Yes / The removal of the ubiquitous phenol and phenolic compounds in industrial wastes is a critical environmental issue due to their harmful threats to wildlife and potential adverse human health effects. The removal of such compounds is therefore of significant importance in water treatment and reuse. In recent years, reverse osmosis (RO) has been successfully utilised in several industrial processes and wastewater treatment including phenol removal. In this paper, a new model based on a spiral-wound RO process is developed for the removal of phenol from wastewater. A simplified mathematical algorithm using an irreversible thermodynamic approach is developed. This results in a set of non-linear Differential and Algebraic Equations (DAEs), which are solved based on a number of optimised model parameters using a combined methodology of parameter estimation and experimental phenol-water data derived from the literature. The effects of several operational parameters on the performance (in terms of removal of phenol) of the process are explored using the model.

Yes / Phenol and phenolic derivatives found in different industrial effluents are highly toxic and extremely harmful to human and the aquatic ecosystem. In the past, trickle bed reactor (TBR), reverse osmosis (RO) and other processes have been used to remove phenol from wastewater. However, each of these technologies has limitations in terms of the phenol concentration in the feed water and the efficiency of phenol rejection rate. In this work, an integrated hybrid TBR-RO process for removing high concentration phenol from wastewater is suggested and model-based simulation of the process is presented to evaluate the performance of the process. The models for both TBR and RO processes were independently validated against experimental data from the literature before coupling together to make the hybrid process. The results clearly show that the combined process significantly improves the rejection rate of phenol compared to that obtained via the individual processes.

L’invasion des ostéoblastes par Staphylococcus aureus (SA) est considérée comme responsable, au moins partiellement, de l’évolution chronique ou récurrente des infections osseuses (IO). Nous avons émis l’hypothèse que des différences d’interactions SA-ostéoblastes pouvaient être associées aux différences de présentation clinique des IO. Nous avons d’abord développé un modèle ex vivo d’infection intracellulaire d’ostéoblastes humains permettant de quantifier l’adhésion, l’invasion, la survie intracellulaire de SA et les dommages subis par les cellules infectées. Grâce ce modèle, nous avons montré que les SA communautaires résistants à la méticilline (CA-MRSA), un groupe polyphylétique de souches hypervirulentes associées à des formes aiguës et sévères d’IO, induisent une cytotoxicité supérieure à celle des MRSA hospitaliers (HA-MRSA) associés à des IO plus souvent chroniques. A l’aide de mutants isogéniques, nous avons pu démontrer que cette cytotoxicité était indépendante de la toxine de Panton-Valentine et l’alphahémolysine mais associée à la surexpression des phenol-soluble modulins (PSM) par les CA-MRSA. Ces résultats ont permis d’identifier un nouveau mécanisme de virulence des CA-MRSA basé sur l’invasion des ostéoblastes et l’activité intracellulaire des PSM. Parallèlement, nous avons montré que certains antibiotiques modifient le niveau de transcription et d’expression des protéines staphylococciques impliquées dans l’invasion des ostéoblastes, sans que nous ne puissions montrer une modification de la capacité d’invasion de S. aureus dans ce même modèle ex vivo. Nos travaux ouvrent de nouvelles perspectives dans la compréhension et la prise en charge des IO due à SA / Osteoblast invasion by Staphylococcus aureus (SA) is currently considered a putative explanatory mechanism for the chronic or recurrent nature of osteomyelitis. We raised the hypothesis that inter-strain differences in the interactions between S. aureus and osteoblasts at the cellular level could correlate with differences in the clinical presentation of osteomyelitis. We first developed an ex vivo model of intracellular bacterial challenge of human osteoblasts to quantify SA adhesion, invasion and intracellular survival as well as SA-induced damage to infected cells. By means of this model, we have demonstrated that community-acquired methicillinresistant SA (CA-MRSA) strains, which belong to a polyphyletic group endowed with high virulence and are associated with severe and acute forms of osteomyelitis, induce more cytotoxicity in osteoblasts as compared to hospital MRSA strains, which in turn are more frequently involved in chronic forms of osteomyelitis. Using isogenic CA-MRSA mutants, we determined that SA-induced osteoblast damage was independent of the production of Panton-Valentin leukocidin and alpha-toxin, but was associated with the overexpression of phenol-soluble modulins (PSMs) by CAMRSA. These findings elucidate a novel virulence strategy of CA-MRSA based on the invasion and PSM-related killing of osteoblasts. In parallel to this research, we demonstrated that several antibiotics alter the transcription and expression levels of SA adhesins involved in osteoblast invasion. However, antibiotics did not induce changes in SA invasiveness in our ex vivo infection model. Collectively, our findings provide new insights into the pathogenesis of SA osteomyelitis

D. Tech. Chemical Engineering / Aims of this research project was to add value to largely wasted South African sawdust by development of low-cost AC of high efficiency for removal of toxic Cr (VI), phenol and glutaraldehyde from dilute aqueous media. The main objectives of the research project were: a) To develop low-cost AC based on South African P. patula sawdust using economical physical superheated steam activation.Characterization of carbon samples for selection of optimum preparation conditions for development of low-cost AC of effective microporosity mesoporosity and surface functionality for enhanced adsorption capacity of Cr (VI) and/or phenol and/or glutaraldehyde from dilute aqueous solution. Acid-amine surface groups modification of optimally developed AC for further enhancement of adsorption capacity for mixed polarized glutaraldehyde molecules from aqueous solution. b) To evaluate the aqueous phase batch adsorption properties of developed AC for Cr (VI) and phenol and, of acid-amine modified developed AC for glutaraldehyde. Determination of optimum pH for adsorption; accurate adsorption isotherm modelling for determination of maximum adsorption capacity, comparison of maximum adsorption capacities for Cr (VI) and phenol of developed AC with commercial AC and literature ACs, and attempt to establish average micropore size for enhanced capacity for Cr (VI) and phenol from dilute aqueous solution.Kinetics reaction and diffusion modelling for determination of adsorption rate constants and diffusion parameters; and determination of adsorption thermodynamic parameters.Evaluation of equilibrium selectivity of developed AC for Cr (VI) and/or phenol in binary aqueous solutions. c) To evaluate aqueous phase fixed-bed adsorption characteristics of developed AC for single Cr (VI) and mixed solution using Rapid Small Scale column Tests (RSSCTs). Generation of breakthrough curves at optimum adsorption conditions for evaluation of column performance indicators at different process conditions, bed regeneration-reusability potential, and dynamic adsorption selectivity of developed AC for Cr (VI) from solution of base metals. Determination of column diffusion parameters; accurate mass transfer and empirical modelling of breakthrough data; determination of applicable RSSCT scaling equation; and optimization of breakthrough data for accurate RSSCT scale-up.

Ce travail avait pour objectif l'étude de l'impact des deux procédés : la déshydratation imprégnation par immersion (DII) et le séchage convectif menés séparément ou combinés sur les transferts couplés d'eau et de saccharose et les principaux critères de qualité de fruit (écart de couleur, teneur en phénols totaux (PT), teneur en acide ascorbique (AA), retrait volumique, activité de l'eau) en prenant la poire Conférences comme modèle. L'effet des procédés sur les morceaux de poire a été appréhendé selon deux approches : (i) une étude globale de l'impact des variables de commandes sur la qualité du produit fini et (ii) une étude cinétique des composés d'intérêt nutritionnel et de la qualité (couleur, retrait, activité de l'eau).Un plan d'expériences composite centré à quatre facteurs et cinq niveaux a été établi (concentration en saccharose de la solution osmotique : 25-65%, température de DII : 20-60 °C, durée de la DII : 0,5-6,5 h, température du séchage convectif : 30-70 °C) pour étudier l'effet global des procédés sur le produit fini. En DII, les paramètres « °Brix, « durée » et « la température de la solution » ont un effet significatif (p < 0,01) sur les pertes en eau, le gain en soluté et les attributs de qualité de morceaux de poire. Les pertes en AA sont plus élevées que les pertes en PT et sont essentiellement dues à l'oxydation et à l'entraînement par l'eau. Durant le séchage convectif, les pertes en PT et en AA dépendent plus de la durée du procédé que de la température d'exposition. Elles atteignent respectivement 80% et 34% après 10 h de séchage à 30 °C. Le changement de couleur de morceaux de poire dépend de la durée et de la température de traitement et est plus prononcé en fin de séchage. Des modèles quadratiques prédictifs ont été proposés pour relier les variables de réponse (aw, différence de couleur, perte en PT et durée totale de traitement) aux paramètres opératoires des deux procédés étudiés. Cependant, la perte en AA décroit linéairement avec la durée de DII. Une optimisation multicritères en utilisant la méthodologie des surfaces de réponse (MSR) a été proposée (pertes minimales en PT et en AA, durée totale du traitement et différence de couleur réduites et une aw inférieure à 0,6) pour la combinaison DII/séchage. Les conditions optimales sont : solution osmotique à 28°C et 25°Brix, une durée de DII de 30 min et un séchage convectif à 60 °C. Par ailleurs, les effets de la température (30, 45 et 60 °C) et de l'imprégnation en saccharose par DII (10 et 65 min, 70°Brix, 30 °C) sur les isothermes de désorption et sur la température de transition vitreuse (Tg) de morceaux de poires, de pommes et d'abricots ont été déterminés. L'imprégnation en saccharose du tissu végétal atténue l'influence de la température sur sa capacité de sorption. Elle engendre un effet dépresseur de l'activité de l'eau et une augmentation de l'hygroscopicité de la poire, la pomme et l'abricot à température élevée. Les isothermes de désorption des abricots frais et enrichis en saccharose présentent un croisement des courbes marquant l'inversement de l'effet de la température sur les isothermes. La Tg dépend de la température, de la teneur en saccharose et de la teneur en eau des fruits. Pour une teneur en eau constante, l'augmentation de la température et la durée de DII se traduisent par l'augmentation de la Tg. Les digrammes de phase (Tg=f(X) et Tg=f(aw)) des fruits ont été établis à 30, 45 et 60°C et les teneurs en eau critiques ainsi que les activités d'eau critiques ont été déterminées. Une teneur en eau en fin de séchage inférieure ou égale à 0,02 g/g M.S. est recommandée pour l'obtention de morceaux de fruit stables aux niveaux microbiologique, physicochimique et rhéologique. / The aim of this work was the study of the impact of both drying processes: dehydration-impregnation by soaking (DIS) and convective drying performed separately or in combination on mass transfers of water and sucrose and on the main quality characteristics of the fruit (total difference of colour, total phenols (TP) and ascorbic acid (AA) contents, shrinking, water activity) by taking the pear Conference as a model. The processes effect on the pieces of pear was apprehended according two approaches: (i) a global study of the impact of the variables of commands on the quality of finished product and (ii) a kinetic study of nutritional compounds and the quality (colour, shrinkage, and water activity). Central Composite Design with four factors (sucrose concentration: 25-65 %, temperature: 20-60 °C, immersion time: 0.5-6.5 hr and drying temperature: 30-70 °C) at five levels each was used for pears processing. During DIS, the variables: immersion time, temperature and concentration of sucrose solution had a significant effect (p<0.01) in the loss of water, the solid gain and the quality attributes of pears. The losses in AA are higher than those in TP and are essentially due to the oxidation and the leaching with water. During the convective drying, the losses in TP and in AA depend more on the time of the process rather than the temperature of exposition. They reach respectively 80% and 34% after 10 h of drying at 30 °C. The color change of pear depends on the time and temperature of treatment and is more pronounced at the end of drying. Predictive and quadratic models were suggested to link the responses variables (aw, total colour difference, TP loss and total time treatment) to operational parameters of both studied processes. The losses in AA decrease linearly with the duration of DIS. A multicriteria optimization using response surface methodology (RSM) was proposed (minimal losses in TP and in AA, reduced total processing time and total difference in colour and an aw inferior to 0.6) for the combination DIS/convective drying. The optimal conditions are: osmotic solution at 28°C and 25°Brix, a DIS lasting 30 min and a convective drying at 60 °C. Otherwise, the temperature effects (30, 45 and 60 °C) and the sucrose impregnation by DIS (10 and 65 min, 70°Brix, 30 °C) upon the desorption isotherms and the transition temperature (Tg) of pears, apples and apricots were determined. The sucrose impregnation diminishes the influence of temperature on its sorption ability. It generates a depressing effect on water activity and a rise of pear hygroscopicity, apple and apricot at a high temperature. The desorption isotherms of fresh and sucrose impregnated apricot present a crossing of curves which mark the inverse of the effect of temperature on isotherms. The Tg depends on the temperature, the sucrose content and the fruit water content (X). For constant water content, the rise of temperature and of the duration de DIS result in the increase of Tg. The phase diagrams (Tg=f(X) et Tg=f(aw)) of fruits were established at 30, 45 and 60°C and the critical water content as well as the critical water activities were determined. Water content at the end of drying inferior or equal to 0.02 g/g d.b. is recommended to obtain stable fruit pieces at microbiological, physiochemical and rheological levels.

Ce mémoire traite de la carbonisation de différents déchets de biomasse par pyrolyse douce dans une première étape. Dans une seconde étape, les charbons produits ont été activés à la vapeur d'eau. Six essences de bois (charme, chêne, douglas, épicéa de Sitka, hêtre et peuplier) ont été carbonisées et l'activation a été étudiée sur 4 essences (chêne, douglas, épicéa et peuplier). La première partie de ce mémoire consiste en une étude bibliographique sur la biomasse et sa valorisation énergétique, la production de charbons et l'activation. La deuxième partie de ce rapport présente les résultats expérimentaux relatifs à la carbonisation. Lorsque la carbonisation est complète, on peut corréler les principales propriétés physiques des charbons produits à partir des propriétés initiales du bois anhydre. Les modifications anatomiques induites par la carbonisation ont été expliquées à partir de mesures sur un porosimètre à mercure et d'observations au microscope électronique. Dans la troisième partie, les charbons obtenus à partir des 4 essences citées ont été activés à la vapeur d'eau à 800 °C pendant une heure. Les principales propriétés physiques caractérisant les charbons activés ont été déterminées. L'adsorption du phénol en phase aqueuse a été étudiée et les isothermes de sorption à 25 °C ont été décrites. L'étude des transferts de matière a montré que l'adsorption du phénol pouvait être caractérisée par un coefficient global de transfert de matière. Pendant l'adsorption, trois étapes limitantes successives ont été observées pendant lesquelles le coefficient global de transfert de matière est assez constant et dont la valeur est divisée par un facteur 10 à chaque changement d'étape / This report concerns the carbonization of different biomass wastes by soft pyrolysis in a first part. In a second part, the charcoals produced have been activated by water vapor. 6 wood species (ash, oak, douglas, Sitka spruce, beech and poplar) have been carbonized and the activation has been investigated on 4 wood species (oak, douglas, spruce and poplar). The first chapter of this report consists in a bibliographical study on biomass, its energetic valorization, production of charcoals and their activation. The second chapter of this report presents the experimental results concerning the carbonization. When the carbonization is complete, the main physical properties of the charcoals produced can be correlated to the initial properties of oven dry woods. The anatomic changes induced by pyrolysis have been explained from measurements performed on a mercury porosimeter and observations on an electronic microscope. In the third chapter, charcoals produced from the 4 wood species cited have been activated with water vapor at 800 °C during 1 hour. The main physical parameters characterizing the activated carbons have been determined. The adsorption of phenol in an aqueous phase has been investigated and the isotherms of sorption at 25 °C have been described. The study of mass transfers shows that the adsorption of phenol can be characterized by a global mass transfer coefficient. During the adsorption, 3 successive limiting steps have been observed. For each step, the mass transfer coefficient is quite constant but its value is divided by about 10 after each change of step

Os compostos fenólicos estão presentes em grande número de efluentes industriais, cujos lançamentos inadequados podem acarretar em riscos ao meio ambiente e à saúde humana. O uso de fungos em reatores biológicos é uma alternativa de tratamento de despejos que possuem compostos persistentes, como fenóis. O objetivo deste trabalho foi estudar a viabilidade do uso de Aspergillus niger em reator biológico para o tratamento de água residuária sintética contendo fenol. O trabalho foi realizado com dois tipos de reatores: em batelada e reatores contínuos com escoamento ascendente. No experimento em batelada, foram utilizados 5 reatores de controle (RC), 5 com fungos (RF) e 5 com fungos e glicose (RFG), verificando-se o uso de glicose (5 g/L), como substrato primário, e a remoção do fenol pelos fungos. Estes apresentaram maior desenvolvimento nos reatores contendo glicose (RFG), alcançando-se remoção de 100% de fenol, no quinto e último dia de experimento. Nestes reatores, a velocidade média de consumo de fenol foi quase o dobro da desenvolvida nos reatores sem glicose (RF). A remoção de matéria orgânica, medida como DQO, foi superior nos reatores contendo glicose (RFG) e atingiu 93%, no quinto dia. Não houve remoção significativa de fenol nos reatores de controle. Nos RF, as maiores remoções de fenol e matéria orgânica foram registradas no quinto dia e foram, respectivamente, de 48% e 27%. As maiores remoções de fenol em relação à de matéria orgânica indicam, possivelmente, a presença de compostos intermediários da degradação do fenol. Os reatores contínuos, cada um com volume total de 4,45 L e com meios suportes de manta de polipropileno (R1) e espuma de poliuretano (R2), foram mantidos sob as mesmas condições operacionais, durante 399 dias, divididos em três tempos de detenção hidráulica: 8 h, dividido em duas fases de alimentação (Fase I – alimentação complementada com glicose e Fase II – alimentação sem complementação de glicose); 4 h e 6 h. As maiores remoções de fenol ocorreram durante o tempo de detenção hidráulica (TDH) de 8 h, tanto com a presença ou não de 0,5 g/L de glicose no afluente, obtendo-se, na Fase I, remoções médias de fenol de 99,5% '+ OU -' 2 (R1) e de 98% '+ OU -' 5 (R2) e, na Fase II, 99,6% '+ OU -' 1(R1) e 92% '+ OU -' 23 (R2). No tempo de detenção hidráulica de 4 h, a remoção média de fenol ficou em torno de 50%, em ambos os reatores. Com o tempo de detenção hidráulica de 6 h, houve melhora na eficiência de remoção, atingindo 72% '+ OU -' 35 (R1) e 78% '+ OU -' 25 (R2). Análises microscópicas revelaram que os fungos cresceram bem nos suportes empregados, porém o uso de espuma de poliuretano provocou maiores problemas operacionais. Apesar dos bons resultados de remoção de matéria orgânica e de fenol, houve crescimento excessivo de biomassa no interior dos reatores contínuos, o que resultou na colmatação do leito, indicando necessidade de se procurar melhor ajuste nutricional do meio para controlar a geração de biomassa. / The phenolic compounds are present in a great quantity in industrial effluents, which inappropriate release can cause serious damage to the environment and to human health. The usage of fungi in biological reactors is an alternative to the treatment of wastes that contain compounds with persistent nature like phenol. The goal of this work was the study of the available usage of Aspergillus niger in a biological reactor treating synthetic wastewater containing phenol. The work was realized in batch and upflow continuous reactors. Five control reactors (CR) were applied in the batch experiment, being five with fungi (FR) and five with fungi and glucose (GFR), in order to verify the application of glucose (5 g/L) as main substrate and the removal of phenol by fungi. These presented better development in the reactors containing glucose, with the achievement of 100% of phenol removal in the fifth and last day of the experiment. In these reactors, the mean consumption velocity of phenol was approximately the double of those that were developed in the reactors without glucose. The organic matter removal (measured as COD) was higher in the reactors containing glucose, achieving 93% in the fifth day. There was no significant phenol removal in the control reactors. The higher removals of 48% for phenol and 27% for organic matter were observed in the RF reactors in the fifth day, indicating the possible presence of intermediate compounds in the phenol degradation. The continuous reactors were built with total volume of 4,45 L each one, with polypropylene blanket as support media in the R1 reactor and polyurethane foam as support media in the R2 reactor. The reactors were kept in the same operational conditions during 399 days. These conditions were divided in three hydraulic detention times (HDT): 8 h, divided in two feeding phases (Phase I – feeding complemented with glucose and Phase II – feeding without complementation of glucose); 4 h and 6 h. The higher phenol removals occurred during the hydraulic detention time of 8 h, in the presence and absence of 0,5 g/L of glucose in the influent. The mean phenol removals of 99,5% '+ OU -' 2 (R1) and 98% '+ OU -' 5 (R2) were attained in the Phase I, and 99,6% '+ OU -' 1 (R1) and 92% '+ OU -' 23 (R2) in the Phase II. The mean phenol removal was around 50% in both reactors when hydraulic detention time of 4 h was applied. With the hydraulic detention time of 6 h, there was improvement in the removal efficiency that achieved 72% '+ OU -' 35 for R1 reactor and 78% '+ OU -' 25 for R2 reactor. The microscopic analyses showed that fungi grew well in the applied support media, but the usage of polyurethane foam caused more operational problems. Even with the good results of the organic matter and phenol removals, there was excessive growth of biomass inside the reactors. This resulted in the clogging of the blanket, indicating the necessity of better nutritional adjustment of the media to control the biomass generation.

Neste trabalho os complexos cis- [Ru(BAF)(bpy)(PPh3)(OH2)](ClO4)2 (monômero B) e cis-[Ru(dmbpy)2(PPh3)(OH2)](OPh)2 (monômero C) foram sintetizados e caracterizados através de métodos espectroscópicos e eletroquímicos, sendo utilizados na construção de novos eletrodos modificados EMs e aplicados na eletrooxidação de substratos orgânicos. A preparação destes EMs consistiu no recobrimento da superfície de eletrodos de feltro de carbono e de bastões de grafite pelos filmes poliméricos ancorados ao rutênio. Os intervalos de potencial aplicados para a polimerização dos complexos foram àqueles correspondentes, respectivamente, aos potenciais de polimerização do contra-íon difenolato e do ligante azóico contendo o grupamento fenol. A atividade catalítica destes EMs foi investigada através de um estudo cinético, através de eletrooxidações heterogêneas acompanhadas por UV/Vis de diversos compostos orgânicos como: safrol, isosafrol, álcool benzílico, fenil etil álcool, etil benzeno, tolueno, benzaldeído, ciclo hexen-2-ol, demonstrando que os EMs podem ser utilizados como catalisadores em reações de eletrooxidações com rendimentos satisfatórios. / In this work the complexes cis-[Ru(BAF)(bpy)(PPh3)(OH2)](ClO4)2 (B monomer) and cis-[Ru(dmbpy)2(PPh3)(OH2)](OPh)2 (C monomer) were synthesized and characterized by spectroscopic and electrochemical methods, and they were utilized in construction of new modified electrodes (MEs) and applied in electrooxidation of organic substrates. The preparation of these new MEs was done by coating the surfaces of carbon felt and carbon rod electrodes by polymeric films where the ruthenium complexes were anchored. The potential range applied to accomplish the polimerization of the complexes corresponds to the potencial ranges of diphenol anion and azoic ligand with the phenolic group, respectively. The catalytic activity of these MEs was studied by kinetic methodology monitoring the heterogeneous electroxidations by UV/Vis of some organic substrates like: safrol, isosafrol, benzylic alcohol, phenil ethyl alcohol, ethyl benzene, toluene, cycle-hexen-2-ol, showing that these EMs can be utilized as catalyst in electrooxidations reactions with goods yields.

Hidroquinona (HQ) é um dos metabólitos do benzeno responsáveis pelos efeitos tóxicos da exposição ao solvente, além de ser componente da dieta, medicamentos, cigarro e poluente do meio ambiente. Considerando a imunotoxicidade desta substância, o grupo de pesquisa do laboratório investiga o papel da exposição à HQ por período prolongado de tempo sobre respostas inflamatórias agudas (RIA). Neste contexto, o presente trabalho avaliou os efeitos desta exposição sobre os mecanismos vasculares e celulares da RIA de diferentes doses diárias de HQ (5, 10 ou 50 mg/kg) em ratos Wistar machos, via i.p., por 17 ou 22 dias, uma vez ao dia, com intervalos de 2 dias a cada 5 doses. Animais controles receberam o veículo (salina com 5% etanol). A resposta inflamatória aguda inata foi induzida pela administração de glicogênio de ostra (1% em PBS, 5 mL) na bolsa subcutânea dorsal ou pela instilação de lipopolissacarídeo de Salmonella abortus (LPS; 100 &#181;L de solução 100 &#181;g/mL); A resposta inflamatória aguda adquirida foi provocada pela inalação de ovalbumina (10 mL de solução de OA 1% PBS, 15 min) em animais previamente sensibilizados (10 &#181;/100mg AI(OH)3 no décimo dia de exposição). Os resultados obtidos mostraram que: 1) o aumento do número de leucócitos na bolsa dorsal de animais expostos a 50 mg/kg de HQ é dependente, pelo menos em parte, da maior interação de leucócitos circulantes à parede vascular da microcirculação, mas não é decorrente de alterações na reatividade microvascular; o aumento de expressão de moléculas de adesão (&#946;2 integrina), que pode ser a responsável pelo aumento de interaçãoleucócito-endotélio e migração celular; 2) a redução da migração de leucócitos para o pulmão inflamado pelo LPS em animais expostos a HQ, nas menores doses, não foi decorrente de modificações na interação leucócito-endotélio, nem da expressão de moléculas de adesão nos leucócitos circulantes ou na célula endotelial do tecido pulmonar; 3) a redução da migração celular para o pulmão durante a RIA alérgica em animais expostos a 5, 10 ou 50 mglkg de HQ é dependente, pelo menos em parte, da menor concentração de anticorpos anafiláticos circulantes e conseqüentemente da desgranulação reduzida de mastócitos teciduais, visualizados no leito mesentérico após desafio in situ pela OA. A menor produção de anticorpos anafiláticos pode ser decorrente da ação da HQ em diferentes tipos celulares, uma vez que foi observada expressão reduzida de moléculas co-estimulatórias em linfócitos do baço (CD45R e CD6), menor atividade microbicida de macrófagos peritoniais frente a Candida albicans e menor secreção de interferon-&#947; por células do peritônio. Em conjunto, os resultados apresentados mostram os mecanismos da HQ sobre a resposta do organismo ao trauma de diferentes origens, interferindo com tipos celulares distintos envolvidos nas reações. / Hydroquinone (HQ) is one of the metabolites of benzene responsible for the toxic effects of exposure to solvent, as well as being part of the diet, medicines, tobacco and polluting the environment. Considering the immunotoxicity of this substance, our laboratory has investigated the role of exposure to HQ by prolonged period of time on acute inflammatory responses (AIR). In this context, this study evaluated the effects of this exposure on the vascular and cellular mechanisms of AIR of different daily doses of HQ (5, 10 or 50 mg/kg) in male rats, via ip, for 17 or 22 days, a once a day, with intervals of 2 days every 5 doses. Control animais received the vehicle (saline with 5% ethanol). Innate AIR was induced by the administration of oysters glycogen (1% in PBS, 5 mL) into subcutaneous back pouch or by instillation of lipopolysaccharide of Salmonella aborius (LPS, 100 &#181;L of solução100 &#181;g/mL); Allergic AIR gained was caused by inhalation of ovalbumin (10 mL solution of 1% OA in PBS, 15 min) in previously sensitized animal (10 &#181;/100mg AI (OH)3 on the tenth day of exposure). Results showed that: 1) the increased number of white blood cells back into the pouch of animais exposed to 50 mg/kg of HQ is dependent, at least in part, of higher interaction of circulating leukocytes to the vascular wall of the microcirculation, but is not due to changes in microvascular reactivity; an increase of expression of molecules of accession (&#946;2 integrin), which may be responsible for the enhanced interaction of leukocyteendothelial and cell migration 2) the reduced migration of leukocytes into the lung inflamed by LPS in animals exposed to 5 or 10 mg/kg was not due to changes in the interactions of leukocyte to endothelium, either the expression of adhesion molecules in circulating white blood cells or in cell endothelial lung tissue, 3) the reduced cell migration to the lungs during the AIR allergic to animais exposed to HQ, in lower doses, is dependent on lower concentration of· circulating anaphylactics antibodies which may be responsible for the mast cell desgranulation. The lower amount of anaphylatic antibodies in the circulation may be due to action of HQ in different cells, as reduced expression of co-stimulatory molecules by Iymphocytes (CD45R and CD6), lower microbicide activity of macrophages and reduced secretion of interferon-&#947; by peritoneal cells were detected. Together, the results show the toxicity of HQ on the body\'s response to trauma from different sources, interfering with different cell types involved in the reactions.

O objetivo principal deste trabalho foi estudar a interferência de íons Cu2+ e Zn2+ na degradação do fenol pela reação de Fenton (Fe2+/Fe3+ + H2O2). Ambos os íons apresentaram efeito catalítico na reação de Fenton, porém atuam em etapas diferentes durante essa reação. Um dos primeiros intermediários da degradação, o catecol, é capaz de reduzir o Fe3+ a Fe2+, que, na presença de H2O2, cria um ciclo redox bastante eficiente. Portanto, este ciclo passa a ser o mecanismo principal da degradação térmica de fenol e seus produtos de oxidação nas etapas iniciais da reação. O íon Zn2+ interfere no tempo de persistência do catecol no meio reacional, provavelmente via estabilização do radical semiquinona correspondente. Um estudo da reação de cupro-Fenton (Cu2+ + H2O2) sugere dois possíveis papéis dos íons cobre: i) A reação de íons Cu1+ com H2O2 pode regenerar Cu2+ via uma reação análoga a de Fenton, formando radicais HO&#8226;. Na presença de um excesso de H2O2, o radical HO&#8226; pode ser consumido por outra molécula de H2O2 para produzir HOO&#8226;- e O2&#8226;-, (ii) Na etapa final da reação, quando o ferro(III) da solução é complexado na forma de ferrioxalato, os íons cobre assumem o papel de principal catalisador da degradação. Deste modo, a associação da reação de Fenton com a de cupro-Fenton resulta num aumento da eficiência global de mineralização do fenol / The principal objective of this work was a study of the interference of Cu2+ and Zn2+ ions on the degradation of phenol by the Fenton reaction (Fe2+/Fe3+ + H2O2). Both ions have a catalytic effect on the Fenton reaction, but act in different stages of the reaction. One of the first intermediates formed in the reaction, catechol, can reduce Fe3+ to Fe2+, which, in the presence of H2O2, forms an efficient catalytic redox cycle. Thus, this cycle becomes the principal route of thermal degradation of phenol and its oxidation products in the initial stages of the reaction. The Zn2+ interferes in the persistence time of catechol, probably via complexation with the corresponding semiquinone radical. A study of the cupro-Fenton reaction (Cu2+ + H2O2) suggests two principal modes of action of copper ions: (i) The reaction of Cu+ with H2O2 can regenerate Cu2+ via a reaction analogous to the Fenton reaction, forming the HO&#8226; radical. In the presence of excess H2O2, the HO&#8226; radical can react with another molecule of H2O2 to produce HOO&#8226;- and O2&#8226;-. (ii) In the final stages of the reaction, when the iron(III) in the solution is complexed in the form of ferrioxalate, the copper ions assume the role of the main catalyst of the degradation. As a result, the association of the Fenton reaction with the cupro-Fenton reaction leads to an overall improvement of the efficiency of the mineralization of phenol.