abstract: DehaloR^2 is a previously characterized, trichloroethene (TCE)-dechlorinating culture and contains bacteria from the known dechlorinating genus, Dehalococcoides. DehaloR^2 was exposed to three anthropogenic contaminants, Triclocarban (TCC), tris(2-chloroethyl) phosphate (TCEP), and 1,1,1-trichloroethane (TCA) and two biogenic-like halogenated compounds, 2,6-dibromophenol (2,6-DBP) and 2,6-dichlorophenol (2,6-DCP). The effects on TCE dechlorination ability due to 2,6-DBP and 2,6-DCP exposures were also investigated. DehaloR^2 did not dechlorinate TCC or TCEP. After initial exposure to TCA, half of the initial TCA was dechlorinated to 1,1-dichloroethane (DCA), however half of the TCA remained by day 100. Subsequent TCA and TCE re-exposure showed no reductive dechlorination activity for both TCA and TCE by 120 days after the re-exposure. It has been hypothesized that the microbial TCE-dechlorinating ability was developed before TCE became abundant in groundwater. This dechlorinating ability would have existed in the microbial metabolism due to previous exposure to biogenic halogenated compounds. After observing the inability of DehaloR^2 to dechlorinate other anthropogenic compounds, DehaloR^2 was then exposed to two naturally occurring halogenated phenols, 2,6-DBP and 2,6-DCP, in the presence and absence of TCE. DehaloR^2 debrominated 2,6-DBP through the intermediate 2-bromophenol (2-BP) to the end product phenol faster in the presence of TCE. DehaloR^2 dechlorinated 2,6-DCP to 2-CP in the absence of TCE; however, 2,6-DCP dechlorination was incomplete in the presence of TCE. Additionally, when 2,6-DBP was present, complete TCE dechlorination to ethene occurred more quickly than when TCE was present without 2,6-DBP. However, when 2,6-DCP was present, TCE dechlorination to ethene had not completed by day 55. The increased dehalogenation rate of 2,6-DBP and TCE when present together compared to conditions containing only 2,6-DBP or only TCE suggests a possible synergistic relationship between 2,6-DBP and TCE, while the decreased dechlorination rate of 2,6-DCP and TCE when present together compared to conditions containing only 2,6-DCP or only TCE suggests an inhibitory effect. / Dissertation/Thesis / M.S. Civil and Environmental Engineering 2012

A presença de substâncias húmicas em águas destinadas ao abastecimento tem ocasionado diversos problemas, decorrentes da formação de subprodutos orgânicos halogenados, principalmente quando se emprega a pré-oxidação com cloro. Os compostos orgânicos halogenados, reconhecidamente carcinogênicos e que podem ser encontrados nas águas tratadas e distribuída à população, são: trialometanos, ácidos haloacéticos, haloaldeidos, halocetonas, halofenóis e halopicrinas. Nas estações de tratamento de água para abastecimento (ETAs), a utilização da etapa de pré-oxidação da água bruta com cloro contribui para a formação desses subprodutos. A presente pesquisa teve como objetivo avaliar o potencial de formação de vinte e dois subprodutos com a utilização dos seguintes pré-oxidantes: cloro, dióxido de cloro, permanganato de potássio, peróxido de hidrogênio, ozônio e peroxônio. O potencial de formação de subprodutos foi simulado em uma água preparada com adição de substâncias húmicas extraídas de solo turfoso, por meio do uso da pré-oxidação, coagulação, filtração e pós-cloração. Os subprodutos foram quantificados por cromatografia gasosa com detetor de captura de elétrons. Os resultados obtidos mostraram que o uso de pré-oxidantes alternativos, tais como: permanganato de potássio; dióxido de cloro; peróxido de hidrogênio; ozônio e peroxônio, associados à coagulação, filtração e pós-cloração formam quantidades mínimas de subprodutos. / The presence of humic substances in water destined for supply has brought many problems, resulting from the formation of halogenated organic byproducts, especially when preoxidation with chlorine is used. Halogenated organic compounds, which are admittedly carcinogenic and can be found in water treated and distributed for the population, are: trihalometano, haloacetic acid, haloaldehyde, haloacetone, halophenol, and halopicrin. In water treatment plants (WTPs), the use of preoxidation with chlorine of the raw water contributes for forming such byproducts. This research aims at evaluating the potential for the formation of twenty two byproducts using the following preoxidants: chlorine, chlorine dioxide, potassium permanganate, hydrogen peroxide, ozone, and peroxone. The potential of byproducts formation was simulated in water prepared with addition of humic substances extracted from peat soil by preoxidation, coagulation, filtration and post-chlorination. Byproducts were quantified by gas chromatography with electron capture detector. The results obtained showed that the use of alternative preoxidants such as: chlorine, chlorine dioxide, potassium permanganate, hydrogen peroxide, ozone, and peroxone, associated with coagulation, filtration, and post-chlorination form a minimum of byproducts.

O pinguim-de-Magalhães é a espécie de pinguim mais presente em águas jurisdicionais brasileiras e frequente na clínica de animais marinhos, vítimas de desorientação, da poluição, da pesca e outras ações antrópicas. Com o estudo objetivou-se estabelecer as concentrações anestésicas mínimas (CAM) do isofluorano e sevofluorano em pinguins-de-Magalhães e posteriormente avaliá-las sob a influência de diferentes frações inspiradas de O2 (FiO2). Foram utilizados 20 animais adultos, saudáveis e sem distinção quanto ao sexo. Durante a primeira etapa, focou-se no estabelecimento da CAM para ambos os anestésicos. Os animais foram inicialmente submetidos à contenção física e sequencialmente induzidos a anestesia com auxílio de máscara facial, seguindo-se a intubação traqueal, após adequada indução e posterior manutenção sob ventilação controlada, para ambos os halogenados. A determinação da CAM foi realizada de acordo com o delineamento \"up-and-down\". Desta forma, cada animal foi exposto uma única vez a uma concentração anestésica pré-determinada, por um período de 15 minutos, seguido da aplicação de um estímulo elétrico. De acordo com a resposta obtida, o próximo animal foi submetido a uma fração aumentada em 0,1 (resposta positiva) ou reduzida em 0,1 (resposta negativa). Para realização da segunda etapa, 12 animais foram distribuídos entre os grupos isofluorano e sevofluorano, com seis indivíduos em cada um. Todos os animais foram anestesiados e mantidos com 1 CAM de cada halogenado, obtido na primeira etapa, sendo ambos os agentes anestésicos diluídos em frações de 1,0, 0,6, 0,4 e 0,2 de O2. As aves foram mantidas sob anestesia por 80 minutos, sendo que a cada 20 minutos era alterada a fração de O2, por sorteio, seguindo-se um modelo de quadrado latino. Foram monitorados durante a anestesia FC, FR, PAS, PAM, PAD, temperatura, pH, HCO3-, PaO2 e PaCO2 e eletrólitos (Na+ e K+). Os valores de CAM para isofluorano e sevofluorano foram de 1,91 V% e 3,53 V% respectivamente. Diante dos resultados obtidos conclui-se que as FiO2 de 1,0, 0,6 e 0,4 mostram-se seguras para pinguins-de-Magalhães anestesiados com 1 CAM de isofluorano ou sevofluorano mantidos sob ventilação controlada. / The Magellanic penguin is the most present penguin species in Brazilian coast. It is frequent in the marine animal clinic, victims of disorientation, pollution, fishing and other anthropic actions. The objective of this study was to establish the minimum anesthetic concentrations (MAC) of isofluorane and sevoflurane in Magellanic penguins and later evaluate them under the influence of different inspired fractions of O2 (FiO2). Twenty adult animals, healthy and without distinction as to sex, were used. During the first stage, we focused on the establishment of MAC for both anesthetics. The animals were initially submitted to physical restraint and sequentially induced anesthesia with the aid of facial mask, followed by tracheal intubation, after adequate induction and subsequent maintenance under controlled ventilation, for both halogenates. MAC determination was performed according to the up-and-down design. In this way, each animal was exposed once to a predetermined anesthetic concentration, for a period of 15 minutes, followed by the application of an electric stimulus. According to the answer obtained, the next animal was submitted increased by 0.1 fraction (positive response) or reduced by 0.1 (negative response). To perform the second step, 12 animals were divided between the isofluorane and sevofluoran groups, with 6 individuals in each. All animals were anesthetized and maintained with 1 MAC of each halogenated, obtained in the first step, both anesthetic agents being diluted in fractions of 1.0, 0.6, 0.4 and 0.2 of O2. The penguins were kept under anesthesia for 80 minutes, and every 20 minutes the O2 fraction was changed, by lot, followed by a Latin square model. They were monitored during anesthesia FC, FR, PAS, MAP, PAD, temperature, pH, HCO3-, PaO2 and PaCO2 and electrolytes (Na+ and K+). The MAC values for isofluorane and sevoflurane were 1.91 V% and 3.53 V% respectively. In view of these results, FiO2 of 1.0, 0.6 and 0.4 were shown to be safe for Magellanic penguins anesthetized with 1 MAC of isofluorane or sevofluorane maintained under controlled ventilation.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22701号 / 工博第4748号 / 新制||工||1742(附属図書館) / 京都大学大学院工学研究科材料化学専攻 / (主査)教授 大塚 浩二, 教授 松原 誠二郎, 教授 秋吉 一成 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Exposure to halogenated phenols and pyridinols is of increasing concern because of their wide use and distribution. This research was initiated to determine the distribution, accumulation, and depletion of a group of halogenated phenols and a pyridinol in selected tissues of male weanling rats at different time intervals following a single oral dose of 0.33 or 1.66 m moles per kg body weight. The halogenated phenols and pyridinol were distributed differently in every tissue sampled following their administration, even though the amount administered was the same in each case. The concentrations in tissue were found in the order: 2,4,5-trichloro-phenol > 4-bromo-2,5-dichlorophenol > 4-iodo-2,5-dichlorophenol > 3,5,6-trichloro-2-pyridonol in kidney and fat, whereas the series 3,5,6-trichloro-2-pyridinol > 4-iodo-2,5-dichlorophenol > 4-bromo-2,5-dichlorophenol > 3,5,6-trichlorophenol occurred in liver. No structurally significant series was observed for their concentrations in blood. All halogenated phenols and pyridinol concentrations in tissues declined rapidly with time but not always in an apparently log linear fashion. Rates were greatest for clearance from blood. The highest concentration of halogenated phenols was in kidney among the tissues studied, whereas the highest concentration of halogenated pyridinol was in liver. Relationships were found between the relative lipophilicity, as indicated by the chromatographic Rm value, and the concentrations of these compounds in tissues. The RH (i.e., relative lipophilicity) was generally very well correlated with the log concentration of compounds in tissues observed 24 h after dosing. The correlation coefficients ranged between .517 and .995 among tissues. Correlations were positive between the Rm values and 24 h concentrations in adipose tissue, and kidney, but negative for the relationship between the Rm and 24 h concentrations in blood and liver.

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Apresentamos resultados para o espectro de ânions e para a dinâmica vibracional induzida pela captura eletrônica, para uma série de moléculas halogenadas. Os estados do ânion foram caracterizados por meio de cálculos de espalhamento elástico realizados na aproximação de núcleos fixos, efetuados com o método multicanal de Schwinger com pseudopotenciais. Cálculos de dinâmica quântica do pacote de onda nuclear foram realizados a partir da propagação desse nas superfícies de energia potencial descritas na aproximação local. Foram alvo de estudo clorometano, cloroeteno, uracila, 5-fluorouracila, 5-clorouracila, 5-bromouracila, 5-iodouracila, 6-clorouracila, 2-tiouracila, adenina, 2-cloroadenina e 8-cloroadenina. Para o clorometano, calculamos seções de choque de excitação vibracional do estiramento C-Cl, e mostramos que esse modo é prontamente ativado pela presença da carga adicional. Para o cloroeteno, demonstramos que o mecanismo direto de dissociação é muito ineficiente, e também revelamos a interessante topologia de suas superfícies de energia potencial complexas. Os derivados de uracila apresentaram ricos espectros aniônicos, contando com três estados delocalizados p*, um estado s* localizado na ligação do átomo substituído com o anel, além de um estado ligado por dipolo. No geral, as energias obtidas estão em ótimo acordo com os valores experimentais. Análises dos espectros aniônicos e das superfícies de energia potencial indicam mecanismos em que o ânion é formado numa ressonância p* de longo tempo de vida, que muda de caráter para o estado dissociativo s*. Na 5-clorouracila em particular, esse acoplamento é mediado pelo movimento do cloro para fora do plano molecular. Conforme os estados do ânion progressivamente estabilizam com o aumento do número atômico do halogênio, os acoplamentos tornam-se mais favoráveis, o que responde pelas crescentes seções de choque de dissociação. Nossos resultados explicam muitas das características observadas na captura eletrônica dissociativa de halouracilas, fornecendo uma base teórica para sua habilidade radiossensibilizadora. Nas cloroadeninas, encontramos uma ressonância s* e quatro ressonâncias p*. Nós sustentamos que elas também poderiam atuar como potenciais radiossensibilizadores. / We present results on the anion spectrum and on the vibrational dynamics induced by electron capture, for a series of halogenated molecules. The anion states were characterized by means of elastic scattering calculations, in the fixed nuclei approximation, performed with the Schwinger multichannel method with pseudopotentials. Quantum dynamics calculations of the nuclear wavepacket were performed by the propagation on potential energy surfaces described in the local approximation. The target molecules comprise chloromethane, chloroethene, uracil, 5-fluorouracil, 5-chlorouracil, 5-bromouracil, 5-iodouracil, 6-chlorouracil, 2-thiouracil, adenine, 2-chloroadenine and 8-chloroadenine. For chloromethane we computed vibrational excitation cross sections for the C-Cl stretching, and showed this mode is promptly activated by the presence of the extra charge. For chloroethene, we demonstrated that the direct mechanism of dissociation is very inefficient, and also revealed the interesting topology of its complex potential energy surfaces. The derivatives of uracil presented rich anionic spectra, as each one has three p* delocalized states, a s* state located at the bond between the substituted atom and the ring, and a dipole bound state. Overall, the obtained energetics are in very good agreement with experimental data. Analysis of the anionic spectra and the potential energy surfaces indicate mechanisms in which the anion is formed in a long-lived p* resonance and changes its character to the dissociative s* state. For 5-chlorouracil in particular, this coupling is mediated by an out-of-plane movement of the chlorine atom. As the anion states progressively stabilize as the halogen atomic number increases, the couplings become more favorable, and account for the increasing dissociation cross sections. Our results explain many of the observed features of dissociative electron attachment to halouracils, providing a theoretical basis for its radiosensitizing ability. In chloroadenines, we found a s* resonance and four p* resonances. We support they could also act as potential radiosensitizers.

A natureza e diversidade das estruturas químicas com atividade farmacológica que se tem encontrado nos organismos marinhos justificam a busca por novos compostos que são de interesse nas mais diversas áreas de aplicação. As espécies de macroalgas vermelhas, em especial Laurencia spp., merecem destaque pela enorme variedade de terpenos e acetogeninas que produzem, sendo consideradas de grande potencial na produção de novos fármacos. O estudo de seus constituintes pode fornecer importantes subsídios para a quimiotaxonomia, ecologia química, caracterização das espécies e avaliação do potencial biotecnológico. Baseado nisso, Laurencia aldingensis, L. dendroidea e Laurenciella sp. foram selecionadas para o presente estudo para isolamento, caracterização e teste de atividades biológicas dos seus compostos. A técnica do DNA barcoding foi utilizada como ferramenta de diagnóstico para garantir a similaridade entre as amostras de cada espécie, que foram coletadas em época e locais diferentes. Do extrato orgânico de Laurencia aldingensis, nove substâncias foram isoladas, sendo quatro esfingosinas (1-4), três terpenos (5-7) e duas novas substâncias halogenadas (8 e 9). Do extrato orgânico de Laurencia dendroidea formam isolados dois terpenos halogenados conhecidos (10, 11) e, do extrato de Laurenciella sp. três novas substâncias halogenadas alifáticas insaturadas (12-14), assim como um ácido graxo (15) e um esterol (16) conhecidos. Dentre elas, a 8 apresentou atividade citotóxica, mas não se mostrou seletivo, e as substâncias 4 e 11 apresentaram atividade esquistossomicida, bastante promissora. No entanto, nenhum deles apresentou atividade antioxidante. Diante desta investigação, podemos dizer que as informações geradas com os estudos de Laurencia aldingensis, L. dendroidea e Laurenciella sp. expandiram significantemente o conhecimento no que tange a diversidade química no gênero e o potencial biológico-farmacêutico dos mesmos. / The nature and diversity of chemical structures with pharmacological activity that have been found in marine organisms justifies the search for new compounds that may have applications in various areas of interest. Species of red seaweeds, especially Laurencia spp., are special because of the unprecedented variety of terpenes and acetogenins they produce that are considered potentially useful for the production of new drugs. Study of their constituents can also provide important insights relating to their chemotaxonomy, chemical ecology, characterization of species and biotechnological potential. On this basis Laurencia aldingensis, L. dendroidea and Laurenciella sp., were selected for study and isolation, characterization, and biological activity assessment of isolatable quantities of their compounds. The technique of DNA barcoding was used as a diagnostic tool to ensure similarity between samples of each species collected at different times and places. From the organic extract of Laurencia aldingensis nine compounds were isolated; four sphingosines (1-4), three terpenes (5-7) and other two new halogenated compound (8, 9). From the organic extract of Laurencia dendroidea two known halogenated terpenes (10, 11) were isolated while from a similar extract of Laurenciella sp., three new halogenated aliphatic compounds (12-14) were isolated together with known fatty acid (15) and sterol (16). Among all isolates, 8 demonstrated unspecific cytotoxic activity and compounds 4 and 11 showed promising schistosomicidal activity. In applied antioxidant assays none of the isolates we noted to have activity. From the overall investigation it is also clear that the information gleaned from the studies of Laurencia aldingensis, L. dendroidea and Laurenciella sp., significantly expanded our knowledge base concerning chemical diversity in the genus Laurencia and their biological-pharmaceutical potential.