Ce travail décrit la réactivité du chlore et de la monochloramine sur les aminophénols en solution aqueuse.Cette étude a ciblé, d'une part la détermination des vitesses réactionnelles de chloration et de monochloramination des aminophénols et d'autre part, l'identification des sous-produits d'oxydation formés.Les demandes en oxydant et le potentiel de formation en composés organohalogénés adsorbables (AOX), chloroforme, acides haloacétiques (HAA) and haloacétonitriles (HAN) ont été déterminés lors de la chloration et la monochloramination des aminophénols. Les 3-aminochlorophénols et le 2-amino-3H-phénoxazin-3-one (APX) ont été respectivement identifiés lors de la monochloramination de 3AP et 2AP.L'étude cinétique de la chloration des aminophénols en réacteur continu a montré que les vitesses sont du même ordre de grandeur pour le 2-aminophénol (2AP) et le 3-aminophénol (3AP) à pH neutre. La modélisation cinétique de la chloration du 3AP a indiqué que la forme aminophénolate est la plus réactive vis-à-vis du chlore.Quant à l'étude cinétique de monochloramination du 3AP en réacteur fermé, elle a permis de conclure que la vitesse de monochloramination diminue en passant du pH 7 à 9 et la forme neutre de 3AP est la plus réactive vis-à-vis de la monochloramine. Par comparaison, la vitesse de chloration du 3AP a été plus importante d'un facteur 105 à celle de la monochloramination. / This work describes the reactivity of chlorine and monochloramine with aminophenols in aqueous solution. Chlorination and monochloramination kinetic rates of aminophenols were investigated, first and final oxidation by-products were identified.Oxidant demands and formation potential of adsorbable organic halides (AOX), chloroform, haloacetic acids (HAA) and halonitriles (HAN) were determined during the chlorination and the monochloramination of aminophenols. The 3-aminochlorophenols and the 2-amino-3H-phenoxazin-3-one (APX) were respectively identified during the monochloramination of 3AP and 2AP.Chlorination of aminophenols in a continuous flow reactor showed that the kinetic rates of 2-aminophenol (2AP) and 3-aminophenol (3AP) have the same order of magnitude at neutral pH. Kinetic modelling of 3AP chlorination indicated that aminophenolate is the most reactive species with chlorine.Monochloramination kinetics of 3AP in a batch reactor showed that the rate of monochloramination decreases when pH increases from 7 to 9 and the neutral form of 3AP is the most reactive with monochloramine. In comparison, chlorination rate of 3AP was estimated to be 105-fold higher than monochloramination rate.

Made available in DSpace on 2015-03-26T13:36:35Z (GMT). No. of bitstreams: 1 texto completo.pdf: 318019 bytes, checksum: f14201c1f1fe349bcc7b8771be868f8e (MD5) Previous issue date: 2006-02-03 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The effects of aluminum on growth, respiratory activities and on some enzymes related to reactive oxygen species (ROS) elimination were examined in roots of two corn seedlings cultivated in nutrient solution, by comparing a susceptible (BR 106) and a tolerant cultivar (BR 206). Growth of the main root decreased in both cultivars, mainly in the susceptible one, at aluminum concentration of 50 and 100 µM. Only in the tolerant cultivar aluminum induced a decrease in the leak of electrolytes. On the contrary, the susceptible cultivar showed significant increase in lipid peroxidation. Aluminum promoted higher activities of superoxide dismutase (SOD) and ascorbate peroxidase (APX), only in the tolerant cultivar. No difference was observed in the activities of catalase (CAT), peroxidases (POX) and glutathione reductase (GR) in both cultivars. Ascorbate content was not altered, but the ascorbate redox state (ratio ascorbate/dehydroascorbate) increased in the tolerant cultivar. In absence of aluminum, respiratory oxygen consumption was higher in the tolerant cultivar, both in states 3 and 4. These respiratory activities were decreased by aluminum in the susceptible cultivar, but were increased in the tolerant one. ADP/O ratios were decreased by aluminum, in both cultivars at a similar extent. The cytochrome c pathway was not altered by aluminum in the tolerant cultivar, but decreased in the susceptible one. Without aluminum, the susceptible cultivar showed a higher alternative oxidase (AOX) activity than the tolerant one. Aluminum promoted a decrease in AOX activity in the susceptible cultivar, the opposite response being observed in the tolerant one. In both cultivars aluminum induced an increase above 120% in the residual oxygen consumption. Activity of the plant uncoupling mitochondrial protein (PUMP) was decreased by aluminum in the susceptible cultivar and enhanced in the tolerant one. These results suggest that the tolerant cultivar possesses a more efficient enzymatic system for ROS removal than the sensitive one. Furthermore, the partial mitochondrial uncoupling, resulting from higher AOX and PUMP activities should have contributed to the higher aluminum stress tolerance showed by cultivar BR 206. / Os efeitos do alumínio sobre o crescimento, a respiração e as atividades de algumas enzimas envolvidas na eliminação de espécies reativas de oxigênio foram avaliadas em plântulas de duas cultivares de milho, uma sensível (BR 106) e outra tolerante ao alumínio (BR 206), cultivadas em solução nutritiva, pH 4,0. O alumínio, nas concentrações de 50 e 100 µM, reduziu o crescimento da raiz principal das duas cultivares, especialmente da cultivar sensível. O alumínio reduziu o extravasamento de eletrólitos, apenas nas raízes da cultivar tolerante e aumentou a peroxidação de lipídios, apenas na cultivar sensível. O tratamento com alumínio resultou em aumentos significativos nas atividades da dismutase do superóxido (SOD) e da peroxidase do ascorbato (APX), apenas na cultivar tolerante. Entretanto, não foram observadas diferenças significativas nas atividades da catalase (CAT), das peroxidades (POX) e da redutase da glutationa (GR), em ambas as cultivares. Os teores de ascorbato também não apresentaram variação significativa, mas foi observado aumento no estado redox (razão ascorbato/desidroascorbato), porém apenas na cultivar tolerante. No tratamento controle, as taxas respiratórias de mitocôndrias isoladas da cultivar tolerante se apresentaram mais elevadas, tanto no estado 3 como no estado 4. Estas taxas foram reduzidas pelo alumínio na cultivar sensível, e aumentadas na cultivar tolerante. As razões ADP/O foram reduzidas pelo tratamento com alumínio, nas duas cultivares, na mesma proporção. A rota do citocromo c não foi alterada pelo alumínio, na cultivar tolerante, mas foi reduzida na cultivar sensível. Na ausência de alumínio, a cultivar sensível apresentou atividade da oxidase alternativa (AOX) mais elevada, que foi reduzida pela presença de alumínio. Ao contrário, o consumo de oxigênio pela rota alternativa foi aumentado, pelo alumínio, na cultivar tolerante. Nas duas cultivares, o alumínio promoveu acréscimos superiores a 120% no consumo residual de oxigênio. A atividade da proteína desacopladora de plantas (PUMP) foi diminuída pelo alumínio, na cultivar sensível, e aumentada, na tolerante. Estes resultados sugerem que a cultivar tolerante possua um mecanismo enzimático mais eficiente de remoção ou neutralização de espécies reativas de oxigênio que a cultivar sensível. Além disso, o parcial desacoplamento mitocondrial observado, resultante do aumento das atividades da oxidase alternativa e da proteína desacopladora, deve contribuir para a maior tolerância da cultivar BR 206 ao estresse por alumínio.

L’objectif de notre travail consiste à caractériser des nanoparticules d’oxyde de fer (Fe3O4) et étudier leur toxicité aiguë chez le rat Wistar. Nos résultats ont montré que l’administration orale aiguë des Fe3O4, entraîne une altération dose- et temps-dépendante des paramètres du stress oxydant ainsi qu’une atteinte hépatique. En ce qui concerne l’étude in vitro sur des mitochondries isolées, nos résultats ont montré que ces nanoparticules n’altèrent ni les différents complexes de la chaîne respiratoire mitochondriale ni le couplage mitochondrial, et ceci dans aucun des organes étudiés (cerveau, cœur, poumon, foie et reins) et quelle que soit la concentration utilisée (100, 200, 300 et 500 μg/ml), alors que les mitochondries hépatiques isolées des rats âgés (18 mois), une altération est observée au niveau de tous les complexes de la chaîne respiratoire mitochondriale hépatique ainsi que pour le couplage mitochondrial quelle que soit la concentration utilisée (250, 300 et 350 μg/ml) alors que pour les rats jeunes (3mois) on n’observe aucune altération. / The objective of our work is to characterize iron oxide nanoparticles (Fe3O4) and study their acute toxicity in Wistar rats. Our results showed that acute oral administration of Fe3O4, results in a dose and time-dependent alteration of oxidative stress parameters as well as liver damage. Regarding the in vitro study on isolated mitochondria, our results showed that these nanoparticles do not adversely affect the various complexes of the mitochondrial respiratory chain or mitochondrial coupling in any of the organs studied (brain, heart, lung, liverand kidneys) and regardless of the concentration used (100, 200, 300 and 500 μg/ml) while the isolated liver mitochondria from aged rats (18 months), an alteration is observed at all the complexes of the liver mitochondrial respiratory chain as well as the mitochondrial coupling regardless of the concentration used (250, 300 and 350 μg/ml), whereas for the young rats (3 months) no change is observed.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The Toxoplasma gondii is a protozoan of great clinical importance can cause functional and biochemical changes in the host cells mainly in the central nervous system. These changes are usually associated with the inflammatory response to tissue damage and cell oxidation in immunocompetent hosts. T. gondii infection stimulate the production of high levels of cytokines such as IL-12 and IFN-γ by cells of the immune system, consisting of a main point in parasite control and disease resistance. As a potent antioxidant, resveratrol has become an important research subject due to its antioxidant and anti-inflammatory properties. However, the mechanism by which resveratrol exerts its effects are hampered by the low solubility and bioavailability. Accordingly, one way to improve the bioavailability of resveratrol is to associate with inclusion complexes. Thus, this study aimed to investigate the benefits of resveratrol associated with sulfamethoxazole-trimethoprim (ST) in the treatment of experimentally infected mice with T. gondii. For the study, 60 mice were divided into two groups: non-infected (n = 24) and infected with T. gondii (n = 36). The two groups were divided into subgroups and treated with resveratrol (free and inclusion complex 2-hydroxypropyl-β-cyclodextrin) isolated and associated with ST. The groups A to D composed by healthy mice and groups E to J consisting of animals infected by T. gondii (VEG strain). The treatment started 20 days post-infection for 10 consecutive days with oral doses of 0.5 mg kg-1 of ST (groups B and F), 100 mg kg-1 of free resveratrol (groups C and G) and inclusion complex of resveratrol (inclusion complex containing resveratrol) (groups D and H), as well as with an association of both drugs (groups I and J). Groups A and E were used as control, untreated. Behavioral tests (memory, anxiety and locomotion) were performed after treatment. Blood samples, liver and brain fragments were collected to evaluate the cytokine profile, pathological changes, brain cysts counts, as well as oxidant/antioxidant profile. Infected animals showed behavioral changes such as anxiety and memory loss. The combination ST and resveratrol was able to restore time latência in passive avoidance task. A reduction of the number of brain cyst was observed on animals treated with the combination of drugs. Infected animals show an increase in pro-inflammatory cytokines and reduction of anti-inflammatory cytokine (IL-10), as well as increased protein oxidation in liver and brain tissue. The combination of resveratrol and ST with free inclusion complex in increased the total antioxidant capacity (TAC) and ferric reducing antioxidant power (FRAP) levels in liver and brain that can be interpreted by the protective effect of resveratrol. In addition, resveratrol in inclusion complex form when combined with ST improved therapeutic effect of ST reducing oxidative damage in liver and brain, reducing the number of cysts in the treatment of mice infected with T. gondii. Therefore, it is possible to suggest that the ST with resveratrol on treatment of infected mice can exerts a protective effect on host cells. The resveratrol in inclusion complex form was the best treatment option, for controlled tissue and serum immune responses, as well as oxidative stress in mice infected with T. gondii. / O Toxoplasma gondii é um protozoário de grande importância clínica capaz de ocasionar alterações bioquímicas e funcionais nas células do hospedeiro, principalmente no sistema nervoso central. Essas alterações, geralmente estão associadas à resposta inflamatória com danos teciduais e oxidação celular em hospedeiros imunocompetentes. A infecção por T. gondii estimula a produção de altos níveis de citocinas, tais como IL-12 e IFN-γ, pelas células do sistema imunológico, consistindo em um ponto principal no controle do parasito e resistência à doença. Como um potente antioxidante, o resveratrol tem se tornado um importante alvo de pesquisas graças a suas propriedades antioxidantes e anti-inflamatórias. No entanto, os mecanismos pelo qual o resveratrol exerce seu efeito são prejudicados pela baixa solubilidade e biodisponibilidade. Nesse sentido, uma forma de melhorar a biodisponibilidade do resveratrol é associá-lo a um complexo de inclusão. Desta maneira, os objetivos deste estudo foram investigar os benefícios do resveratrol associado a sulfamethoxazol-trimetropin (ST) no tratamento de camundongos infectados experimentalmente com T. gondii. Para o estudo, 60 camundongos foram divididos em dois grupos: não-infectados (n=24) e infectados com T.gondii (n=36). Os dois grupos foram subdivididos em subgrupos (n= 10) e tratados com resveratrol (livre e em complexo de inclusão 2- hidroxipropil-β-ciclodextrina) isolado e associado com ST. Os grupos A-D foram compostos por animais saudáveis; grupos E-J consistiram de animais infectados por T. gondii (cepa VEG). O tratamento foi iniciado 20 dias após a infecção e manteve-se por 10 dias consecutivos nas doses orais de 0.5 mg kg-1 de ST (grupos B e F), 100 mg kg-1 de resveratrol livre (grupos C e G) e na forma de complexo de inclusão (grupos D e H), bem como na associação de ambas drogas (grupos I e J). Grupos A e E foram usados como controles, não tratados. Testes comportamentais (memória, ansiedade e locomoção) foram avaliados após o tratamento. Amostras de sangue, fragmentos de fígado e cérebro foram coletados a fim de avaliar os níveis de citocinas, alterações histopatológicas, contagem de cistos cerebrais, como também perfil oxidativo/antioxidante. Animais infectados com T. gondii apresentaram alterações comportamentais como ansiedade e perda de memória. A combinação com ST e resveratrol foi capaz de restaurar o tempo de latência no teste de esquiva inibitória. Uma redução na contagem de cistos foi observada nos animais tratados com a associação de drogas assim como redução das lesões teciduais. Animais infectados apresentam aumento de citocinas pró-inflamatórias e redução da citocina anti-inflamatória (IL-10), assim como maior oxidação proteica em tecido hepático e cerebral. A combinação de ST com resveratrol livre e em complexo de inclusão aumentou os a capacidade antioxidante total (TAC) e os produtos de redução férrica (FRAP) em fígado e cérebro que pode ser interpretado pelo efeito protetor do resveratrol. Além disso, o resveratrol na forma de complexo de inclusão quando combinado à ST melhorou o efeito terapêutico da ST reduzindo os danos oxidativos, lesões hepáticas e número de cistos cerebrais no tratamento de camundongos infectados com T. gondii. Portanto, é possível sugerir que a combinação de ST com resveratrol em camundongos infectados parece exercer um efeito protetor nas células hospedeiras. O resveratrol na forma de complexo de inclusão foi a melhor opção terapêutica, pois controlou as respostas imunológicas séricas e teciduais, assim como o estresse oxidativo em camundongos infectados com T. gondii.

MSc (Chemistry) / Department of Chemistry

Nitrogen dioxide (NO2) levels were measured inside and adjacent to canopies of urban trees in Springfield, MA, over two growing seasons. Nitrogen dioxide levels were consistently and significantly higher inside tree canopies compared to levels outside. During the second growing season, ozone (O3), temperature, and relative humidity (RH) were also measured using samplers co-located with the NO2 samplers. Ozone levels were significantly lower inside the canopy whereas temperatures were higher inside the canopy, and RH was not different between inner and outer canopy locations. The results corroborate theoretical models predicting elevated NO2 and depressed O3 levels inside tree canopies based on photochemistry, but put into question the mechanisms involved in generating these levels. In a separate study, the use of a common urban street tree (Acer rubrum) as a tool for measuring NO2 uptake under field conditions was evaluated using a model previously applied only to potted herbaceous plants and coniferous trees. Using potted saplings of A. rubrum located at locations with high or low NO2 levels in Springfield, MA, and Amherst, MA, we measured 15N stable isotope signatures (δ15N) and total N (%N) of leaves throughout the growing season. There was no significant difference in leaf δ15N or %N change between sites over the course of the season. Changes in δ15N were likely the result of input from N sources in the nutrient solution. Changes in %N followed a natural seasonal decline reported elsewhere in the literature. The study highlights the difficulties in applying this particular model to deciduous trees and suggests work needed to overcome these challenges.

Research on development of water soluble anti-cancer drugs is one of the great challenges of modern medicinal chemistry. Resveratrol (Res) is one of the many phytoalexins producing stilbenoids present in several medicinal plants, grape skin, peanuts, and red wine. It has been found to exhibit anti-cancer, anti-inflammatory, and anti-oxidant properties. Water solubility and bioavailability are some of the setbacks of this interesting compound. In view of this, effort has been made to synthesize amino acid derivative of resveratrol to improve its bioavailability and solubility in water. Methyl 4-{-[(1E)-2-(3, 5-dihydroxyphenyl)-ethenyl] - phenoxy} butyrate (7), a novel ester intermediate, has been synthesized and could be subjected to further chemical transformations to obtain amino acid derivatives.

No description available.

Ce travail a pour objectif d'étudier la formation des aérosols organiques secondaires (AOS) formés dans l'atmosphère à partir de l'oxydation en phase gazeuse de composés organiques volatils en présence d’oxydants atmosphériques (ozone, radicaux hydroxyle, chlore et nitrate). Parmi eux, les hydrocarbures aromatiques polycycliques (HAP) ont été proposés comme étant une source potentiellement importante d’AOS d’origine anthropique. Ainsi, l’oxydation de quatre HAP gazeux majoritaires (naphtalène, acénaphtylène, acénaphtène et phénanthrène) en présence des principaux oxydants atmosphériques a été menée afin de déterminer la formation d’AOS. La caractérisation des phases gazeuse et particulaire par spectrométrie de masse et spectroscopie optique a permis d’identifier les principaux produits d’oxydation afin de proposer des mécanismes réactionnels conduisant à la formation d’AOS. Les différents rendements de formation ont également été déterminés dans le but d'évaluer l'impact de l'oxydation des HAP en phase gazeuse comme source d’aérosols. Les expériences ont été conduites en chambres de simulation atmosphérique ainsi qu'en réacteur à écoulement. L'évolution de l'AOS au cours de son vieillissement a également été étudiée pour identifier les différents processus oxydatifs mis en jeu au sein de l'aérosol organique. / This work deals with the secondary organic aerosol (SOA) formation from gas phase oxidation of volatile organic compounds in the presence of atmospheric oxidants (ozone, hydroxyl radical, chlorine and nitrate radical). Among them, polycyclic aromatic hydrocarbons (PAHs) have been proposed as an important potential source of anthropogenic SOA. The oxidation of 4 main gaseous PAHs (naphthalene, acenaphthylene, acenaphthene and phenanthrene) in the presence of main atmospheric oxidants has been performed in order to investigate the SOA formation. Characterization of both gas and particulate phases has been carried out using mass spectrometry and optical spectroscopy allowing the identification of products in both phases. Then, chemical mechanisms have been proposed in order to explain SOA formation. SOA yields have been also determined to evaluate the impact of the gas phase oxidation of PAHs in SOA formation. Experiments have been carried out using flow tube and atmospheric simulation chambers. SOA fate has been investigated to determine the different oxidation processes involved in SOA aging.

Natural oils are regularly used in cosmetics and as treatment for numeral skin conditions (Nielsen, 2006:575). The natural products industry is a multibillion dollar industry and has grown tremendously over the past few years. Natural oils used in cosmetics contain a range of fatty acids which contribute to several valuable properties in cosmetic- and personal care products. Fatty acids are divided into saturated acids and unsaturated acids (Vermaak et al., 2011:920,922). Because of the popularity and wide diversity of skin care products, it is necessary to create products that will distinguish themselves from the rest of the commercial products. To include natural oils in skin care products is a new way to prevent skin ageing, as well as other dermatological conditions. In this study, a natural oil, namely crocodile oil was used. Crocodile oil is obtained from the fat of the Nile crocodile (Crocodylus niloticus). Crocodile oil has the same composition as human skin oil. It only differs with regard to the percentages of the ingredients present. Crocodile oil contains saturated and unsaturated fatty acids. Because of the similar composition as human skin oil, crocodile oil will rarely be allergenic when applied to human skin and therefore will be a very accepted and harmless product to use (Croc city, 2012). There are many claims of positive results when crocodile oil containing products have been used. It includes fading of freckles, treatment of acne and pimple marks, dark lines, wrinkles and laugh lines. It also includes vanishing of dark shadows, sun spots and other discolorations. It helps prevent discolorations from forming and makes the skin softer, brighter and more attractive. It also controls rashness and dryness (Croc city, 2012). Because of crocodile oil’s anti-ageing, anti-fungal and anti-bacterial effects claimed by crocodile oil suppliers, and due to the fact that little scientific data is available on crocodile oil, it was decided to investigate the claims. In this study, the aims and objectives were to use natural oil, namely crocodile oil, and investigate the fatty acid profile, anti-microbial and anti-fungal activity, anti-oxidant activity, toxicity studies, stability determination of crocodile oil lotion and clinical efficacy testing of the anti-ageing effects. To determine the fatty acid profile of crocodile oil, fatty acid methyl ester (FAME) analysis with gas chromatography were used. Identification of FAME peaks in the samples was made by comparing the relative retention times of FAME peaks from samples to those of reference standards. The composition of fatty acids in crocodile oil compared well to fatty acids found in human skin oil. Anti-microbial and anti-fungal tests were done by Envirocare Laboratories, North-West University, Potchefstroom. Staphylococcus aureus, Esterichia coli, Pseudomanas aeruginosa, Candida albicans, Brasiliensis, Propionibacterium acnes and Trichophyton rubrum cultures were used to determine the anti-microbial and anti-fungal activity of crocodile oil. Unfortunately no activity was observed. The anti-oxidant properties of crocodile oil and crocodile oil lotion were determined by using the most commonly used method for measuring Malondialdehyde (MDA) in biological samples, namely the thiobarbituric acid (TBA) test. This method is based on spectrophotometric quantification of the pink complex formed after reaction of MDA with two molecules of TBA. No anti-oxidant activity was observed in the oil or the lotion. Toxicity studies were performed by Dr. D. Goosen (BVSc Hons. Pret.) from Tswane University of Technology (Pretoria, South Africa). The studies showed that the lotion had no toxicity in the skin sensitisation, acute dermal toxicity and acute dermal irritation studies. To determine the stability of the crocodile oil lotion, the formulated products were store at 25 °C / 60% RH (relative humidity), 30 °C / 60% RH and 40 °C / 75% RH for 6 months in the original packaging as well as a glass container. The stability tests included pH, viscosity, visual appearance assessment, zeta-potential, droplet size and mass loss. The crocodile cream lotion was stable over the 6 months period in both containers. Clinical efficacy testing was performed at the CEL (Clinical Efficacy Laboratory) of the North-West University, Potchefstroom, South Africa. A short-term study over a period of 3 h was performed to investigate the hydrating effects of crocodile oil lotion. A long-term study over a period of 12 weeks was performed to examine the anti-ageing effects of crocodile oil lotion. An erythema study was also conducted to test the anti-erythema properties of crocodile oil lotion. Although the crocodile oil lotion as well as the placebo lotion showed an increase in skin hydration, there was no significant difference between the two treatments. Crocodile oil lotion also showed no anti-erythema properties. / Thesis (PhD (Pharmaceutics))--North-West University, Potchefstroom Campus, 2013.