An investigation into the oxidation of organic sulphides, organic selenides and simple hydrocarbons by Mortierella isabellina NRRL 1757

The work presented in this thesis is divided into three separate sections 4!> Each' 'section is involved wi th a different problem, however all three are involved with a microbial oxidation of a substrate~ A series of 'aryl substituted phenyl a.nd be,nzyl methyl sulphides were oxidized to the corre~pondi~g sulphoxides by 'Mo:rtierellai's'a'b'e'llina NRR.L17'S7 @ For this enzymic Qxidation, based on 180 labeled experiments, the oxygen atom is derived fr'orn the atmosphere and not from water. By way of an u~.traviolet analysis, the rates of oxidation, in terms of sulphox~ de appearance, were obtained and correlated with the Hatnmett p s~grna constants for the phenyl methyl sulphide series. A value of -0.67 was obtained and, is interpreted in terms of a mechanism of oxidation that involves an electrophilic attack on the sulphide sulphur by an enzymic ironoxygen activated complex and the conversion of the resulti!lg sulphur cation to sulphoxide. A series of alkyl phenyl selen~des have been incubated with the fu~gi, Aspergillus niger ATCC9l42, Aspergillus fO'etidus NRRL 337, MIIJisabellina NF.RLl757 and'He'lminth'osparium sp'ecies NRRL 4671 @l These fu?gi have been reported to be capable of carrying out the efficient oxidation of sulphide to sulphoxide, but in no case was there any evidence to supp'ort the occurrence of a microbialox,idation. A more extensive inves·t~gation was carried out with'M,e 'i's'a'b'e'l'l'i'na, this fu~gus was capable of oxidizing the correspondi~g sulphides to sulphoxi.de·s·$ Usi:ng a 1abel.edsubstra.te, [Methyl-l4c]-methyl phenyl selenide, the fate of this compound was invest~gated followi!lg an i'ncubation wi th Me isabellina .. BeSUldes th. e l4C-ana1YS1Q S-,'. a quant"ltta"lve selen'lum ana1Y"S1S was carried out with phenyl methyl selenide. These techniques indicate that thesel'enium was capable of enteri!1g thefu!1gal cell ef'ficiently but that s'ome metabolic cleav~ge of the seleni'um-carbon bond' may take plac'e Ie The l3c NMR shifts were assigned to the synthesized alkyl phenyl sulphides and selenides@ The final section involved the incubation ofethylben~ zene and p-e:rtr.hyltoluene wi th'M ~ 'isab'e'llina NRRL 17574b Followi~ g this incubation an hydroxylated product was isolated from the medium. The lH NMR and mass spectral data identify the products as I-phenylethanol and p-methyl-l-phenylethanol. Employi!lg a ch'iral shift re~gent,tri~ (3-heptafluorobutyl-dcamphorato)'- europium III, the enantiomeric puri ty of these products was invest~gated. An optical rotation measurement of I-phenylethanol was in ~greement with the results obtained with the chiral shift re~gen,te 'M.isabe'l'lina is capable of carryi~g out an hydroxylation of ethylbenzene and p-ethyltoluene at the ~ position.

Synthesis and properties of some 4H-1, 3, 4 benzothiadiazines /|nby Darko J. Vukov. -- 260 St. Catharines, Ont. : [s. n.],

The work herein has been divided into five sections. In the first section, a new method of converting N-aroyl- hydrazines to hydrazidic halides is described. The second section deals with the products of reaction of hydrazidic halides with thioacetate ion in acetonitrile at room temperature. A number of new acetylthiohydrazides has been isolated together with corresponding hyclrazidic sulphides. Examination of x-ray data for bis-[~ -(2,6- dibromophenylhydrazono) - benZYl] sulphide revealpd the symmetrical structure as the most probable. In the third section, which consists of the three subsections, the synthesis of the 4H-l,3,4 benzothiadiazine ring system has been extended to 4H-l,3,4 benzothiadiazines with substituents in the 5 and 6-positions. Extension of synthesis also involves 4H-l,3,4 benzothiadiazines with mora than one substituent. Nuclear magnetic resonance spectra of 5 and 6 substituted 4H-l,3,4 benzothiadiazines have been ,. recorded. The section ends with a discussion of the mass spectra of some 4H-l.3,4 benzothiadiazines. In the fourth section, which is divided into two sub- -sections, preparation of 7-nitro substituted 4H-l,3,4 benzothiadiazine from N-thiobenzoyl hydrazine and2,4-dinitro -fluorobenzene is found to be satisfactory. Thiohydrazides react with acetic anhydride, in some cases, to give products identical with acetylthiohydrazides obtained from the hydrazidic halides with thioacetate ion at room temperature. In most of the cases thiohydrazides are found to give anomalous products on reaction with acetic anhydride and mechanisms for their formation are discussed. In the fifth section, which forms three subsections, the 4H-l,3,4 benzothiadiazine ring system with a halogen substituent in the 7-position undergoes electrophilic attack preferentially in 5-posi tion. \fuen the 5-posi tion is occupied by a halogen atom, electrophilic substitution occurs at the 7-position of 4H-l,3,4 benzothiadiazine ring system. Substitution at the 4-nitrogen atom in 4H w l,3,4 benzo- -thiadiazine is extremely slow, probably due to delocalisa- -tion of the nitrogen lone pair in the system. Oxidation of 4H-l,3,4 benzothiadiazines occurs at the sulphur atom under relatively mild conditions. t The Appendix deals with the reaction of N-benzoyl-N - -(2,5-dibromophenyl)hydrazine with p-nitrothiophenol~ The proposed p-nitrothiophenoxy - intermediate may undergo benzothiadiazine formation in a proton exchange system.

The suppression of the Haller-Bauer scission for synthetic purposes /|nby S. M. Vines. -- 260 St. Catharines, Ont. : [s. n.],

A number of 2-chlorobenzophenones, containing electron releasing groups (e.g. hydroxy, thiomethoxy and methoxy) in the 4' - position, were prepared by the Friess rearrangement, or the Friedel-Crafts reaction. These ketones, when treated with potassamide in liquid ammonia, underwent partial Haller-Bauer scission, unlike 2-chlorobenzophenone which is known to undergo complete scission. Under similar conditions 4-nitrobenzophenone also underwent partial scission, but the main reaction in this case was nucleophilic amination of the nitro containing ring. This amination reaction was shown not to be a useful general reaction for aromatic nitro compounds. 3-Methylxanthone was then prepared by treatment of 2- and 3- chloro-2'-hydroxy-5'-methylbenzophenone with . little, if any, attendant scission. The corresponding 2fluoro- compound also gave the xanthone, but as the 3-fluoro compound did not, it was concluded that the 2-fluoro compound reacted through a nucleophilic substitution mechanism, rather than the benzyne mechanism invoked for the chloro and bromo compounds. 3-Methylthioxanthone was synthesised by treatment of methyl 4-tolyl sulphide and 2-chlorobenzoyl chloride with aluminum chloride in carbon disu1phide, followed.by heating. This compound was also prepared by treatment of 3-chloro-2'thiomethoxy- 5'-methylbenzophenone with potassamide in liquid ammonia.

Preparation and characterisation of certain II-VI, I-III-VI2 semiconductor thin films and transparent conducting oxides

There is an increasing demand for renewable energies due to the limited availability of fossil and nuclear fuels and due to growing environmental problems. Photovoltaic (PV) energy conversion has the potential to contribute significantly to the electrical energy generation in the future. Currently, the cost for photovoltaic systems is one of the main obstacles preventing production and application on a large scale. The photovoltaic research is now focused on the development of materials that will allow mass production without compromising on the conversion efficiencies. Among important selection criteria of PV material and in particular for thin films, are a suitable band gap, high absorption coefficient and reproducible deposition processes capable of large-volume and low cost production. The chalcopyrite semiconductor thin films such as Copper indium selenide and Copper indium sulphide are the materials that are being intensively investigated for lowering the cost of solar cells. Conversion efficiencies of 19 % have been reported for laboratory scale solar cell based on CuInSe2 and its alloys. The main objective of this thesis work is to optimise the growth conditions of materials suitable for the fabrication of solar cell, employing cost effective techniques. A typical heterojunction thin film solar cell consists of an absorber layer, buffer layer and transparent conducting contacts. The most appropriate techniques have been used for depositing these different layers, viz; chemical bath deposition for the window layer, flash evaporation and two-stage process for the absorber layer, and RF magnetron sputtering for the transparent conducting layer. Low cost experimental setups were fabricated for selenisation and sulphurisation experiments, and the magnetron gun for the RF sputtering was indigenously fabricated. The films thus grown were characterised using different tools. A powder X-ray diffractometer was used to analyse the crystalline nature of the films. The energy dispersive X-ray analysis (EDX) and scanning electron microscopy i (SEM) were used for evaluating the composition and morphology of the films. Optical properties were investigated using the UV-Vis-NIR spectrophotometer by recording the transmission/absorption spectra. The electrical properties were studied using the two probe and four probe electrical measurements. Nature of conductivity of the films was determined by thermoprobe and thermopower measurements. The deposition conditions and the process parameters were optimised based on these characterisations.

Bioremediation in Shrimp Culture Systems

Budidaya menghasilkan sejumlah besar limbah, terdiri dari metabolisme oleh-produk, makanan sisa, materi feses dan residu dari masukan profilaksis dan terapeutik, mengarah pada penurunan kualitas air dan wabah penyakit. Bioremediasi, aplikasi mikroba / enzim untuk tambak, adalah metode yang sedang digunakan untuk meningkatkan kualitas air dan menjaga kesehatan dan stabilitas sistem akuakultur. Bioremediasi melibatkan mineralisasi bahan organik menjadi karbon dioksida, memaksimalkan produktivitas primer yang merangsang produksi udang, nitrifikasi dan denitrifikasi untuk (1) menghilangkan kelebihan nitrogen dari tambak dan (2) mempertahankan beragam dan stabil masyarakat kolam dimana patogen dikeluarkan dari sistem dan spesies diinginkan mendapatkan didirikan. Selain dari bahan organik merendahkan (detritivorous) bakteri heterotrofik, nitrifikasi, bakteri denitrifikasi dan fotosintesis umumnya digunakan dalam bioremediasi.

Unraveling a Benchmark for Sulphur Akin in the Cochin Estuarine System

The thesis deals with a benchmark study of dissolved and sedimentary sulphur compounds which play prominent roles in the prevailing redox conditions in the selected sites of Cochin estuarine system. Sulphur and its analogues play prominent roles in estuarine biochemical processes. A complete knowledge on the sulphur involvement in these processes is restricted due to the lacking of data on the organic sulphur compounds. Sulphate and sulphide in surface and bottom water and Sulphate, acid volatile sulphide and total sulphur in sediments were studied and correlated to know their interrelations in determining the redox condition of the environment. It also characterises the sediments of the sites on the basis of total organic carbon: total sulphur ratio. The study had attempted to decrease the concentration levels of sulphur in the sedimentary environment by the application of a remedial measure. Knowledge of sulphur uptake by plants from prior literatures has prompted to use phytoremediation for decreasing the sulphur concentration. Phytoremediation is an emerging technology that uses plants to clean up or remediate contaminated soil, sludges, sediments, and ground water through contaminant removal, degradation or containment. The plant selected was wheat grass since earlier studies have shown that wheat grass is effective in remediating pollutants particularly trace metals. So reduction in the concentration of selected trace metals was also focussed.

Fluorescenec Emission of SrS:Eu2+ Phosphor-Energy Level Splitting of Eu2+

A method of preparation of strontium sulphide phosphors doped with europium is given. Nitrogen laser excited fluorescence emission spectra of these phosphors in the visible region are recorded. A band with line structure in the region 350-430 nm and a new broad band at 460 nm are observed. The splitting pattern for the 6p levels of Eu 2+ are given.

Investigations On The Electrical Characteristics Of Certain Semiconductor Films And Polymerized Para-Toluidine Films

The thesis is a report of the attempts made to prepare semiconducting and dielectric thin films and to study their electrical properties. It consists of (i) studies on the preparation and electrical characteristics of compound semiconductor thin films of silver sulphide and ferric hydroxide, and (ii) investigations on the electrical and dielectric properties of plasma polymerized thin films of para-toluidine element

Retting Of Coconut Husk - A Unique Case Of Water Pollution On The South West Coast Of India

The extensive backwaters of Kerala are the sites for a flourishing cottage industry - the coir industry. This enterprise almost exclusively located along the 590 km coastal belt of Kerala, provides direct employment to over half a million people in the state and produces nearly 90% of the total coir goods in the world. The shallow bays and lagoons of the 30 backwater systems of the state are traditional areas for the retting of coconut husk for the production of the coir fibre. The paper examines the environmental status of the retting grounds in Kerala, in relation to the biotic communities. The study revealed that retting activity has caused large scale organic pollution along with the mass destruction of the flora and fauna, converting sizeable sections of the backwaters into virtual cesspools of foul smelling stagnant waters. High values of hydrogen sulphide, ammonia, BOD5 associated with anoxic conditions and low community diversity of plankton, benthic fauna, fish, shell fish, wood boring and fouling organisms were the outstanding feature of the retting zones.

Water quality status and Primary productivity of Valanthakad Backwater in Kerala

The water quality and primary productivity of Valanthakad backwater (9° 55 10. 24 N latitude and 76° 20 01. 23 E longitude) was monitored from June to November 2007. Significant spatial and temporal variations in temperature, transparency, salinity, pH, dissolved oxygen, sulphides, carbon dioxide, alkalinity, biochemical oxygen demand, phosphatephosphorus, nitrate-nitrogen, nitrite-nitrogen as well as primary productivity could be observed from the study. Transparency was low (53.75 cm to 159 cm) during the active monsoon months when the intensity of solar radiation was minimum, which together with the run off from the land resulted in turbid waters in the study sites. The salinity in both the stations was low (0.10 ‰ to 4.69 ‰) except in August and November 2007. The presence of total sulphide (0.08 mg/ l to 1.84 mg/ l) and higher carbon dioxide (3 mg/ l to 17 mg/ l) could be due to hospital discharges and decaying slaughter house wastes in Station 1 and also from the mangrove vegetation in Station 2. Nitrate-nitrogen and phosphate-phosphorus depicted higher values and pronounced variations in the monsoon season. Maximum net primary production was seen in November (0.87 gC/ m3/ day) and was reported nil in September. The chlorophyll pigments showed higher values in July, August and November with a negative correlation with phosphate-phosphorus and nitrite-nitrogen. The study indicated that the water quality and productivity of Valanthakad backwater is impacted and is the first report from the region

Primary Productivity Of The Retiing Zones In The Kadinamkulamestuary, South-West Coastof India

Retting.of coconut husk is one of the major problems of pollution in the estuaries (Kayals) of Kerala. This paper discusses the salient features associated with the variation in gross and net primary productivity values in the Kadinarnkularn Kayal based on lortnightlydala from twosclected stations frorn Octobcr1987 to September 1988.The gross primary productivity value in the surface water ranged from 0.06 to 0.29gC/m3/day at Station Iand from 0.06 to 1.49gC/rn3/dayatstation II. In the bottom wateritrangcdfrorn oto 0.21 gC/m2/ day at station I whereas that at station II from 0.03 to 1.41gC/m3j day. The net productivity in the surface water at station I varied from 0 to 024 gC/m Iday Whereas that atstation II varied from 0.02to 1.44gC/m3Iday.AI the bottomwaterilvaried from ato 0.19gC/m3/ day at station I and from 0.01 to 1.21gC/m3/day at station II. The monsoon period showed the highest mean seasonal value at stations I and II. The total depletion of dissolved oxygen giving rise to anoxic condition coupled with the production of large quantities of hydrogen sulphide was found to be detrimental to the gross and net productivity values in the retting zone

Current status and biodiversity modification in the coastal wetland ecosystems of India with objectives for its sustainable management

The South West (S.W.) coast of India is blessed with a series of wetland systems popularly referred to as backwaters covering a total area of 46128.94 ha. These backwaters are internationally renowned for their aesthetic and scientific values including being a repository for several species fish and shell fishes. This is more significant in that three wetlands (Vembanad, Sasthamcotta and Ashtamudi) have recently been designated as Ramsar sites of international importance. Thirty major backwaters forming the crux of the coastal wetlands form an abode for over 200 resident or migratory fish and shellfish species. The fishing activities in these water bodies provide the livelihood to about 200,000 fishers and also provide full-time employment to over 50,000 fishermen. This paper describes the changes on the environmental and biodiversity status of selected wetlands, during 1994-2005 period. The pH was generally near neutral to alkaline in range. The salinity values indicated mixohaline condition ranging from 5.20-32.38 ppt. in the 12 wetlands. The productivity values were generally low in most of the wetlands during the study, where the gross production varied from 0.22 gC/m3/day in Kadinamkulam to 1.10 gC/m3/day in the Kayamkulam. The diversity of plankton and benthos was more during the pre-monsoon compared to the monsoon and post-monsoon periods in most of the wetlands. The diversity of plankton and benthos was more during the pre-monsoon compared to the monsoon and post-monsoon periods in most of the wetlands. The average fish yield per ha. varied from 246 kg. in Valapattanam to 2747.3 kg. in Azhikode wetland. Retting of coconut husk in most of the wetlands led to acidic pH conditions with anoxia resulting in the production of high amounts of sulphide, coupled with high carbon dioxide values leading to drastic reduction in the incidence and abundance of plankton, benthic fauna and the fishery resources. The major fish species recorded from the investigation were Etroplus suratensis, E. maculatus, Channa marulius, Labeo dussumieri, Puntius sp. Lutianus argentimaculatus, Mystus sp., Tachysurus sp. and Hemiramphus sp. The majority of these backwaters are highly stressed, especially during the pre monsoon period when the retting activity is at its peak. The study has clearly reflected that a more restrained and cautious approach is needed to manage and preserve the unique backwater ecosystems of South-west India

Formation of anoxia and denitrification in the bottom waters of a tropical estuary, southwest coast of India

Hydrographic characteristics of the southwest coast of India and its adjoining Cochin backwaters (CBW) were studied during the summer monsoon period. Anomalous formation of anoxia and denitrification were observed in the bottom layers of CBW, which 5 have not been previously reported elsewhere in any tropical estuarine systems. The prevalent upwelling in the Arabian Sea (AS) brought cool, high saline, oxygen deficient and nutrient-rich waters towards the coastal zone and bottom layers of CBW during the high tide. High freshwater discharge in the surface layers brought high amount of nutrients and makes the CBW system highly productive. Intrusion of AS waters seems 10 to be stronger towards the upstream end ( 15 km), than had been previously reported, as a consequence of the lowering of river discharges and deepening of channels in the estuary. Time series measurements in the lower reaches of CBW indicated a low mixing zone with increased stratification, 3 h after the high tide (highest high tide) and high variation in vertical mixing during the spring and neap phases. The upwelled waters 15 (O2 40 μM) intruded into the estuary was found to lose more oxygen during the neap phase (suboxic O2 4 μM) than spring phase (hypoxic O2 10 μM). Increased stratification coupled with low ventilation and presence of high organic matter have resulted in an anoxic condition (O2 = 0), 2–6 km away from barmouth of the estuary and leads to the formation of hydrogen sulphide. The reduction of nitrate and formation of nitrite 20 within the oxygen deficient waters indicated strong denitrification intensity in the estuary. The expansion of oxygen deficient zone, denitrification and formation of hydrogen sulphide may lead to a destruction of biodiversity and an increase of green house gas emissions from this region

Spray pyrolysed In2S3 thin films: A potential electron selective layer for large area inverted bulk-heterojunction polymer solar cells

In this paper, we report the results of investigations on the potential of spray pyrolysis technique in depositing electron selective layer over larger area for the fabrication of inverted bulk-heterojunction polymer solar cells. The electron selective layer (In2S3) was deposited using spray pyrolysis technique and the linear heterojunction device thus fabricated exhibited good uniformity in photovoltaic properties throughout the area of the device. An MEH-PPV:PCBM inverted bulk-heterojunction device with In2S3 electron selective layer (active area of 3.25 3.25 cm2) was also fabricated and tested under indoor and outdoor conditions. Fromthe indoor measurements employing a tungsten halogen lamp (50mW/cm2 illumination), an opencircuit voltage of 0.41V and a short-circuit current of 5.6mA were obtained. On the other hand, the outdoor measurements under direct sunlight (74mW/cm2) yielded an open-circuit voltage of 0.46V and a short-circuit current of 9.37mA