Candida albicans is an opportunistic fungal pathogen that may cause mucutaneous infection and/or disseminated candidasis if the host defense system is impaired (such as those in HIV patients). Cell surface of C. albicans is the frontier where initial interplay between host-pathogen takes place and therefore is of great importance in understanding the mechanism of hostpathogen interaction. MALDI-TOF-MS analysis of intact fungal cells yielded mass signatures for rapid species differentiation, strain grouping and yeast morphogenesis monitoring. Cell surface biotinylations at low temperature (4°C), enzymatic digestion of the intact fungal cell surface proteins ("whole cell shaving"), biotin-avidin affinity enrichment of biotinylated peptides, liquid chromatography mass spectrometry (LC-MS) based proteomic approach were employed for unambiguous identification of cell wall/cell wall associated proteins and the exposed peptide segments of these proteins. SILAC (Stable Isotope Labeling by Amino acids in Cell Culture) based CWP quantification analyses were performed to monitor CWP accumulation level change in response to hyphae induction. Information on surface exposed peptide segments and regulation of cell wall/surface protein during morphogenesis provided new candidates to the pool of potential peptide targets for protective vaccine development. A New type of "fluorous" (fluorinated alkane) affinity gained popularity due to its low level nonspecific protein/peptide binding. Fluorous labeling reagents that target primary amine groups in proteins/peptides were synthesized and characterized. The acid labile linker in the labeling reagents allows cleavage of the bulky fluorous tag moiety and the long oligo ethylene glycol (OEG) spacer after fluorous affinity purification. Upon collision induced decomposition, the labeled peptide ion yielded a characteristic fragment that could be retrieved from the residual portion of fluorous affinity tag, and serve as a marker to indicate that the relevant peptide had been successfully labeled. Results showed that both the protein/peptide labeling and affinity enrichment/separation process were highly efficient.

Por meio das mudanças de paradigmas relacionados à gestão ambiental e elevação dos custos de lançamento de efluente, captação e tratamento de água, as indústrias passam por processos de inovação que resultam em melhor utilização dos recursos e maior diminuição dos custos. Além disso, as empresas estão sujeitas a maiores exigências quanto à legislação ambiental vigente impulsionando-as a implantar sistemas de reúso de efluentes. Apesar de representar uma importante atividade econômica, a indústria de laticínios é responsável pela geração de efluentes líquidos com alto potencial poluidor. O presente trabalho teve como objetivo a redução de contaminantes e melhoria da biodegradabilidade de efluentes de laticínios utilizando tratamentos combinados, em destaque, coagulação/floculação, processos com membranas e oxidação/redução química fotocatalítica. Os efluentes foram provenientes de uma indústria da região, oriundos da etapa de nanofiltração do soro ultrafiltrado. Eles foram divididos em duas correntes, denominadas de concentrado de nanofiltração (corrente 1) e permeado de nanofiltração (corrente 2). Para o tratamento da corrente 1 foi proposto inicialmente coagulação/floculação utilizando diferentes agentes coagulantes naturais (quitosana, derivado de tanino e extrato de moringa), seguido do uso de processos com membranas do tipo microfiltração (0,40 ?m em polieterimida) e ultrafiltração (50 kDa em polietersulfona). Para a corrente 2 foi proposto a utilização de Processos Oxidativos e Redutivos Avançados. Em todas as etapas foi utilizada a Metodologia da Superfície de Resposta para identificação das condições otimizadas. Para o tratamento de coagulação/floculação da corrente 1 foram avaliadas as influências do pH, dos coagulantes naturais e da agitação sobre as variáveis resposta reduções de carbono orgânico total (COT), demanda química de oxigênio (DQO) e turbidez. Na condição indicada como ótima foram alcançadas reduções de 18,3% de COT, 12,7% de DQO e 19,6% de turbidez. A partir da condição otimizada a corrente 1 foi submetida aos processos com membranas, sendo selecionada a microfiltração como melhor tratamento. O uso dessas membranas possibilitou reduções de 1,25% em COT, 5,21% em DQO e 87,4% em turbidez. A combinação destas tecnologias possibilitou a eliminação de 20,1%, 18,0%, 89,8% em COT, DQO e turbidez, respectivamente. Para o tratamento da corrente 2 foram utilizados diferentes tipos de processos oxidativos avançados sendo eles, foto-Fenton (íons ferrosos) e foto-Fenton avançado (uso de ferro metálico). Nestes casos foram avaliadas a influência das concentrações de peróxido de hidrogênio e íon ferroso e ferro metálico considerando como variáveis resposta reduções de COT e DQO. Os resultados otimizados obtidos para o POA foto-Fenton permitiram reduções de 89,9% em COT e 50,8% em DQO, enquanto os resultados otimizados para POA foto-Fenton avançado foram reduções de 74,9% de COT e 41,0% de DQO. / Through the paradigm changes related to environmental management and rising costs of effluent discharge, water abstraction and treatment, industries undergo innovation processes that result in better use of resources and greater reduction in costs. Moreover, companies are submitted to greater requirements regarding environmental regulations driving them to deploy reuse of wastewater systems. Despite representing an important economic activity, the dairy industry is responsible for producing wastewater with high pollution potential. The present work was carried out in order to reduce contaminants and improve the biodegradability of dairy effluent by using an hybrid wastewater treatment based on coagulation/flocculation, membrane process and photocatalytic chemical oxidation/reduction. The effluents came from a regional industry and originating from the nanofiltration step of an ultrafiltrate whey. They were divided into two streams, called nanofiltration concentrate (stream 1) and nanofiltration permeate (stream 2). For the treatment of stream 1 was initially proposed coagulation/flocculation using different natural coagulant agents (chitosan, derivative tannin and moringa extract), followed by membrane processes type of microfiltration (0.40 ?m in polyetherimide) and ultrafiltration (50 kDa in polyethersulfone). For the stream 2 Advanced Oxidation and Reductive Processes were performed. In all steps of the work Response Surface Methodology was used to identify the optimum conditions. For the coagulation/flocculation treatment, the influence of the pH, natural coagulants and agitation were evaluated on the response variables total organic carbon (TOC), chemical oxygen demand (COD) and turbidity reductions. The optimized results reduced of 18.3% TOC, 12.7% COD and 19.6% turbidity. From the indicated condition stream 1 was submitted to membrane processes, being selected the microfiltration as the best treatment. The use of theses membranes provided 1.25% TOC, 5.21% COD and 87.4% turbidity reductions. The combination of these technologies has enabled the elimination of 20.1%, 18.0%, 89.8% in TOC, COD and turbidity, respectively. For the treatment of the stream 2 different types of Advanced Oxidation Processes were used being them, photo-Fenton (ferrous ions) and advanced photo-Fenton (metallic iron). In this cases the influence of the hydrogen peroxide, ferrous ion and metallic iron concentrations were evaluated, considering as response variables TOC and COD reductions. The optimized results for the photo-Fenton AOP allowed 89.9% TOC and 50.8% COD reductions, while the results optimized for advanced photo-Fenton AOP were 74.9% TOC and 41.0% COD reductions.

O chorume in natura utilizado foi proveniente do aterro sanitário da cidade de Cachoeira Paulista no interior do estado de São Paulo. Possui baixa razão de biodegradabilidade (DBO/DQO = 0,094) evidenciado principalmente através das análises de caracterização dos parâmetros COT (618,1 mg C/L), DQO (4345,88 mg O2/L) e DBO5 (409,7 mg O2/L) que estão acima do limite permitido pela legislação. Em função disso, os processos oxidativos avançados (POA´s) surgem como alternativa para o seu pré-tratamento. O foco principal desse trabalho foi utilizar a aplicação da fotocatálise homogênea, empregando concomitantemente a luz solar com o reagente Fenton (H2O2 + Fe2+) num reator aberto com volume constante da amostra (3L) em sistema semi-batelada para verificar a eficiência do processo na remoção da carga orgânica. O reator solar possui um suporte de madeira que está direcionado ao Equador com um ângulo de inclinação de 23º, com uma placa metálica sem pigmentação denominada branco, numa vazão constante (13 L / min) em períodos com maior intensidade de radiação UV e monitorados pelo radiômetro. Após o ajuste do chorume de acordo com a planilha experimental, o volume do reagente Ferro (0,82 mol) foi adicionado totalmente no início da reação e o peróxido de hidrogênio (30% m/v) durante 30 min do tempo total de 1 hora, através de uma bureta dosadora, de maneira controlada que o peróxido de hidrogênio fosse consumido integralmente na reação de degradação, aumentando assim sua eficiência. O chorume tratado foi bombeado até a parte superior da placa, percolando-a uniformemente enquanto recebia a radiação solar sobre a placa. O processo fotocatalítico foi otimizado por um planejamento fatorial (23) com duplicata e triplicata no ponto central contendo 19 experimentos com variáveis de entrada: pH (3, 3,5 e 4) , quantidade de [H2O2] ( 73,2 g , 85,4 g e 97,6 g ) e quantidade de [Fe2+ ] (4,0 g , 5,0 g e 6,0 g ). As variáveis respostas do processo utilizadas foram: eficiência de remoção de COT (Carbono Orgânico Total) e DQO (Demanda Química de Oxigênio). As maiores reduções percentuais de DQO e COT, respectivamente, 89,19% e 86,12%, além do aumento de sua biodegradabilidade para 0,55 com um custo de R$ 0,3558 / 3L. Desta forma, o processo fotocatalítico mostrou grande viabilidade técnica e econômica em relação à degradação da carga orgânica de chorume. / The leachate used was fresh from the landfill of the city of Cachoeira Paulista in the state of São Paulo. Has a low ratio of biodegradability (BOD / COD = 0.094) demonstrated mainly through the analysis parameters characterizing the TOC (618,1 mg C / l) COD (mg O2 4345,88 / L) and BOD5 (mg O2 409,7 / L) that are above the limit allowed by law. As a result, the advanced oxidation processes (AOP\'s) are an alternative to their pre-treatment. The main focus of this work was to use the application of photocatalysis homogeneous, employing concurrently sunlight with Fenton\'s reagent (H2O2 + Fe2+) in an open reactor with constant volume of sample (3L) in the semi-batch to verify the efficiency of the process in removal of organic matter. The solar reactor has a wooden support that is directed to the equator with a tilt angle of 23 º, with a metal plate without pigmentation called white, a constant flow rate (13 L / min) in periods with higher UV intensity and monitored by radiometer. After adjusting the leachate according to the experimental sheet, the volume of reagent iron (0,82 mol) was added entirely at the beginning of the reaction and hydrogen peroxide (30% w / v) for 30 min to 1 hour total time through a dosing burette so controlled that the hydrogen peroxide was consumed entirely in the degradation reaction, thus increasing its efficiency. The treated leachate was pumped to the top of the plate evenly percolating while receiving the solar radiation on the plate. The photocatalytic process was optimized by a factorial design (23) with duplicate and triplicate center point experiments containing 19 input variables: pH (3, 3,5 and 4), the amount of [H2O2] (73,2 g, 85,4 g 97,6 g) and the amount of [Fe 2+] (4,0 g, 5,0 g and 6,0 g). The response variables of the process were: removal efficiency of TOC (Total Organic Carbon) and COD (Chemical Oxygen Demand). The largest percentage reductions of COD and TOC, respectively, 89,19% and 86,12%, besides increasing its biodegradability to 0,55 at a cost of R $ 0,3558 / 3L. Thus, the photocatalytic process showed great technical and economic feasibility in relation to the degradation of the organic leachate.

O chorume in natura utilizado foi proveniente do aterro sanitário da cidade de Cachoeira Paulista no interior do estado de São Paulo. Possui baixa razão de biodegradabilidade (DBO/DQO = 0,094) evidenciado principalmente através das análises de caracterização dos parâmetros COT (618,1 mg C/L), DQO (4345,88 mg O2/L) e DBO5 (409,7 mg O2/L) que estão acima do limite permitido pela legislação. Em função disso, os processos oxidativos avançados (POA´s) surgem como alternativa para o seu pré-tratamento. O foco principal desse trabalho foi utilizar a aplicação da fotocatálise homogênea, empregando concomitantemente a luz solar com o reagente Fenton (H2O2 + Fe2+) num reator aberto com volume constante da amostra (3L) em sistema semi-batelada para verificar a eficiência do processo na remoção da carga orgânica. O reator solar possui um suporte de madeira que está direcionado ao Equador com um ângulo de inclinação de 23º, com uma placa metálica sem pigmentação denominada branco, numa vazão constante (13 L / min) em períodos com maior intensidade de radiação UV e monitorados pelo radiômetro. Após o ajuste do chorume de acordo com a planilha experimental, o volume do reagente Ferro (0,82 mol) foi adicionado totalmente no início da reação e o peróxido de hidrogênio (30% m/v) durante 30 min do tempo total de 1 hora, através de uma bureta dosadora, de maneira controlada que o peróxido de hidrogênio fosse consumido integralmente na reação de degradação, aumentando assim sua eficiência. O chorume tratado foi bombeado até a parte superior da placa, percolando-a uniformemente enquanto recebia a radiação solar sobre a placa. O processo fotocatalítico foi otimizado por um planejamento fatorial (23) com duplicata e triplicata no ponto central contendo 19 experimentos com variáveis de entrada: pH (3, 3,5 e 4) , quantidade de [H2O2] ( 73,2 g , 85,4 g e 97,6 g ) e quantidade de [Fe2+ ] (4,0 g , 5,0 g e 6,0 g ). As variáveis respostas do processo utilizadas foram: eficiência de remoção de COT (Carbono Orgânico Total) e DQO (Demanda Química de Oxigênio). As maiores reduções percentuais de DQO e COT, respectivamente, 89,19% e 86,12%, além do aumento de sua biodegradabilidade para 0,55 com um custo de R$ 0,3558 / 3L. Desta forma, o processo fotocatalítico mostrou grande viabilidade técnica e econômica em relação à degradação da carga orgânica de chorume. / The leachate used was fresh from the landfill of the city of Cachoeira Paulista in the state of São Paulo. Has a low ratio of biodegradability (BOD / COD = 0.094) demonstrated mainly through the analysis parameters characterizing the TOC (618,1 mg C / l) COD (mg O2 4345,88 / L) and BOD5 (mg O2 409,7 / L) that are above the limit allowed by law. As a result, the advanced oxidation processes (AOP\'s) are an alternative to their pre-treatment. The main focus of this work was to use the application of photocatalysis homogeneous, employing concurrently sunlight with Fenton\'s reagent (H2O2 + Fe2+) in an open reactor with constant volume of sample (3L) in the semi-batch to verify the efficiency of the process in removal of organic matter. The solar reactor has a wooden support that is directed to the equator with a tilt angle of 23 º, with a metal plate without pigmentation called white, a constant flow rate (13 L / min) in periods with higher UV intensity and monitored by radiometer. After adjusting the leachate according to the experimental sheet, the volume of reagent iron (0,82 mol) was added entirely at the beginning of the reaction and hydrogen peroxide (30% w / v) for 30 min to 1 hour total time through a dosing burette so controlled that the hydrogen peroxide was consumed entirely in the degradation reaction, thus increasing its efficiency. The treated leachate was pumped to the top of the plate evenly percolating while receiving the solar radiation on the plate. The photocatalytic process was optimized by a factorial design (23) with duplicate and triplicate center point experiments containing 19 input variables: pH (3, 3,5 and 4), the amount of [H2O2] (73,2 g, 85,4 g 97,6 g) and the amount of [Fe 2+] (4,0 g, 5,0 g and 6,0 g). The response variables of the process were: removal efficiency of TOC (Total Organic Carbon) and COD (Chemical Oxygen Demand). The largest percentage reductions of COD and TOC, respectively, 89,19% and 86,12%, besides increasing its biodegradability to 0,55 at a cost of R $ 0,3558 / 3L. Thus, the photocatalytic process showed great technical and economic feasibility in relation to the degradation of the organic leachate.

Por meio das mudanças de paradigmas relacionados à gestão ambiental e elevação dos custos de lançamento de efluente, captação e tratamento de água, as indústrias passam por processos de inovação que resultam em melhor utilização dos recursos e maior diminuição dos custos. Além disso, as empresas estão sujeitas a maiores exigências quanto à legislação ambiental vigente impulsionando-as a implantar sistemas de reúso de efluentes. Apesar de representar uma importante atividade econômica, a indústria de laticínios é responsável pela geração de efluentes líquidos com alto potencial poluidor. O presente trabalho teve como objetivo a redução de contaminantes e melhoria da biodegradabilidade de efluentes de laticínios utilizando tratamentos combinados, em destaque, coagulação/floculação, processos com membranas e oxidação/redução química fotocatalítica. Os efluentes foram provenientes de uma indústria da região, oriundos da etapa de nanofiltração do soro ultrafiltrado. Eles foram divididos em duas correntes, denominadas de concentrado de nanofiltração (corrente 1) e permeado de nanofiltração (corrente 2). Para o tratamento da corrente 1 foi proposto inicialmente coagulação/floculação utilizando diferentes agentes coagulantes naturais (quitosana, derivado de tanino e extrato de moringa), seguido do uso de processos com membranas do tipo microfiltração (0,40 ?m em polieterimida) e ultrafiltração (50 kDa em polietersulfona). Para a corrente 2 foi proposto a utilização de Processos Oxidativos e Redutivos Avançados. Em todas as etapas foi utilizada a Metodologia da Superfície de Resposta para identificação das condições otimizadas. Para o tratamento de coagulação/floculação da corrente 1 foram avaliadas as influências do pH, dos coagulantes naturais e da agitação sobre as variáveis resposta reduções de carbono orgânico total (COT), demanda química de oxigênio (DQO) e turbidez. Na condição indicada como ótima foram alcançadas reduções de 18,3% de COT, 12,7% de DQO e 19,6% de turbidez. A partir da condição otimizada a corrente 1 foi submetida aos processos com membranas, sendo selecionada a microfiltração como melhor tratamento. O uso dessas membranas possibilitou reduções de 1,25% em COT, 5,21% em DQO e 87,4% em turbidez. A combinação destas tecnologias possibilitou a eliminação de 20,1%, 18,0%, 89,8% em COT, DQO e turbidez, respectivamente. Para o tratamento da corrente 2 foram utilizados diferentes tipos de processos oxidativos avançados sendo eles, foto-Fenton (íons ferrosos) e foto-Fenton avançado (uso de ferro metálico). Nestes casos foram avaliadas a influência das concentrações de peróxido de hidrogênio e íon ferroso e ferro metálico considerando como variáveis resposta reduções de COT e DQO. Os resultados otimizados obtidos para o POA foto-Fenton permitiram reduções de 89,9% em COT e 50,8% em DQO, enquanto os resultados otimizados para POA foto-Fenton avançado foram reduções de 74,9% de COT e 41,0% de DQO. / Through the paradigm changes related to environmental management and rising costs of effluent discharge, water abstraction and treatment, industries undergo innovation processes that result in better use of resources and greater reduction in costs. Moreover, companies are submitted to greater requirements regarding environmental regulations driving them to deploy reuse of wastewater systems. Despite representing an important economic activity, the dairy industry is responsible for producing wastewater with high pollution potential. The present work was carried out in order to reduce contaminants and improve the biodegradability of dairy effluent by using an hybrid wastewater treatment based on coagulation/flocculation, membrane process and photocatalytic chemical oxidation/reduction. The effluents came from a regional industry and originating from the nanofiltration step of an ultrafiltrate whey. They were divided into two streams, called nanofiltration concentrate (stream 1) and nanofiltration permeate (stream 2). For the treatment of stream 1 was initially proposed coagulation/flocculation using different natural coagulant agents (chitosan, derivative tannin and moringa extract), followed by membrane processes type of microfiltration (0.40 ?m in polyetherimide) and ultrafiltration (50 kDa in polyethersulfone). For the stream 2 Advanced Oxidation and Reductive Processes were performed. In all steps of the work Response Surface Methodology was used to identify the optimum conditions. For the coagulation/flocculation treatment, the influence of the pH, natural coagulants and agitation were evaluated on the response variables total organic carbon (TOC), chemical oxygen demand (COD) and turbidity reductions. The optimized results reduced of 18.3% TOC, 12.7% COD and 19.6% turbidity. From the indicated condition stream 1 was submitted to membrane processes, being selected the microfiltration as the best treatment. The use of theses membranes provided 1.25% TOC, 5.21% COD and 87.4% turbidity reductions. The combination of these technologies has enabled the elimination of 20.1%, 18.0%, 89.8% in TOC, COD and turbidity, respectively. For the treatment of the stream 2 different types of Advanced Oxidation Processes were used being them, photo-Fenton (ferrous ions) and advanced photo-Fenton (metallic iron). In this cases the influence of the hydrogen peroxide, ferrous ion and metallic iron concentrations were evaluated, considering as response variables TOC and COD reductions. The optimized results for the photo-Fenton AOP allowed 89.9% TOC and 50.8% COD reductions, while the results optimized for advanced photo-Fenton AOP were 74.9% TOC and 41.0% COD reductions.

The thesis describes the development of new and improved methods for analyzing degradation markers from organophosphorus Chemical Warfare Agents (CWAs). Paper I and II describes an innovative and significantly improved method for the enrichment, derivatization (trimethysilylation) and GC-MS analysis of a broad range of organophosphorus CWAs degradation markers, namely the alkylphosphonic acids and a zwitterionic compound. That was achieved using solid phase disc extraction in combination with solid phase derivatization. The new method overcomes most limitations observed with existing techniques: it offers almost 100 % recoveries, requires no elution or evaporation steps, facilitates miniaturization of the solid sorbent and reagent, is compatible with in-vial derivatization, and minimizes the chromatographic background due to the use of a highly selective anion exchange sorbent disc. Paper III describes the development of new fluorinated diazomethane derivatization reagents and their evaluation for rapid and high sensitivity screening and identification of nerve agent degradation markers. The reagents are water-tolerant to some extent, which simplifies the derivatization step. The best reagent identified was 3,5-bis(trifluoromethyl)benzyl diazomethane, which outperformed the other reagent isomers tested and also the established commercial alternative, pentafluorobenzylbromide, allowing for the rapid (5 min) and direct derivatization of a 25 μL aqueous sample in acetonitrile. The spectra of the formed derivatives (high-energy collision induced fragmentation MS/MS) were used to construct a database (Paper IV) that proved to be superior in terms of match factor and probability compared to EI data gathered for trimethylsilyl derivatives. The study also focused on efforts towards achieving detailed structure information on the alkyl chains of the compounds in question using diagnostic ion interpretation. The final paper (paper V) describes the first rapid direct derivatization method for analyzing nerve agent metabolites in urine at trace levels. The method is based on the derivative from the paper III and the unambiguous identification was proven using a combination of low resolution and high resolution negative ion chemical ionization selected ion monitoring techniques. Novel results presented in these papers include: the first in-situ derivatization of alkylphosphonic acids on an SPE disc; the first direct derivatization of nerve agent markers in water and biomedical samples; the first high sensitivity GC-MS screening for these markers; and the first highly reproducible high-energy isomer specific CID MS/MS library. Overall, the results presented in this thesis represent significant contributions to the analysis of nerve agent degradation products.

Chapter 2 of the thesis describes a highly efficient in situ method for the reduction of amides to aldehydes and aryl O-carbamates to phenols and other transformations involving hydrozirconations. The method, as a three-component-type reaction, involves in situ generation of the Schwartz reagent (Cp2Zr(H)Cl) from Cp2ZrCl2 and the reductant, LiAlH(O-t-Bu)3, and immediate reaction with a substrate. Substrates include aliphatic and aromatic tertiary amides which are reduced to aldehydes, aryl O-carbamates which are reduced to phenols, and alkynes which undergo other transformations via hydrozirconation. Compared to prior methods, this method has advantage in that reagents are inexpensive and stable, reaction times are short, and reaction temperatures are generally conveniently at room temperature. The use of the in situ method described herein instead of the requirement for the synthesis of the commercially available Schwartz reagent is estimated to provide more than 50% reduction in cost. Chapter 3 of the thesis describes the discovery and development of efficient and regioselective Ru-catalyzed amide-directed C-H, C-N, C-O activation/C-C bond forming reactions, ester-directed C-O activation/C-C bond forming reaction, and amide-directed C-O activation/hydrodemethoxylation reactions under a simple RuH2(CO)(PPh3)3/toluene catalytic system. Of these, the amide-directed C-H activation/cross coupling reaction proceeds well but uniquely on furan 3-amide substrates while the ester-directed C-O activation is effective on the 2-MeO-1-naphthoic acid methyl ester. On the other hand, the amide-directed C-N and C-O activation/coupling reactions are broadly applicable on benzamides and naphthamides. All of these achievements of directed C-H, C-N, C-O activation/coupling reactions complement and may supercede the DoM (directed ortho metalation)-cross coupling strategy, and establish the catalytic base-free DoM-cross coupling process at non-cryogenic temperature as a convenient, economical and green alternative. The new catalytic amide-directed ortho-hydrodemethoxylation reaction has potential value in links to aromatic electrophilic substitution and DoM chemistries. Furthermore, a new borylation reaction via Ru-catalyzed amide-directed C-H activation/C-B bond forming process is also reported herein. / Thesis (Ph.D, Chemistry) -- Queen's University, 2010-12-21 11:12:35.564

The aqueous phase photo-oxidation of water soluble organic compounds (WSOC) extracted from α-pinene ozonolysis secondary organic aerosol (SOA) was investigated using high resolution time-of-flight chemical ionization mass spectrometry (CI-ToFMS). The results have shown that WSOC get more functionalized and fragmented as the reaction proceeds. The capabilities of three reagent ions, were assessed; specifically, (H2O)nH+ ionizes organic compounds with carbon oxidation state (OSC) ≤ 1.3, whereas CH3C(O)O- and I(H2O)n- ionize highly oxygenated organics with OSC up to 4, with I(H2O)n- showing more selectivity. The aqueous phase OH oxidation of cis-pinonic acid and tricarballylic acid (a surrogate for 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA), recognized as a tracer of α-pinene SOA) were also studied. The respective rate constants at 301 K were measured to be 3.4(±0.5)×10^9 M^-1s^-1 at pH=2 and 3.1(±0.3)×10^8 M^-1s^-1 at pH=4.6. This work also illustrates possible aqueous phase mechanism for MBTCA formation from cis-pinonic oxidation.

The aqueous phase photo-oxidation of water soluble organic compounds (WSOC) extracted from α-pinene ozonolysis secondary organic aerosol (SOA) was investigated using high resolution time-of-flight chemical ionization mass spectrometry (CI-ToFMS). The results have shown that WSOC get more functionalized and fragmented as the reaction proceeds. The capabilities of three reagent ions, were assessed; specifically, (H2O)nH+ ionizes organic compounds with carbon oxidation state (OSC) ≤ 1.3, whereas CH3C(O)O- and I(H2O)n- ionize highly oxygenated organics with OSC up to 4, with I(H2O)n- showing more selectivity. The aqueous phase OH oxidation of cis-pinonic acid and tricarballylic acid (a surrogate for 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA), recognized as a tracer of α-pinene SOA) were also studied. The respective rate constants at 301 K were measured to be 3.4(±0.5)×10^9 M^-1s^-1 at pH=2 and 3.1(±0.3)×10^8 M^-1s^-1 at pH=4.6. This work also illustrates possible aqueous phase mechanism for MBTCA formation from cis-pinonic oxidation.

Orientador: Rodnei Bertazzoli / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-08-07T06:34:47Z (GMT). No. of bitstreams: 1 Badellino_Carla_M.pdf: 4439168 bytes, checksum: 0e434b627394c712d54234bcc01ad717 (MD5) Previous issue date: 2006 / Resumo: Nest trabalho foi investigada a desempenho do peróxido de hidrogênio eletrogerado a partir de redução do oxigênio na superfície de um catodo de carbono vítreo reticulado para a oxidação do herbicida ácido 2,4-diclorofenoxiacético. Inicialmente, foram feitas voltametrias cíclicas para verificar se o 2,4-D para verificar a existência de pares redox. O eletrólito suporte usado foi o K2SO4 0,3 mol L-1, pH 10, em meio saturado de N2. Após a verificação da ausência de reação redox para o 2,4-D, fez-se a otimização da eletrogeração de peróxido de hidrogênio. Usando como catodo um eletrodo rotatório cilíndrico de carbono vítreo reticulado de 60 ppi e um anodo de platina, em meio de K2SO4 0,3 mol L-1, pH 10, saturado com O2 e 900 rpm, determinou-se que o melhor potencial para eletrogeração de H2O2 foi de ¿ 1,6 V vs. ECS a uma temperatura de 8 0C. Em etapa subseqüente, verificou-se a degradação do herbicida 2,4-D em solução, na concentração de 100 mg L-1 por diferentes três processos: H2O2 eletrogerado, UV/H2O2, e fotoeletro-Fenton, este último realizado em pH 2,5. Para tanto foram feitas injeções no Cromatógrafo Líquido de Alta Eficiência, além de análise de Carbono Orgânico Total e Demanda Química de Oxigênio. Dos processos estudados, o mais vantajoso foi o catalisado com radiação UV e sais de Fe2+ (Reagente de Fenton), com uma redução do COT de 69 % do valor inicial. Dando continuidade os estudos, foi construído um reator em escala piloto do tipo filtro prensa com fluxo transversal para eletrogeração de peróxido de hidrogênio. Composto por dois compartimentos anódicos e um catódico, separado por membranas catiônicas Nafion ®N242, o reator foi otimizado em três diferentes parâmetros: o potencial de trabalho, a velocidade de vazão do fluido e a vazão de oxigênio. Os valores ótimos encontrados para eletrogeração de H2O2 em eletrólito suporte de K2SO4 0,3 mol L-1 foram: potencial de -1,6 V vs. Pt, velocidade do fluido de 500 L h-1 e vazão de oxigênio de 6 L s-1. Com o reator otimizado e acumulando cerca de 1100 mg L-1 de H2O2 em 5 horas de processo, foram feitos ensaios de degradação do 2,4-D em seis deferentes métodos: dois ensaios em meio básico com e sem incidência de radiação ultravioleta, e em seguida, mais quatro ensaios em meio ácido, também com e sem a incidência de radiação ultravioleta, na presença do reagente de Fenton, e por fim, um ensaio catalisado com radiação ultravioleta e na presença do reagente de Fenton. Os ensaios em meio ácido e catalisado, mais uma vez se mostraram mais eficientes e a remoção do COT seguiu uma cinética de pseudo-primeira ordem. Mesmo não havendo muita variação no tempo de degradação o gráfico de ln[C(t)/C(0)] vs. tempo, mostra que o processo mais vantajoso é aquele catalisado com UV/Fenton, com uma constante de redução do COT uma ordem de grandeza maior do que para o processo apenas com incidência de radiação UV. Os valores foram, respectivamente, 9,4x10-5 s-1 e 1,75x10-4 s / Abstract: In this work, the performance of the H2O2 electrogeneration process from O2 reduction on a reticulated vitreous carbon cathode was investigated. The process was also use for the oxidation of the herbicide 2,4-dichlorophenoxyacetic acid. Firstly, cyclic voltammetries were used for the identification of possible reduction reactions of the herbicide. The supporting electrolyte used was a 0,3 mol L-1 K2SO4, pH 10, nitrogen saturated solution. Then, the optimization of hydrogen peroxide electrogeneration it was carried out. As a cathode, a reticulated vitreous carbon-rotating cylinder, shaped from a 60 ppi RCV plate was used. A platinum foil was used as anode and a saturated calomel electrode was used as reference. Supporting electrolyte was always K2SO4 0,3 mol L-1, in an O2 saturated solution. The experiments were run in a 150 mL electrode cell, with a water jacket to keeping temperature in the range from 8 0C. The best potential to produce hydrogen peroxide in these conditions was -1,6 V vs. SCE. In following stage, the degradation of 2,4-D was investigated by tree different process: H2O2 electrogenerated, H2O2/UV and photo electro-Fenton being the last at pH 2,5. The degradation of 2,4-D was followed by HPLC, moreover TOC and COD analyses. The most efficient process was the catalyzed UV/Fe2+ process that presented a TOC reduction of 69 %. In a sequence, a pilot scale reactor was mounted for hydrogen peroxide electrogeneration. The reactor is formed by two anolytes and one catholyte compartments, separated by a N424 Nafion® membrane. The reactor was optimized considering three different parameters: the applied potential, oxygen flow and the electrolyte flow. Best operational parameters electrogeneration rate of hydrogen peroxide in a K2SO4 0,3 mol L-1 electrolyte support were: -1,6 V vs. Pt, 500 L h-1 of electrolyte flow and 6 L s-1 of oxygen flow. Considering these results, the experiments for the degradation of 2,4-D were conducted with the optimized reactor. In this new series of experiments, six different processes were tested. In alkaline medium, the degradation occurred only with H2O2 and H2O2, catalyzed by UV radiation. Four processes were used in acidic medium: H2O2, H2O2 catalyzed by UV radiation, Fe2+ (electro Fenton process) and H2O2 with Fe2+ catalyzed by UV radiation (photo-electro Fenton process). In catalyzed experiments in acidic medium, degradation rates were higher TOC decay presented a pseudo-first order kinetic. The differences between electro Fenton and photo-electro Fenton processes appeared only when TOC reduction was considered. A greater degree of organics combustion was observed for the last process, with 95 % of TOC was eliminated. / Mestrado / Engenharia de Materiais / Mestre em Engenharia Mecânica