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Analysis of organochlorine pesticide residues in Malaysian paddy fish and the health risk to human consumptionChen, Donald Fook Koh. January 1982 (has links)
Thesis (DR. P.H.)--University of Michigan.
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Development and demonstration of a biodegradation model for non-aqueous phase liguids in groundwater /De Blanc, Phillip Charles, January 1998 (has links)
Thesis (Ph. D.)--University of Texas at Austin, 1998. / Vita. Includes bibliographical references (leaves 342-347). Available also in a digital version from Dissertation Abstracts.
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Thermal rearrangement of functionalized 6-exo-(1-alkenyl)bicyclo\3.1.0]hex-2-enes application to the total synthesis of (+)-sinulareneJung, Grace Lorena January 1985 (has links)
This thesis describes firstly, a study involving the thermal rearrangement of substituted 6-e̲x̲o̲-(1-alkenyl) bicyclo-[3.1.0]hexenes, and secondly, the application of this type of transformation to a total synthesis of (±)-sinularene (1̲2̲5̲).
The 6-e̲x̲o̲-(1-alkenyl)bicyclo[3.1.0]hexenes (1̲8̲7̲, 1̲8̲9̲, 1̲9̲2̲, 1̲9̲4̲, 2̲4̲0̲, 2̲7̲4̲ and 340) were prepared and thermolyzed in sealed tubes to afford the corresponding bicyclo[3.2.1]octa-2,6-dienes (1̲8̲8̲, 1̲9̲0̲, 1̲9̲3̲, 1̲9̲5̲, 2̲4̲1̲, 2̲7̲6̲ and 3̲4̲1̲) in generally excellent yields. With the exception of 1̲9̲0̲, the thermolysis products were subjected to acid-catalyzed hydrolysis to give the respective bicyclo[3.2.1]octenones. From this study, it is clear that a) the Cope rearrangement of substrates, such as 2̲7̲4̲ and 3̲4̲0̲, containing even sterically bulky substituents on the 6-alkenyl side chain presents a viable means of generating
functionalized bicyclo [ 3.2.1] octa-2 , 6-dienes, b) this methodology provides for the placement of synthetically useful functionalities on any of the carbon bridges of the bicyclo-[3.2.1]octane skeleton, and c) the transformations 2̲4̲0̲→2̲4̲1̲ and 2̲7̲4̲→2̲7̲6̲ provide strong evidence for the stereospecificity of the rearrangement process.
In the total synthesis of (±)-sinularene (1̲2̲5̲), the key step involved the thermal rearrangement of 3̲2̲2̲ to afford the bicyclo[3.2.1]octadiene 3̲2̲1̲. The compound 3̲2̲2̲̲ was readily prepared as follows. 1-Lithio-3-methyl-1-butyne was treated with methacrolein to furnish the allylic alcohol 3̲3̲1̲, which was transformed into the ester 3̲3̲2̲ v̲i̲a̲ an orthoester Claisen rearrangement (hot triethyl .orthoacetate, propionic acid). Hydrolysis of the ester 3̲3̲2̲, followed by reaction of the resultant
acid with oxalyl chloride in refluxing hexane gave the corresponding acid chloride 3̲3̲4̲. Treatment of 3̲3̲4̲ with a cold, ethereal solution of diazomethane afforded the diazo ketone 3̲3̲5̲, which in the presence of copper (II) acetoacetonate in refluxing benzene, underwent an intramolecular carbenoid cyclization
to furnish the bicyclic ketone 3̲3̲6̲. Semihydrogenation of 3̲3̲6̲ using Lindlar’s catalyst gave stereoselectively the c̲i̲s̲-alkenyl ketone 3̲3̲7̲. The enone 3̲3̲8̲ was obtained by oxidizing the trimethylsilyl enol ether of 3̲3̲7̲ using palladium (II) acetate in acetonitrile. When the enone 3̲3̲8̲ was treated with lithium divinylcuprate, the two epimeric products 3̲3̲9̲ and 3̲4̲6̲ were obtained in a ratio of 9:1, respectively, and were sus-sequently separated by column chromatography. Trapping the lithium enolate of 3̲3̲9̲ with t̲-butyldimethylsilyl chloride led to the required enol ether 3̲3̲2̲. Thermolysis (220°C, sealed tube) of 3̲3̲2̲ in benzene produced exclusively in 86% yield the desired bicyclic triene 3̲2̲1̲. Subjection of 3̲2̲1̲ to hydroboration
using disiamylborane gave, after oxidative workup, the alcohol 3̲4̲7̲, which on treatment with p̲-toluenesulfonyl chloride in the presence of 4-dimethylaminopyridine, afforded the ketone 3̲4̲9̲. Successive hydrogenation of 3̲4̲9̲ and Wittig olefination of the resultant ketone 2̲8̲0̲ completed the total synthesis of (±)-sinularene (1̲2̲5̲). [formula omitted] / Science, Faculty of / Chemistry, Department of / Graduate
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Prenatal exposure to organochlorine pesticides and its association with birth outcomesFang, Jing 26 August 2019 (has links)
Organochlorine pesticides (OCPs) were extensively applied in agriculture, industry and public health programs for decades. Based on the persistence and the lipophilicity of OCPs, these chemicals are ubiquitous in the environment and can be accumulated in fatty tissues of animals through the food chain. Even being restricted for years, OCPs are still detected in human bodies. In this thesis, analytical methods for the determination of OCPs were developed and applied for the analysis of cord serum samples. The evaluation of prenatal exposure to OCPs and its effects on birth outcomes as well as the postnatal growth were investigated. Due to the toxicology and carcinogenesis, biomonitoring of the OCP exposure to human is needed. Therefore, an analytical method with high sensitivity and specificity is required to detect OCPs at trace levels in serum. We compared two data acquisition modes of mass spectrometry (MS), namely selected ion monitoring (SIM) and multiple reaction monitoring (MRM). Higher sensitivity and selectivity were achieved by MRM because the background noise was reduced by lowering the matrix effects. Different ionization techniques, including electron ionization (EI), chemical ionization (CI) and atmospheric pressure chemical ionization (APCI) were evaluated. The EI source is a universal ionization technique available with the MS library for the compound identification. The negative chemical ionization (NCI) is more suitable to analyze compounds with high electronegativity. The novel ionization technique APCI was coupled to gas chromatography-tandem mass spectrometry (GC-MS/MS). The APCI source was evaluated by terms of ionization and fragmentation performance. APCI was a soft ionization technique generating molecular ions with high intensity. The selectivity and sensitivity of APCI were comparable or better than the EI source. As one of the largest consumers and producers of OCPs, China has suffered severe OCP pollution. Previous monitoring studies reported detectable levels of OCPs in human bodies. However, studies concerning the prenatal exposure to OCPs in China are limited. Due to the vulnerability of fetuses, the effects of prenatal exposure to OCPs could be more severe than those of adults. We collected cord serum samples during the delivery period in Wuhan, China and measured the OCP concentrations to assess the prenatal exposure by using GC-MS/MS. Compared with other areas in China, the OCP levels in Wuhan were comparable in this population. The identified predominant OCPs were β-HCH and p,p'- DDE, with geometric means of 8.67 and 33.9 ng/g lipid, respectively. Slight positive associations were found between α-HCH and β-HCH, and between o,p′- DDT and p,p′-DDT, which indicated similar exposure source of these chemicals. The obtained results showed that HCH levels were associated with maternal age, body mass index (BMI) before pregnancy, education levels, and passive smoking. Associations between the prenatal exposure of OCPs and birth outcomes were investigated. The sex-specific relationships between the OCP exposure and birth size were indicated. Concentrations of β-HCH were inversely associated with birth weight and ponderal index for boys, while for girls these associations were not significant. Our results suggested that the prenatal exposure to OCPs exerted negative effects on the fetal growth, and precautions should be taken even though the OCP levels were relatively low.
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METABOLISM OF 2,2, - BIS (P-CHLOROPHENYL)-1, 1-DICHLOROETHYLENE (DDE) BY THE BOVINE.MOHAMMAD, KASSIM HASSAN. January 1984 (has links)
Twelve lactating Holstein dairy cows were randomly divided into four groups of three animals each. Group A served as the control, group B was dosed at 0.05ppm/day of DDE (2,2-bis(P-chlorophenyl-1, 1-dichloroethylene), cows in group C were dosed at 0.1ppm DDE/day, while group D cows were dosed at 1.0ppm DDE/day. DDE was administered in a residue free peanut oil solution for 32-consecutive days. Milk samples were taken daily during the 32 day dosing period and for an additional 32 days after the dosing period. Quantitative analysis of DDE residue in milk fat was determined by using a Tracor MT-220 gas chromatograph with a Tritium electron capture detector. The average increase in DDE milk fat concentration during the dosing period was directly related to intake levels. DDE was the only organochlorine compound detected in the milk fat. The general slope and shape of the curves of milk fat DDE levels were similar for all treatments. The levels of DDE increased rapidly after the onset of dosing. After 15 days of dosing and throughout the remaining 17 days of the dosing period, milk fat DDE increased at a relatively slow rate. The level of milk fat DDE declined rapidly as soon as the DDE residue source was withdrawn. At the end of the 32-day post-dosing period, one cow from each group was slaughtered and samples were taken from muscles, brain, lung, lymph, spleen, kidney fat, heart, gonad, placenta, udder, and kidney for DDE analysis. Considerable DDE was found in the muscle, lymph, kidney fat, and udder tissues.
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THE POSSIBLE TRANSLOCATION OR SUBLIMATION OF DDE IN ALFALFA.Lingafeldt, Nancy Elizabeth. January 1982 (has links)
No description available.
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Determinação de compostos organoclorados e hidrocarbonetos poliaromáticos na Lagoa de Carapicuíba - SP / Determination of organochlorine compounds and polycyclic aromatic hidrocarbons in Lagoa de Carapicuiba- SPSantos, Allan Patrick dos 20 April 2007 (has links)
Em 2002, deu-se início na região metropolitana de São Paulo às obras de alargamento e rebaixamento da calha do rio Tietê, como um instrumento para evitar as periódicas enchentes que acontecem nesta região. O andamento da obra contou com a retirada de grande quantidade de sedimentos, rochas e lixo de dentro do rio e com o depósito deste mesmo material na lagoa de Carapicuíba que deveria ser parcialmente aterrada segundo o projeto que prevê a implantação de um parque público no local. Compostos organoclorados e hidrocarbonetos poliaromáticos são classificados como micropoluentes para ecossistemas. Seus impactos sobre o meio ambiente e toxicidade aos seres humanos têm sido amplamente discutidos pela comunidade científica nas últimas décadas. Neste trabalho obtiveram-se dados ambientais referentes ao diagnóstico de organoclorados e hidrocarbonetos poliaromáticos em amostras retiradas da lagoa de Carapicuíba. O método de extração dos compostos estudados (gama-BHC, Heptacloro, Aldrin, Heptacloro-epóxido; Benzo(a)pireno, Fluoreno, Naftaleno) dos sedimentos foi realizado por aparelho Soxhlet e de amostras de lixiviados e solubilizados por Extração em Fase Sólida. Uma etapa de \"clean-up\" se mostrou necessária para a remoção de interferentes. Para a identificação de organoclorados e hidrocarbonetos poliaromáticos nos extratos de lixiviados e solubilizados foi utilizada a cromatografia gasosa acoplada a espectrometria de massas. Os extratos dos sedimentos foram injetados em um cromatógrafo a gás com detector de captura de elétrons para a identificação e quantificação de organoclorados. A metodologia para extração e quantificação se mostrou satisfatória com índices de recuperação e desvio padrão relativo aceitos internacionalmente. Os valores de concentração dos organoclorados encontrados nos extratos de lixiviados e solubilizados ficaram abaixo do limite de detecção do aparelho. Os valores de concentração de organoclorados encontrados nos extratos dos sedimentos variaram de 9 a 175 µg kg-1. Foram identificados resíduos de hidrocarbonetos poliaromáticos em poucos extratos de lixiviados e solubilizados. / In 2002, started the workmanships of widening and deepening of the gutter of the river Tietê in the metropolitan area of Sao Paulo, as a tool to prevent the periodic floods that happen in this region. A large amount of sediment, rocks and garbage have been removed from the river and this same material has been deposited in the lagoa de Carapicuíba, which should be partially filled with earth according to a project that foresees the implement of a public park in the place. Organochlorine compounds and polycyclic aromatic hydrocarbons are classified as micropollutants to the ecosystems. Their impacts on the environment have been widely discussed by the scientific community in the past decades. Environmental data were obtained from the diagnosis of organochlorine compounds and polycyclic aromatic hydrocarbons in samples of water and sediment from this lagoon. The extraction method of the studied compounds (gama-BHC, Heptachlor, Aldrin, Heptachlor epoxid, Benzo(a)Pirene, Fluorine, Naphatalene) of the sediments has been made by Soxhlet apparatus and Solid Phase Extraction method were used for the leached and solubilizated extracts. A stage of clean-up was necessary to remove substances which could modify results. Gas Chromatography/Mass Spectrometry has been used to identify organochlorine compounds and polycyclic aromatic hydrocarbons in the leached and solubilizated extracts. The extracts of the sediment have been injected in a Gas Chromatograph apparatus with detector of eletron capture for the identification and quantification of organochlorine compounds. The methodology used in the extraction and quantification was considered satisfactory, with recovery indexes and relative standard deviation values internationally accepted. The concentration values of the organochlorines obtained in the leached and solubilizated extracts were under the chromatograph detection limits. The concentration of organoclhorine compounds found in extracts of the sediments values varied from 9 to 175 ?g kg-1. Polycyclic aromatic hydrocarbons were identified in few leached and solubilizated extracts.
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Formation of disinfection by-products and mutagenicity upon chlorination of algal-derived organic materialsLui, Yuen Shan 01 January 2010 (has links)
No description available.
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Determinação de compostos organoclorados e hidrocarbonetos poliaromáticos na Lagoa de Carapicuíba - SP / Determination of organochlorine compounds and polycyclic aromatic hidrocarbons in Lagoa de Carapicuiba- SPAllan Patrick dos Santos 20 April 2007 (has links)
Em 2002, deu-se início na região metropolitana de São Paulo às obras de alargamento e rebaixamento da calha do rio Tietê, como um instrumento para evitar as periódicas enchentes que acontecem nesta região. O andamento da obra contou com a retirada de grande quantidade de sedimentos, rochas e lixo de dentro do rio e com o depósito deste mesmo material na lagoa de Carapicuíba que deveria ser parcialmente aterrada segundo o projeto que prevê a implantação de um parque público no local. Compostos organoclorados e hidrocarbonetos poliaromáticos são classificados como micropoluentes para ecossistemas. Seus impactos sobre o meio ambiente e toxicidade aos seres humanos têm sido amplamente discutidos pela comunidade científica nas últimas décadas. Neste trabalho obtiveram-se dados ambientais referentes ao diagnóstico de organoclorados e hidrocarbonetos poliaromáticos em amostras retiradas da lagoa de Carapicuíba. O método de extração dos compostos estudados (gama-BHC, Heptacloro, Aldrin, Heptacloro-epóxido; Benzo(a)pireno, Fluoreno, Naftaleno) dos sedimentos foi realizado por aparelho Soxhlet e de amostras de lixiviados e solubilizados por Extração em Fase Sólida. Uma etapa de \"clean-up\" se mostrou necessária para a remoção de interferentes. Para a identificação de organoclorados e hidrocarbonetos poliaromáticos nos extratos de lixiviados e solubilizados foi utilizada a cromatografia gasosa acoplada a espectrometria de massas. Os extratos dos sedimentos foram injetados em um cromatógrafo a gás com detector de captura de elétrons para a identificação e quantificação de organoclorados. A metodologia para extração e quantificação se mostrou satisfatória com índices de recuperação e desvio padrão relativo aceitos internacionalmente. Os valores de concentração dos organoclorados encontrados nos extratos de lixiviados e solubilizados ficaram abaixo do limite de detecção do aparelho. Os valores de concentração de organoclorados encontrados nos extratos dos sedimentos variaram de 9 a 175 µg kg-1. Foram identificados resíduos de hidrocarbonetos poliaromáticos em poucos extratos de lixiviados e solubilizados. / In 2002, started the workmanships of widening and deepening of the gutter of the river Tietê in the metropolitan area of Sao Paulo, as a tool to prevent the periodic floods that happen in this region. A large amount of sediment, rocks and garbage have been removed from the river and this same material has been deposited in the lagoa de Carapicuíba, which should be partially filled with earth according to a project that foresees the implement of a public park in the place. Organochlorine compounds and polycyclic aromatic hydrocarbons are classified as micropollutants to the ecosystems. Their impacts on the environment have been widely discussed by the scientific community in the past decades. Environmental data were obtained from the diagnosis of organochlorine compounds and polycyclic aromatic hydrocarbons in samples of water and sediment from this lagoon. The extraction method of the studied compounds (gama-BHC, Heptachlor, Aldrin, Heptachlor epoxid, Benzo(a)Pirene, Fluorine, Naphatalene) of the sediments has been made by Soxhlet apparatus and Solid Phase Extraction method were used for the leached and solubilizated extracts. A stage of clean-up was necessary to remove substances which could modify results. Gas Chromatography/Mass Spectrometry has been used to identify organochlorine compounds and polycyclic aromatic hydrocarbons in the leached and solubilizated extracts. The extracts of the sediment have been injected in a Gas Chromatograph apparatus with detector of eletron capture for the identification and quantification of organochlorine compounds. The methodology used in the extraction and quantification was considered satisfactory, with recovery indexes and relative standard deviation values internationally accepted. The concentration values of the organochlorines obtained in the leached and solubilizated extracts were under the chromatograph detection limits. The concentration of organoclhorine compounds found in extracts of the sediments values varied from 9 to 175 ?g kg-1. Polycyclic aromatic hydrocarbons were identified in few leached and solubilizated extracts.
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Effects of ethanol media on chlorine dioxide and extraction stages for kraft pulp bleachingBrogdon, Brian N. 08 1900 (has links)
No description available.
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