The compound p-(2-hydroxyethylsulfone) aniline was isolated from a reduced solution of a fiber-reactive azo dye. The identity and purity of this product was assessed through elemental composition analysis, high performance liquid chromatography (HPLC), gas chromatography/mass spectroscopy (GC/MS), and nuclear magnetic resonance spectroscopy (NMR). The toxicity of this purified compound was measured with Microtox and Daphnia pulex tests. Microtox tests were also performed on compounds with similar structures to p- (2-hydroxyethylsulfone) aniline. Wastewater samples containing textile dye wastes from a Publicly Owned Treatment Works (POTW) that treated textile dye wastes were monitored for the presence of p-(2-hydroxyethylsulfone) aniline using HPLC. Microtox testing was performed on these samples. Analytical tests confirmed the identity and purity of p-(2-hydroxyethylsulfone) aniline as the reduced product. Microtox tests revealed the concentration at which 50% of the light output was reduced (EC₅₀) after 5 minutes of exposure was 12.8 mg/L. Daphnia pulex testing yielded the concentration which was lethal to 50% of the tested organisms (LC₅₀) to be 113 mg/L. The 5-minute Microtox EC₅₀, values of aniline, sulfanilamide, 2-hydroxyethylsulfone, and 4-ethylaniline were 106.7, 8.15, >80, and 2.05 mg/L, respectively. The reduction product, p-(2-hydroxyethylsulfone)aniline, was not detected in textile-containing wastewater from the Martinsville POTW. The Microtox EC₅₀, for this wastewater, ranged from 6.05 to >75 mg/L. / Master of Science

S'ha desenvolupat una nova estratègia per la síntesi ràpida i eficient de L-[metil-11C]metionina basada en el captive solvent method. La reacció de L-homocisteína (dissolució bàsica en aigua/etanol 1:1) amb [11C]CH3I en un loop de HPLC va permetre la formació del radiotraçador desitjat amb elevat rendiment radioquímic (38.4 ± 4.1%) en un temps curt (< 12 min). Tots el paràmetres analítics compleixen les especificacions requerides per la versió actual de la Farmacopea Espanyola, tot i que els valors d'activitat específica obtinguts van ser relativament baixos. Degut a això, es van estudiar i quantificar les principals fonts que contribueixen a la contaminació de carboni-12 durant les síntesis de [11C]CH3I efectuades segons el "wet" method. Es va observar que la principal font de contaminació de CO2 no radioactiu (contribució>90%) és el propi procés de bombardeig, probablement degut a la combustió (causada per les altes temperatures i pressions assolides durant la irradiació) dels compostos que contenen carboni i que es troben al gas irradiat (o a l'interior del blanc). Es van establir procediments generals per realitzar abans, durant i després de la radiosíntesi per prevenir la contaminació exterior i, d'aquesta manera, augmentar l'activitat específica dels radiotraçadors sintetitzats.En quant al marcatge amb nitrogen-13, s'ha desenvolupat un procés totalment automàtic per a la producció de [13N]NO2- a partir de [13N]NO3- generat en el ciclotró. El precursor radioactiu [13N]NO2- s'ha utilitzat per la radiosíntesi de compostos amb interès biològic com ara S-nitrosotiols (donadors de NO.), N-nitrosamines (molècules amb potencials efectes carcinogènics) i azo compostos (amb possible aplicació com a radiotraçadors per a la detecció in vivo de plaques de &#946;-amiloide). En tots els casos es van obtenir excel·lents conversions radioquímiques (48.7% - 74.5% per S-[13N]nitrosotiols, 45.6% - 53.4% per N-[13N]nitrosamines i 40.0% - 58.3% per 13N-azo compostos) i bons rendiments radioquímics (33.8% - 60.6% per S-[13N]nitrosotiols, 34.0% - 37.8% per N-[13N]nitrosamines i 20.4% - 47.2% per 13N-azo compostos). A més a més, s'ha dissenyat i implementat un mòdul automàtic amb control remot pel marcatge de molècules amb 13N. / Se ha desarrollado una nueva estrategia para la síntesis rápida y eficiente de L-[metil-11C]metionina basada en el captive solvent method. La reacción de L-homocisteína (disolución básica en agua/etanol 1:1) con [11C]CH3I en un loop de HPLC permitió la formación del radiotrazador deseado con elevado rendimiento radioquímico (38.4 ± 4.1%) en un tiempo corto (< 12 min). Todos los parámetros analíticos cumplían las especificaciones requeridas por la versión actual de la Farmacopea Española, aunque los valores de actividad específica obtenidos fueron relativamente bajos. Por ello, se estudiaron y cuantificaron las principales fuentes que contribuyen a la contaminación de carbono-12 durante las síntesis de [11C]CH3I efectuadas según el "wet" method. Se observó que la principal fuente de contaminación de CO2 no radiactivo (contribución>90%) es el propio proceso de bombardeo, probablemente debido a la combustión (causada por las altas temperaturas y presiones alcanzadas durante la irradiación) de los compuestos que contienen carbono y que se encuentran presentes en el gas irradiado (o en el mismo cuerpo del blanco). Se establecieron procedimientos generales para realizar antes, durante y con posterioridad a la radiosíntesis para prevenir la contaminación exterior y, de esta manera, aumentar la actividad específica de los radiotrazadores sintetizados.Respecto al marcaje con nitrógeno-13, se ha desarrollado un proceso totalmente automático para la producción de [13N]NO2- a partir del [13N]NO3- generado en el ciclotrón. El precursor radiactivo [13N]NO2- se ha utilizado para la radiosíntesis de compuestos con interés biológico tales como S-nitrosotioles (donadores de NO.), N-nitrosaminas (moléculas con potenciales efectos carcinogénicos) y azo compuestos (con posible aplicación como radiotrazadores para la detección in vivo de placas de &#946;-amiloide). En todos los casos se obtuvieron excelentes conversiones radioquímicas (48.7% - 74.5% para S-[13N]nitrosotioles, 45.6% - 53.4% para N-[13N]nitrosaminas y 40.0% - 58.3% para 13N-azo compuestos) y buenos rendimientos radioquímicos (33.8% - 60.6% para S-[13N]nitrosotioles, 34.0% - 37.8% para N-[13N]nitrosaminas y 20.4% - 47.2% para 13N-azo compuestos). Además, se ha diseñado e implementado un módulo automático con control remoto para el marcaje de moléculas con 13N. / A new strategy for the fast and efficient synthesis of L-[methyl-11C]methionine based on the captive solvent method has been developed. The in loop reaction of a basic water/ethanol 1:1 solution of L-homocysteine with [11C]CH3I led to the formation of the desired radiotracer with high radiochemical yield (38.4 ± 4.1%) in short production time (< 12 min). All analytical parameters were within the specifications of the current version of the Spanish Pharmacopoeia, although specific radioactivity values were relatively low. Thus, the main sources of carbon-12 during the synthesis of [11C]CH3I by the "wet" method were studied and the contribution attributable to each individual source was quantified. The most relevant contamination of non-radioactive CO2 (contribution>90%) was shown to be generated during the bombardment process, probably due to the combustion (caused by high temperature and pressure during irradiation) of carbon carrier compounds present in the irradiated gas (or target body). General procedures to be performed before, during and after the radiosynthesis were established to prevent external contamination and to improve the specific radioactivity of 11C-labeled radiotracers synthesized from [11C]CH3I produced via the "wet" method. Concerning 13N-labeling, a fully automatic process for the production of [13N]NO2- from cyclotron generated [13N]NO3- has been developed. The radioactive precursor [13N]NO2- has been used for the synthesis of biologically interesting 13N-labeled compounds such as S-nitrosothiols (well-known NO. donors), N-nitrosamines (molecules with potent carcinogenic effects) and azo compounds (with putative application as imaging probes for in vivo detection of &#946;-amyloid plaques). In all cases, excellent radiochemical conversion (48.7% - 74.5% for S-[13N]nitrosothiols, 45.6% - 53.4% for N-[13N]nitrosamines and 40.0% - 58.3% for 13N-labeled azo compounds) and good radiochemical yields (33.8% - 60.6% for S-[13N]nitrosothiols, 34.0% - 37.8% for N-[13N]nitrosamines and 20.4% - 47.2% for 13N-labeled azo compounds) were achieved. An automatic remote controlled synthesis module for the preparation of 13N-labeled structures has been designed and implemented.

CI Disperse Blue 291 (CI DB 291) é um corante dinitrobromoaminoazobenzeno com atividade mutagênica para S. typhimurium, aumentada na presença de nitrorredutase, o-acetiltransferase e enzimas microssomais (S9). Neste estudo foram isolados e caracterizados quatro produtos da redução de DB 291 com ditionito de sódio (in vitro), sendo denominados 2- fenilbenzotriazóis não clorados (não-ClPBTAs). Os espectros de absorbância não apresentam o pico correspondente à ligação azo (?&#955;=613 nm), indicando a redução dessa ligação. Espectros de massas e 1H RMN mostram que os produtos são dois pares de tautômeros com m/z 465 [M+H]+ e m/z 449 [M+H]+. Esses produtos foram acetilados com piridina/anidrido acético e espectros de massas desses produtos indicam adição de grupamento acetil na molécula e formação de produtos com m/z 507 [M+H]+ e m/z 491 [M+H]+. Esses compostos foram reagidos com dGuo e obtivemos dois produtos com m/z 632 [M+H]+ e m/z 683 [M+H]+, sendo os possíveis adutos. A partir do composto não clorado com m/z 449 obtido após redução com ditionito de sódio, sintetizamos o análogo clorado (PBTA) após reação de cloração. Espectros de massa confirmam a formação do composto clorado com m/z 483 [M+H]+. Também incubamos o corante CI DB 291 com nitrorredutase/NADH. Análises por HPLC/ESI/MS indicam a formação de não-ClPBTA (m/z 449). Uma vez que não-ClPBTAs são mais mutagênicos para linhagens de S. typhimurium (com fração S9) que seus dinitrofenilazo corantes precursores, a conversão enzimática do corante para não-ClPBTAs pode ser uma via importante para sua bioativação. / C.I. Disperse Blue 291 (C.I. DB 291) is a dinitrobromoaminoazobenzene dye with mutagenic activity to S. typhimurium, that is increased in the presence of nitroreductase, o-acetyltransferase and microsomal enzymes (S9). In this study were isolated and characterized four products of the reduction of DB 291 with sodium dithionite (in vitro), named non- chlorinated 2- phenylbenzotriazoles (non-ClPBTAs). The absorbance spectra do not present the peak corresponding to the band of azo bond (&#955;= 613 nm), indicating that the reduction of this bond occured. Mass spectra and 1H NMR show that the products are two pairs of tautomers with m/z 465 [M+H]+ and m/z 449 [M+H]+. These compounds were acetylated with pyridine/acetic anhydride and their mass spectra indicate the addition of an acetyl group to the molecules and formation of products with m/z 507 [M+H]+ e m/z 491 [M+H]+. After reaction of these compounds with dGuo we have got two products with m/z 632 [M+H]+ and m/z 683 [M+H]+, which are possible adducts. Starting from the non chlorinated compound with m/z 449, obtained through the dye reduction with sodium dithionite, we have synthesized the chlorinated analogous (PBTA) after chlorination reaction. Mass spectrum confirms formation of the chlorinated product with m/z 483 [M+H]+. The DB 291 dye was also incubated with nitroreductase NADH. HPLC/ESI/MS analyses indicate the formation of a non chlorinated PBTA (m/z 449). Since non- chlorinated PBTAs are more mutagenic to S. typhimurium strains (with S9 mix) than the parent phenylbenzotriazole dye, enzymatic conversion of this type of dye non chlorinated PBTAs may be an important way for its bioactivation.

Polímeros contendo grupos azo-benzênicos têm sido estudados devido a sua capacidade para óptica não linear, formação de superfícies de relevo e de birrefringência fotoinduzida. O fator que possibilita essas aplicações é a propriedade de fotoisomerização reversível trans-cis-trans do grupo azo que produz a sua reorientação molecular. Neste trabalho foram produzidos filmes casting do poliuretano MDI-DR19 derivado de azo-benzeno. Estudou-se o crescimento e decaimento da birrefringência para diferentes valores de potência da luz de excitação da fotoisomerização. Os resultados experimentais do crescimento e decaimento foram analisados usando duas exponenciais e eles mostraram que o polímero MDI-DR19 apresenta boas características para utilização em armazenamento óptico pois cerca de 65% da birrefringência induzida no material permanece por longos intervalos de tempo. Ilustramos o processo de armazenamento de informação gravando uma imagem de birrefringência num filme de MDI-DR19. Foram também produzidas grades de relevo em filmes de MDI-DR19 utilizando franjas de interferência produzidas com luz de polarização P e S. Essas grades apresentaram alta uniformidade e características compatíveis com as mostradas na literatura. / Polymers containing azobenzenic groups have been studied due to their applications on non-linear optics, surface relief gratings (SRG) and photoinduced anisotropy for optical storage. The reversal photoisomerization trans-cis-trans property of the azo group induces a molecular reorientation. In this work, cast films of na azobenzene derivative, the polyurethane MDI-DR19, were studied. The build-up and decay of the birefringence were studied as a function of the photoisomerization exciting light power. The data of the build-up and decay of the birefringence were fitted with a bi-exponential function, which shows the stability of the MDI-DR19 for application in optical storage, since 65% of the induced birefringence remains after a long time. The optical storage is illustrated by recording a birefringence image in a film of MDI-DR19. It was also performed a SRG over films of MDI-DR19 applying an interference finger pattern with a P and S polarized light. The light induced gratings shows good uniformity and characteristics compatible with those presented in the literature.

Os processos oxidativos avançados (POA) são uma alternativa para complementar os processos clássicos de tratamento de efluentes que podem não ser eficientes para remoção de alguns tipos de poluentes como, por exemplo, os poluentes emergentes. Os POA se baseiam na geração de espécies altamente reativas (radicais hidroxila), a partir de peróxido de hidrogênio (H2O2), que oxidam os poluentes. O H2O2 pode ser eletrogerado in situ pela reação de redução de oxigênio (RRO) no meio reacional. O uso de eletrodos de difusão gasosa (EDG) altamente porosos proporciona o suprimento de oxigênio na interface eletrodo/solução podendo aumentar a velocidade da RRO. O uso de modificadores como quinonas e azocompostos imobilizados à matriz de carbono dos EDG podem aumentar a geração de H2O2. Portanto, os modificadores orgânicos Sudan Red 7B (SR7B), metil-p-benzoquinona (MPB), ácido antraflávico (AA) e antraquinona-2-ácido carboxílico (A2CA) foram adicionados em diferentes teores ao carbono Printex L6 (CP) e microcamadas porosas destes materiais foram estudados por voltametria cíclica e de varredura linear em eletrodo de disco-anel rotatório (RRDE). Os materiais contendo 0,5% de SR7B e 5,0% de MPB levaram a aumento na eficiência de geração de H2O2 para 86,2 e 85,5%, respectivamente, em relação ao CP puro que levou a 82,8%. EDG de CP modificados com 0,5% de SR7B foram construídos com telas metálicas em sua faces externas e a aplicação de densidades de corrente de 75, 100 e 150 mA cm-2 levou a uma maior eletrogeração de H2O2. Em densidades de corrente de 75 mA cm-2, o EDG modificado gerou 1020,1 mg L-1 de H2O2 com consumo energético de 118,0 kWh kg-1 de H2O2, constante cinética aparente de 37,3 mg L-1 min-1 e eficiência de corrente de 17,9%, enquanto o EDG de CP puro gerou menor concentração de H2O2; 717, 3 mg L-1, com maior consumo energético; 168,5 kWh kg-1, menor constante cinética aparente; 21,4 mg L-1 min-1, e menor eficiência de corrente; 12,6%. Portanto, o EDG modificado poderia ser empregado em sistemas que precisem de altas gerações de H2O2. / The advanced oxidation processes (AOP) are an alternative to the classical processes of treatment of effluents that may not be effective for the removal of some types of pollutants such as emerging pollutants. The AOP are based on the highly reactive species (hydroxyl radicals) from hydrogen peroxide (H2O2), which oxidize pollutants. H2O2 can be electrogenerated in situ by the oxygen reduction reaction (ORR) in the reaction medium. The use of highly porous gas diffusion electrodes (GDE) provides the supply of oxygen at the electrode/solution interface, which can increase the RRO speed. The use of modifiers such as quinones and azocompounds immobilized on the carbon matrix of GDE may increase H2O2 generation. Therefore, the organic modifiers Sudan Red 7B (SR7B), methyl-p-benzoquinone (MPB), anthraflavic acid (AA) and anthraquinone-2-carboxylic acid (A2CA) were added in different contents to carbon Printex L6 (CP) and microporous layers of these materials were studied by cyclic voltammetry and linear sweep voltammetry on a rotating ring- disc electrode (RRDE). Materials with 0.5% of SR7B and 5.0% of MPB increased the current efficiency for electrogeneration of H2O2 to 86.2 and 85.5%, respectively, in relation to pure CP that leaded to 82.8%. GDE of CP modified with 0.5% of SR7B were constructed with metallic screens on their outer faces and an application of current densities of 75, 100 and 150 mA cm-2 led to a greater electrogeneration of H2O2. At current densities of 75 mA cm-2, the modified GDE generated 1020.1 mg L-1 of H2O2 with energy consumption of 118.0 kWh kg-1 of H2O2, apparent kinetic constant of 37.3 mg L-1 min-1 and current efficiency of 17.9%, while GDE of pure CP generated lower H2O2 concentration; 717, 3 mg L-1, with higher energy consumption; 168.5 kWh kg-1, lower apparent kinetic constant; 21.4 mg L-1 min-1, and lower current efficiency; 12.6%. Therefore, the modified GDE could be applied in systems that require high generations of H2O2.

por fatores químicos e físicos, promovendo infecções hospitalares relacionadas ao uso de cateteres e demais instrumentos hospitalares, elevando os índices de mortalidade e morbidade de pacientes. Portanto, garantir a correta desinfecção capaz de impedir contaminações e infecções em ambientes hospitalares é de extrema importância. Para este fim, neste estudo explorou-se a seleção de uma substância capaz de marcar e ser biocida contra biofilmes fúngicos em superfícies de aço inox, a partir de nove candidatos benzimidazóis fluorescentes, com códigos NB1 a NB9 e oito sais imidazólicos de corantes azóicos, denominados C4MImErioCr, C10MImMO, C16MImMO, (C10)2MImMO, C4MImMO, C10MImORANGEII, C16MImORANGEII e (C10)2MImORANGEII. Desenvolveu-se para este fim um roteiro metodológico para determinar quais destas substancias são capazes de marcar e eliminar biofilmes de forma eficaz e segura. Os métodos utilizados para avaliar as substâncias foram (1) a Concentração Mínima Inibitória (MIC) conforme protocolo do CLSI M27-A3, (2) microscopias verificando capacidade das substâncias em marcar células, (3) ensaios com deposição sobre superfície do corpo de prova (placas de aço inox) com biofilme, (4) verificação da atividade biocida sobre biofilmes utilizando microscopias e (5) ensaios de citotoxicidade. Essas substâncias foram testadas frente a nove cepas de Candida spp., incluindo C. tropicalis, C. albicans e C. parapsilosis Na avaliação das substâncias, SI de corantes azóicos inibiram o crescimento celular de fungos, já o benzimidazol fluorescente NB7 apresentou atividades simultâneas de detecção e ação biocida sobre o biofilme. Todas as cepas testadas foram sensíveis a essa substância. Além disso, os biofilmes formados pelas cepas ATCC 18804 (C. albicans,) ATCC 22019 (C. parapsilosis) e ATCC 750 (C. tropicalis) na superfície de aço inox 304 sofreram ação biocida, quando expostas por 15 segundos a NB7, sendo um potencial sanitizante. / Biofilms provide an environment capable of protecting microbial cells from damage by chemical and physical factors of the immune system, and hinder the penetration of various antimicrobial agents, promoting nosocomial infections related to catheters, increasing mortality and morbidity of patients. Therefore, it is important to ensure proper hygiene to prevent contamination and infections in hospital environments. For this purpose, this study explored the identification of a substance that both detects and have biocide activity against fungal biofilms on stainless steel surfaces. Both nine fluorescent benzimidazole substances, coded NB1 to NB9 and eight imidazolium salts of azo dyes, named denominados C4MImErioCr, C10MImMO, C16MImMO, (C10)2MImMO, C4MImMO, C10MImORANGEII, C16MImORANGEII e (C10)2MImORANGEII were tested as candidates. These substances were tested applying a methodology developed to determine if a substance is able detecting and have biocide activity against fungal biofilms. Overall, this study involved the following methods: (1) Minimum Inhibitory concentration test following the CLSI protocol (M27-A3; the substances were tested against nine fungal strains, including C. tropicalis, C. albicans and C. parapsilosis.), (2) microscopy to determine the marker capacity, (3) spraying tests of the substances on surfaces (stainless steel) with fungal biofilms, (4) tests to verify the capability of the substances to both stain and were biocide against fungal biofilms, applying microscopic techniques and (5) cytotoxicity tests Within the set of seventeen substances, benzimidazole derivative NB7 was identified with the desired capabilities, staining and biocide activity against fungal biofilms at the same time. All tested fungal strains were sensible to this substance. A biocide activity was identified on the biofilms of ATCC 18804 (C. albicans), ATCC 22019 (C. parapsilosis) and ATCC 750 (C .tropicalis), grown on stainless steel 304, when exposed fifteen seconds to substance NB7. Although this substance showed being cytotoxic, it represents a promising candidate for sanitization purposes, including medical tools.

CI Disperse Blue 291 (CI DB 291) é um corante dinitrobromoaminoazobenzeno com atividade mutagênica para S. typhimurium, aumentada na presença de nitrorredutase, o-acetiltransferase e enzimas microssomais (S9). Neste estudo foram isolados e caracterizados quatro produtos da redução de DB 291 com ditionito de sódio (in vitro), sendo denominados 2- fenilbenzotriazóis não clorados (não-ClPBTAs). Os espectros de absorbância não apresentam o pico correspondente à ligação azo (?&#955;=613 nm), indicando a redução dessa ligação. Espectros de massas e 1H RMN mostram que os produtos são dois pares de tautômeros com m/z 465 [M+H]+ e m/z 449 [M+H]+. Esses produtos foram acetilados com piridina/anidrido acético e espectros de massas desses produtos indicam adição de grupamento acetil na molécula e formação de produtos com m/z 507 [M+H]+ e m/z 491 [M+H]+. Esses compostos foram reagidos com dGuo e obtivemos dois produtos com m/z 632 [M+H]+ e m/z 683 [M+H]+, sendo os possíveis adutos. A partir do composto não clorado com m/z 449 obtido após redução com ditionito de sódio, sintetizamos o análogo clorado (PBTA) após reação de cloração. Espectros de massa confirmam a formação do composto clorado com m/z 483 [M+H]+. Também incubamos o corante CI DB 291 com nitrorredutase/NADH. Análises por HPLC/ESI/MS indicam a formação de não-ClPBTA (m/z 449). Uma vez que não-ClPBTAs são mais mutagênicos para linhagens de S. typhimurium (com fração S9) que seus dinitrofenilazo corantes precursores, a conversão enzimática do corante para não-ClPBTAs pode ser uma via importante para sua bioativação. / C.I. Disperse Blue 291 (C.I. DB 291) is a dinitrobromoaminoazobenzene dye with mutagenic activity to S. typhimurium, that is increased in the presence of nitroreductase, o-acetyltransferase and microsomal enzymes (S9). In this study were isolated and characterized four products of the reduction of DB 291 with sodium dithionite (in vitro), named non- chlorinated 2- phenylbenzotriazoles (non-ClPBTAs). The absorbance spectra do not present the peak corresponding to the band of azo bond (&#955;= 613 nm), indicating that the reduction of this bond occured. Mass spectra and 1H NMR show that the products are two pairs of tautomers with m/z 465 [M+H]+ and m/z 449 [M+H]+. These compounds were acetylated with pyridine/acetic anhydride and their mass spectra indicate the addition of an acetyl group to the molecules and formation of products with m/z 507 [M+H]+ e m/z 491 [M+H]+. After reaction of these compounds with dGuo we have got two products with m/z 632 [M+H]+ and m/z 683 [M+H]+, which are possible adducts. Starting from the non chlorinated compound with m/z 449, obtained through the dye reduction with sodium dithionite, we have synthesized the chlorinated analogous (PBTA) after chlorination reaction. Mass spectrum confirms formation of the chlorinated product with m/z 483 [M+H]+. The DB 291 dye was also incubated with nitroreductase NADH. HPLC/ESI/MS analyses indicate the formation of a non chlorinated PBTA (m/z 449). Since non- chlorinated PBTAs are more mutagenic to S. typhimurium strains (with S9 mix) than the parent phenylbenzotriazole dye, enzymatic conversion of this type of dye non chlorinated PBTAs may be an important way for its bioactivation.

Os processos oxidativos avançados (POA) são uma alternativa para complementar os processos clássicos de tratamento de efluentes que podem não ser eficientes para remoção de alguns tipos de poluentes como, por exemplo, os poluentes emergentes. Os POA se baseiam na geração de espécies altamente reativas (radicais hidroxila), a partir de peróxido de hidrogênio (H2O2), que oxidam os poluentes. O H2O2 pode ser eletrogerado in situ pela reação de redução de oxigênio (RRO) no meio reacional. O uso de eletrodos de difusão gasosa (EDG) altamente porosos proporciona o suprimento de oxigênio na interface eletrodo/solução podendo aumentar a velocidade da RRO. O uso de modificadores como quinonas e azocompostos imobilizados à matriz de carbono dos EDG podem aumentar a geração de H2O2. Portanto, os modificadores orgânicos Sudan Red 7B (SR7B), metil-p-benzoquinona (MPB), ácido antraflávico (AA) e antraquinona-2-ácido carboxílico (A2CA) foram adicionados em diferentes teores ao carbono Printex L6 (CP) e microcamadas porosas destes materiais foram estudados por voltametria cíclica e de varredura linear em eletrodo de disco-anel rotatório (RRDE). Os materiais contendo 0,5% de SR7B e 5,0% de MPB levaram a aumento na eficiência de geração de H2O2 para 86,2 e 85,5%, respectivamente, em relação ao CP puro que levou a 82,8%. EDG de CP modificados com 0,5% de SR7B foram construídos com telas metálicas em sua faces externas e a aplicação de densidades de corrente de 75, 100 e 150 mA cm-2 levou a uma maior eletrogeração de H2O2. Em densidades de corrente de 75 mA cm-2, o EDG modificado gerou 1020,1 mg L-1 de H2O2 com consumo energético de 118,0 kWh kg-1 de H2O2, constante cinética aparente de 37,3 mg L-1 min-1 e eficiência de corrente de 17,9%, enquanto o EDG de CP puro gerou menor concentração de H2O2; 717, 3 mg L-1, com maior consumo energético; 168,5 kWh kg-1, menor constante cinética aparente; 21,4 mg L-1 min-1, e menor eficiência de corrente; 12,6%. Portanto, o EDG modificado poderia ser empregado em sistemas que precisem de altas gerações de H2O2. / The advanced oxidation processes (AOP) are an alternative to the classical processes of treatment of effluents that may not be effective for the removal of some types of pollutants such as emerging pollutants. The AOP are based on the highly reactive species (hydroxyl radicals) from hydrogen peroxide (H2O2), which oxidize pollutants. H2O2 can be electrogenerated in situ by the oxygen reduction reaction (ORR) in the reaction medium. The use of highly porous gas diffusion electrodes (GDE) provides the supply of oxygen at the electrode/solution interface, which can increase the RRO speed. The use of modifiers such as quinones and azocompounds immobilized on the carbon matrix of GDE may increase H2O2 generation. Therefore, the organic modifiers Sudan Red 7B (SR7B), methyl-p-benzoquinone (MPB), anthraflavic acid (AA) and anthraquinone-2-carboxylic acid (A2CA) were added in different contents to carbon Printex L6 (CP) and microporous layers of these materials were studied by cyclic voltammetry and linear sweep voltammetry on a rotating ring- disc electrode (RRDE). Materials with 0.5% of SR7B and 5.0% of MPB increased the current efficiency for electrogeneration of H2O2 to 86.2 and 85.5%, respectively, in relation to pure CP that leaded to 82.8%. GDE of CP modified with 0.5% of SR7B were constructed with metallic screens on their outer faces and an application of current densities of 75, 100 and 150 mA cm-2 led to a greater electrogeneration of H2O2. At current densities of 75 mA cm-2, the modified GDE generated 1020.1 mg L-1 of H2O2 with energy consumption of 118.0 kWh kg-1 of H2O2, apparent kinetic constant of 37.3 mg L-1 min-1 and current efficiency of 17.9%, while GDE of pure CP generated lower H2O2 concentration; 717, 3 mg L-1, with higher energy consumption; 168.5 kWh kg-1, lower apparent kinetic constant; 21.4 mg L-1 min-1, and lower current efficiency; 12.6%. Therefore, the modified GDE could be applied in systems that require high generations of H2O2.

The degradation of wool keratin under conditions relevant to those of wool dyeing was investigated using the techniques of gel permeation chromatography (GPC), ion exchange gel chromatography, and amino acid analysis. Physical testing of the treated and untreated wool was also carried out to determine the physical changes occurring, parameters used being percentage elongation at the break, and the breaking strain of the fibre. Samples of wool keratin were immersed in various aqueous solutions at 1000C for 24 hours and the filtered, aqueous, oxidised extracts were analysed* The solutions used varied only in the dye, or dye intermediate present in the treatment solution. All treatment baths contained 10% owf 1.02 x 10 -2 MSulphuric VI acid; 10%owf 7.04x 10 -3 MSodium sulphate VI ; A 100 :1 liquor ratio was used in each case. Some of the dye intermediates showed a marked catalytic effect, particularly in their effect on breaking strain, a decrease of 40% in some cases. The GPC profiles of the extracted proteins were examined in detail and compared against previous workers' results. An explanation of the behaviour of the dyes and intermediates was proposed. The amino acid composition data of the extracted and fractionated proteins were compared against various morphological components extracted by other workers, as was the total gelatin obtained from each treatment.

Wastewaters from textile industry contain organic dyes, which cannot be easily treated by biological methods. Therefore, pretreatment by an advanced oxidation process (AOP) is needed in order to produce more readily biodegradable compounds and to remove color and chemical oxygen demand (COD) simultaneously. In this research, ozone (O3) is combined with hydrogen peroxide (H2O2) for the advanced oxidation of an azo dye solution, namely aqueous solution of Acid Red 151, which is called as &ldquo / Peroxone process&rdquo / . The aim of the study is to enhance the ozonation efficiency in treating the waste dye solution. The effects of pH, initial dye and initial ozone concentrations and the concentration ratio of initial H2O2 to initial O3 on color and COD removals were investigated. Also, the kinetics of O3-dye reaction in the presence of H2O2 was approximately determined. As a result of the experimental study, it was seen that an increase in the initial dye concentration at a constant pH and initial ozone concentration did not change the COD % removal significantly, from a statistical analysis of the data. The results obtained at pH values of 2.5 and 7 gave higher oxidation efficiencies in terms of color and COD removals compared to those at pH of 10. The best initial molar ratio of H2O2 to O3 was found to be 0.5, which yielded highest treatment efficiency for each pH value studied. The results of the excess dye experiments suggest that the ozonation of Acid Red 151 follows an average first order reaction with respect to ozone at pH=2.5 and pH=7 whereas it is around 0.56 at pH=10. By Initial Rate Method, the orders with respect to individual reactants of O3 and dye were determined as one, the total order of the reaction being two for all the studied pH. As a conclusion, a further study of the peroxone process at a pH of 10 can be recommended to determine the reaction kinetics and mechanism at this pH, where radicals play an important role.