific organic intermediates and fine chemicals in high selectivity. In this thesis an attempt has been made to compare the catalytic activity of some medium and large pore zeolites in a few alkylation and acylation reactions. The work reported in the present study is basically centered around the following zeolites namely, ZSM-5, mordenite, zeolite Y and beta. The major reactions carried out were benzoylation of o-xylene, propionylation of toluene and anisole and benzylation of oxylene. . The programme involves the synthesis, modifications and characterization of the zeolite catalysts by various methods. The influence of various parameters such as non-framework cations, Si/Al ratio of zeolites, temperature of the reaction, catalyst concentration, molar ratio of the reactants and recycling of the catalysts were also examined upon the conversion of reactants and the formation of the desired products in the alkylation/ acylation reactions. The general conclusions drawn by us from the results obtained are summarized in the last chapter of the thesis. Zeolite beta ofi'ers interesting opportunities as a potential catalyst in alkylation reactions and the area of catalysis by medium and large pore zeolites is very fascinating and there is plenty of scope for further research in this field. Moreover, zeolite based catalysts are effective in meeting current industrial processing and more stringent environment pollution limits.

Learning From Cross Country Experiences In Housing: A Micro Finance Approach For Inclusive Housing In India

Housing is one of the primary human needs. It is second only to the need for food and clothing. From a macro perspective, housing is an industry that can prove itself to be a growth engine for a nation, particularly a developing nation like India. Housing has been one of the top priorities for the various governments in India since the seventies. The need for housing has been increasing at a phenomenal pace in India and so also the need for housing finance. Since the growth in supply of housing could not keep pace with the growth in its demand, housing shortage has been on the rise over the years. Housing finance industry which was relatively dormant till the early nineties underwent sweeping changes ever since the initiation of financial sector deregulation measures. Financial deregulation measures brought about several changes in this industry, the first and foremost being the fast growth rate in the industry coupled with cutthroat competition among the industry players. This trend has been quite prominent since the entry of commercial banks into this arena. Accordingly, there has been a surge in the growth of retail (personal) loans segment, particularly in respect of housing loans. This is evident from the fact that housing loans disbursed by banks as a percentage of their total loans has increased from just 2.79% as of end-March 1997 to as high as 12.52% as of end-March 2007. Thus, there has been an unprecedented growth rate in the disbursement of housing loans by banks, and as of 31 March 2007 the outstanding balance of housing loans by all banks in India stands at Rs.230689 Crore, as against just Rs.7946 Crore as of 31 March 1997, the growth rate being 35.82 %CAGR (for the eleven years’ period, FY 1997-‘2007). However, in spite of the impressive growth in housing finance over the years, there are growing apprehensions regarding its inclusiveness, i.e. accessibility to the common man, the underprivileged sections of the society to housing finance etc. Of late, it is widely recognized that formal housing finance system, particularly the commercial banks (CBs) – most dominant among the players – is fast becoming exclusive in operations, with nearly 90% of the total housing credit going to the rich and upper middle income group, primarily the salaried class. The case of housing finance companies (HFCs) is quite similar in this regard. The poor and other marginalized sections are often deprived of adequate credit facilities for housing purpose. Studies have revealed that urban housing poverty is much more acute than the rural probably because of the very fast process of urbanization coupled with constant rural to urban migration

Novel [3+2] annulation reaction of nitrones with Burgess reagent and a few related reactions

Burgess reagent first prepared by E. M. Burgess in 1968, is a mild and selective dehydrating agent for secondary and tertiary alcohols and due to the amphipolar nature it is gainfully employed in a number of creative synthetic ventures. A close examination of the structure of Burgess reagent reveals that it can act as a 1,2-dipole. To the best of our knowledge, no attempts have been made to tap full synthetic potential of the amphipolar nature of this reagent and no reports on 1,3-dipolar addition to a σ-bond in acyclic systems are available in literature. In this context, we propose to unravel novel applications of Burgess reagent based on its amphipolar nature. Rich and multifaceted chemistry of nitrones form the basis of many successful chemical transformations used in attractive synthetic strategies. For the last 50 years special attention has been given to nitrones due to their successful application as building blocks in the synthesis of various natural and biologically active compounds. Our interest in nitrones stems out of its unique character: i.e. it is a 1,3-dipole exhibiting distinct nucleophilic activity. We reasoned that 1,3-dipole possessing significant nucleophilicity should react with amphipolar Burgess reagent with elimination of triethylamine to give the corresponding five-membered ring product by formal dipolar addition to a σ bond. To test this hypothesis we studied the reaction of nitrones with Burgess reagent. This thesis reveals our attempts to explore the [3+2] annulation reaction of nitrones with Burgess reagent which was found to be followed by a rearrangementinvolving C-to-N aryl migration, ultimately resulting in diarylamines and carbamates. We have also examined the reaction of cyanuric chloride with nitrones in DMF with a view to exploit the nucleophilicty of nitrones and to unravel the migratory aptitude, if any, observed in this reaction

Exploration of Novel Organic Reactions Catalyzed by Nucleophilic Heterocyclic Carbenes (NHCs)

The thesis entitled “Exploration of Novel Organic Reactions Catalyzed by Nucleophilic Heterocyclic Carbenes (NHCs)” embodies the results of the investigations carried out to explore the synthetic potential of N–heterocyclic carbenes (NHCs) as organocatalyst towards various electrophiles for the synthesis of heterocyclic and carbocyclic systems. Recent investigations in the generation of homoenolates by the addition of NHCs to conjugated aldehydes have made it possible to study the reactivity of this unique three carbon synthon.

Investigations on electron transfer reactions of a few anthracenemethyl sulfides with suitable electron acceptors and related studies

Cochin University of Science & Technology

Community Participation in Ecotourism: An Inclusive Development Option for Kerala

The inferences obtained from the study are presented in coherent area-specific levels so as to understand the ecotourism and its sub-sector areas for the researchers and policy makers about the issues, importances and potentialities of the sector. An analysis of the tourism sector in Kerala has shown tremendous growth both in terms of tourist arrivals and in terms of revenue generation from direct and indirect sources. The foreign tourist visitors in Kerala in 2014 was 9,23,336 which shows 7.60 percent increase from the last year and the domestic tourist visitors were 1,16,95,411 which again shows 7.71 percent increase, is a clear evidence of its potential. In 2014 the industry contributed revenue of 24885.44 crores from direct and indirect sources giving rise to an increase of 12.11 percent from the last year. A dichotomy of tourists and ecotourists shows that tourists in the ecotourism destinations come to 42.6 percent of the total, shows the scope, significance and its potential. Correlation of zone-wise tourist arrivals based on the ecotourism destinations highlights the fact that with only 19 of the 64 destinations that come in the central zone are the most preferred centres (around 54 percent) for the domestic as well as foreign tourists. The north zone encompassing 6 districts with rich biodiversity shows that the tourists‟ arrival patterns exhibit less promising results. Though the north zone has 31 ecotourism destinations of the state receives only 6.19 percent of the foreign visitors. The ecotourism activities in the state are primarily managed by the Eco-Development Committees (EDCs) and the Vana Samrakshana Samithies (VSS) under the Forest Development Agency of Kerala. Social class-wise categorization of membership shows that 13142 families have membership in 190 EDCs with SC (28 percent), ST (33 percent) and other marginalised communities (39 percent). But this in the VSS shows that 400 VSS have 59085 members actively engaged in ecotourism activities and social category of the VSS makes clear that majority are from the other marginalized fringe households with 62 percent where as the participation of SC is 12 percent and ST is 26 percent. An evaluation of the socio-economic and demographic matrix of the community members involved in ecotourism activities brings out region specific differences. About 75.70 percent of the respondents are males and the rest are females. Majority of the respondents (about 60 percent) are in the age group of 20 to 40 years, followed by the age group of 40-50 (20 percent). The average age of respondents in the three zones is between 35 and 37 years. The majority of the respondents are married, a few are unmarried. Average family size is 4-5 members and differences are identified among zones. Average number of adults per household is 3 and child per household is 2. Majority have an education of 10th class and below i.e. about 60 percent of the sample have only basic school education like primary, secondary and high school (i.e. up to SSLC but not passed) level. About 18 percent are SSLC passed, 10 percent are undergraduates whereas 6 percent constitute respondents having qualification of graduation and above. Majority of the „graduates and above‟ are from south and central zone. Inter-zone differences in educational profile are also identified with lesser number of „graduates and above‟ are identified in the north zone compared to the other two zones. Investigating into the income and livelihood options of the respondents gives insight about the prominence of ecotourism as an employment and livelihood option for the community members, as more than 90 percent of the respondents have cited tourism sector as their main employment option. Most (49.30 percent) of respondents get 100 percent income from tourism related activities, followed by 37.30 percent of community members have income between 75-99 percent from tourism whereas the rest (13 percent) have less than 74 percent of their income from tourism and there exists difference between zones and percentage of income. Financial habit shows that about 49.7 percent hold active bank accounts, 61 percent have savings behaviour and 73.8 percent have indebtedness. Analysis about the ownership of house brings to light that 37 percent of respondents live in their own house followed by 25.7 percent in government funded/provided house and 21 percent in their parent‟s house and 3.5 percent in rented house. About 12 percent of the respondents have other kinds of accommodation facilities such as staff quarters, etc. But in the case of north zone majority i.e. 52 percent primarily depend on the government funded house indicating the effectiveness of government housing programme. Standard of living measured in SLI frameworks shows that majority of the respondents have medium SLI values (42.3 percent); the remaining 47.7 percent have low SLI and 10 percent have high SLI. The community members have been benefitted immensely from forest and its resources. Since the ecotourism destinations are located amidst the wildlife settings, majority of them depend on forest for their livelihood. The information on the tourist‟s demographic characteristics like age, sex, educational qualification and annual income show that the age category of domestic and foreign tourists falls below the age group of less than 35 years (about 65 percent), whereas only 16 percent of tourists are aged above 46 years. The age group below 25 years consists of more international tourists (31.3 percent) compared to the proportion of domestic tourists (12.5 percent). Male-female ratio shows that the males constitute 56 percent of the sample and females with 44 percent. The factors determining the impact of ecotourism programmes in the community was evaluated with the aid of a factor analysis with 12 selected statements. The worries and concerns of the community members about the impact of ecotourism on the environment are well understood from this analysis. It can be drawn that environment protection and the role of ecotourism in improving the income and livelihood options of the local communities is the most important factor concerning the community members.

SHGs and Cooperatives in the Fishing Sector: An Inclusive Development Option for the Fisher folk of Kerala

The Kerala model of development mostly bypassed the fishing community, as the fishers form the main miserable groups with respect to many of the socio-economic and quality of life indicators. Modernization drive in the fishing sector paradoxically turns to marginalization drives as far as the traditional fishers in Kerala are concerned. Subsequent management and resource recuperation drives too seemed to be detrimental to the local fishing community. Though SHGs and cooperatives had helped in overcoming many of the maladies in most of the sectors in Kerala in terms of livelihood and employment in the 1980s, the fishing sector by that time had been moving ahead with mechanization and export euphoria and hence it bypassed the fishing sector. Though it has not helped the fishing sector in the initial stages, but because of necessity, it soon has become a vibrant livelihood and employment force in the coastal economy of Kerala. Initial success made it to link this with the governmental cooperative set up and soon SHGs and Cooperatives become reinforcing forces for the inclusive development of the real fishers.The fisheries sector in Kerala has undergone drastic changes with the advent of globalised economy. The traditional fisher folk are one of the most marginalized communities in the state and are left out of the overall development process mainly due to the marginalization of this community both in the sea and in the market due to modernization and mechanization of the sector. Mechanization opened up the sector a great deal as it began to attract people belonging to non-fishing community as moneylenders, boat owners, employers and middle men which often resulted in conflicts between traditional and mechanized fishermen. These factors, together with resource depletion resulted in the backwardness experienced by the traditional fishermen compared to other communities who were reaping the benefits of the overall development scenario.The studies detailing the activities and achievements of fisher folks via Self Help Groups (SHGs) and the cooperative movement in coastal Kerala are scant. The SHGs through cooperatives have been effective in livelihood security, poverty alleviation and inclusive development of the fisher folk (Rajasenan and Rajeev, 2012). The SHGs have a greater role to play as estimated fall in demand for marine products in international markets, which may result in reduction of employment opportunities in fish processing, peeling, etc. Also, technological advancement has made them unskilled to work in this sector making them outliers in the overall development process resulting in poor quality of physical and social infrastructure. Hence, it is all the more important to derive a strategy and best practice methods for the effective functioning of these SHGs so that the