Desenvolvimento de biossensores enzimáticos amperométricos para a determinação de compostos de importância clínica

Este trabalho descreve a preparação e caracterização de eletrodos modificados com azul da Prússia e materiais relacionados e a sua aplicação na construção de biossensores enzimáticos amperométricos para a detecção de oxalato e de glicose. Os materiais utilizados na modificação dos eletrodos foram azul da Prússia e compostos híbridos formados por hexacianoferrato de níquel e polipirrol ou hexacianoferrato de cobre e polipirrol. Os materiais lubridos mostraram-se capazes de mediar na eletroredução de peróxido de hidrogênio, mesmo em eletrólitos contendo Na+, apresentando melhor desempenho analítico quando comparados aos respectivos hexacianoferratos sem a presença do polímero condutor. Estes materiais foram utilizados com êxito na construção de biossensores para oxalato e para glicose, imobilizando as enzimas Oxalato Oxidase e Glicose Oxidase, respectivamente. Também foi estudada a preparação de um biossensor para a detecção de glicose utilizando a técnica de automontagem eletrostática camada por camada. Esta técnica permite otimizar o processo de immobilização da enzima, obtendo excelente desempenho analítico com pouca quantidade de enzima. Finalmente, são apresentadas a síntese, caracterização e aplicação de nanopartículas de azul da Prússia na determinação de peróxido de hidrogênio. Foi possível preparar nanopartículas com um diâmetro médio de 5 nm, as quais foram imobilizadas em eletrodos mediante a técnica de automontagem eletrostática camada por camada, a fim de estudar seu comportamento eletroquímico.

Aplicação de tecnologias eletroquímicas (oxidação via radicais hidroxila, oxidação mediada via cloro ativo e eletrocoagulação) para o tratamento de efluentes reais ou sintéticos

In this work the degradation of real and synthetic wastewater was studied using electrochemical processes such as oxidation via hydroxyl radicals, mediated oxidation via active chlorine and electrocoagulation. The real effluent used was collected in the decanter tank of the Federal University of Rio Grande do Norte (ETE-UFRN) of Effluent Treatment Plant and the other a textile effluent dye Ácido Blue 113 (AB 113) was synthesized in the laboratory. In the electrochemical process, the effects of anode material, current density, the presence and concentration of chloride as well as the active chlorine species on site generated were evaluated. Electrodes of different compositions, Ti/Pt, Ti/Ru0,3Ti0,7O2, BDD, Pb/PbO2 and Ti/TiO2-nanotubes/PbO2 were used as anodes. These electrodes were subjected to electroanalytical analysis with the goal of checking how happen the anodic and cathodic processes across the concentrations of NaCl and supporting electrolyte used. The potential of oxygen evolution reaction were also checked. The effect of active chlorine species formed under the process efficiency was evaluated by removing the organic matter in the effluent-ETE UFRN. The wastewater treatment ETE-UFRN using Ti/Pt, DDB and Ti/Ru0,3Ti0,7O2 electrodes was evaluated, obtaining good performances. The electrochemical degradation of effluent-UFRN was able to promote the reduction of the concentration of TOC and COD in all tested anodes. However, Ti/Ru0,3Ti0,7O2 showed a considerable degradation due to active chlorine species generated on site. The results obtained from the electrochemical process in the presence of chloride were more satisfactory than those obtained in the absence. The addition of 0.021 M NaCl resulted in a faster removal of organic matter. Secondly, was prepared and characterized the electrode Ti/TiO2-nanotubes/PbO2 according to what the literature reports, however their preparation was to disk (10 cm diameter) with surface area and higher than that described by the same authors, aiming at application to textile effluent AB 113 dye. SEM images were taken to observe the growth of TiO2 nanotubes and confirm the electrodeposition of PbO2. Atomic Force Microscope was also used to confirm the formation of these nanotubes. Furthermore, was tested and found a high electrochemical stability of the electrode Ti/TiO2-nanotubes/PbO2 for applications such as long-term indicating a good electrocatalytic material. The electrochemical oxidation of AB 113 using Ti/Pt, Pb/PbO2 and Ti/TiO2-nanotubes/PbO2 and Al/Al (electrocoagulation) was also studied. However, the best color removal and COD decay were obtained when Ti/TiO2-nanotubes/PbO2 was used as the anode, removing up to 98% of color and 92,5% of COD decay. Analysis of GC/MS were performed in order to identify possible intermediates formed in the degradation of AB 113.

Remoção de nitratos em água utilizando diferentes materiais e processos

The need to preserve the environment has led to the search for new materials for efficient disposal of chemical compounds that alter the stability of our natural resources. Among these resources, stands in first place the water, as a precious commodity and scarce, leading to the proper use and reuse. As a result, the World Health Organization has established maximum permissible values in drinking water, such as: 50 mg/L, 0, 1 mg/L and 0, 5 mg/L to at-3, at-2, NH 4, respectively. For these reasons, assesses the implementation of new materials and water treatment processes aiming at the removal of these compounds, such as alumina, in the form of powder or as a support for a catalytic system using inorganic membranes capable of supporting more severe conditions of temperature and pressure by opening new possibilities for applications of membrane reactors; and also for electrochemical treatments with doped diamond bobo electrodes (BDD) as anode and copper as cathode. For such purpose, was conducted the study of adsorption of nitrate in different times to assess the time required to achieve equilibrium by employing three commercial alumina called: acidic, basic and neutral alumina, with subsequent treatment only in the acidic alumina impregnating metals (PdCu/Al2O3) for the catalytic reaction. The materials were previously characterized by XRD, SEM techniques and ABET. Aluminas presented a considerable adsortive capacity of nitrate in the first thirty minutes, equivalent to 50% of removal reaching equilibrium in that time. After treatment, using alumina as catalyst for the reaction in batch reactor (Pd-Cu/Al2O3), the results were more favourable, totalling 64% reduction of ion NO3-at the end of three hours. On the other hand, the results for the catalytic reaction using the catalytic support Pd-Cu/TiO2 in membrane reactor proved to be low. -if, in this way, improve the conditions of catalytic system to optimize the process. Already, for the electrochemical tests using DDB1 electrodes as anode, and Cu, as cathode, there was a fairly significant nitrate reduction, approximately 80% of ion removal during three hours and cost viable applications.

Tecnologia eletroquímica como tratamento alternativo de efluentes derivados da indústria têxtil e petroquímica

In this work, the treatment of wastewater from the textile industry, containing dyes as Yellow Novacron (YN), Red Remazol BR (RRB) and Blue Novacron CD (NB), and also, the treatment of wastewater from petrochemical industry (produced water) were investigated by anodic oxidation (OA) with platinum anodes supported on titanium (Ti/Pt) and boron-doped diamond (DDB). Definitely, one of the main parameters of this kind of treatment is the type of electrocatalytic material used, since the mechanisms and products of some anodic reactions depend on it. The OA of synthetic effluents containing with RRB, NB and YN were investigated in order to find the best conditions for the removal of color and organic content of the dye. According to the experimental results, the process of OA is suitable for decolorization of wastewaters containing these textile dyes due to electrocatalytic properties of DDB and Pt anodes. Removal of the organic load was more efficient at DDB, in all cases; where the dyes were degraded to aliphatic carboxylic acids at the end of the electrolysis. Energy requirements for the removal of color during OA of solutions of RRB, NB and YN depends mainly on the operating conditions, for example, RRB passes of 3.30 kWh m-3 at 20 mA cm-2 for 4.28 kWh m-3 at 60 mA cm-2 (pH = 1); 15.23 kWh m-3 at 20 mA cm-2 to 24.75 kWh m-3 at 60 mA cm-2 (pH 4.5); 10.80 kWh m-3 at 20 mA cm-2 to 31.5 kWh m-3 at 60 mA cm-2 (pH = 8) (estimated data for volume of treated effluent). On the other hand, in the study of OA of produced water effluent generated by petrochemical industry, galvanostatic electrolysis using DDB led to the complete removal of COD (98%), due to large amounts of hydroxyl radicals and peroxodisulphates generated from the oxidation of water and sulfates in solution, respectively. Thus, the rate of COD removal increases with increasing applied current density (15-60 mAcm-2 ). Moreover, at Pt electrode, approximately 50% removal of the organic load was achieved by applying from 15 to 30 mAcm-2 while 80% of COD removal was achieved for 60 mAcm-2 . Thus, the results obtained in the application of this technology were satisfactory depending on the electrocatalytic materials and operating conditions used for removal of organic load (petrochemical and textile effluents) as well as for the removal of color (in the case of textile effluents). Therefore, the applicability of electrochemical treatment can be considered as a new alternative like pretreatment or treatment of effluents derived from textiles and petrochemical industries.

Síntese e caracterização de PSFC (Pr0,5Sr0,5Fe1-xCuxO3-δ, sendo x=0,2 e x=0,4) para aplicação como catodo de células a combustível de óxido sólido

The PSFC (Pr0.5Sr0.5Fe1-xCuxO3-δ) is a new mixed oxide perovskite and has been studied and evaluated the cathode materials for intermediate temperature solid oxide fuel cells (IT-SOFCs), mainly due to its good compatibility with the electrolyte (CGO) and its high ionic conductivity and electronic in intermediate temperature. In this work, PSFC powders with two different compositions (Pr0,5Sr0,5Fe0,8Cu0,2O3- PSFC5582 and Pr0,5Sr0,5Fe0,6Cu0,4O3-PSFC5564) were synthesized by the citrate method using a new route. The powders obtained were characterized by thermal analysis (Differential Scanning Calorimetry and Thermogravimetry), and the material calcined at 800, 900 and 1000 °C for 5h were analyzed by X-ray diffractometry (XRD), with the Rietveld refinement of the diffraction data and dilatometry. PSFC5582 composite films were obtained by screen printing of powder calcined at 1000 °C. The films were deposited on substrate ceria doped with gadolinia (CGO) and then sintered at 1050 °C for 2h. The electrochemical performance of the electrodes was evaluated by impedance spectroscopy and the interface electrode/electrolyte was observed by scanning electron microscopy (SEM). The specific resistance area (ASR) was 0.44 Ω.cm² at 800 °C, slightly lower than those reported in the literature for cathodes containing cobalt. The thermal expansion coefficients of both the PSFC compositions were obtained and varied between 13 and 15 x 10-6 °C-1 , in a temperature range of 200 to 650 °C, demonstrating the good thermal compatibility of cathodes with Ce0,9Gd0,1O1,95 electrolytes (CET = 12 x 10-6 °C).

Estudo da eficiência eletroquímica para tratamento de chorume gerado em aterro sanitário brasileiro

This work was performing effluent degradation studies by electrochemical treatment. The electrochemical oxidation (EO) hydroquinone (H2Q) was carried out in acid medium, using PbO2 electrode by galvanostatic electrolysis, applying current densities of 10 and 30 mA/cm2 . The concentration of H2Q was monitored by differential pulse voltammetry (DPV). The experimental results showed that the galvanostatic electrolysis process performance significantly depends on the applied current density, achieving removal efficiencies of 100% and 80 % and 10 applying 30 mA/cm2 , respectively. Furthermore, the electroanalytical technique was effective in H2Q be used as a detection method. In order to test the efficiency of PbO2 electrode, the electrochemical treatment was conducted in an actual effluent, leachate from a landfill. The liquid waste leachate (600ml effluent) was treated in a batch electrochemical cell, with or without addition of NaCl by applying 7 mA/cm2 . The efficiency of EO was assessed against the removal of thermo-tolerant coliforms, total organic carbon (TOC), total phosphorus and metals (copper, cobalt, chromium, iron and nickel). These results showed that efficient removal of coliforms was obtained (100%), and was further decrease the concentration of heavy metals by the cathode processes. However, results were not satisfactory TOC, achieving low total removal of dissolved organic load. Because it is considered an effluent complex were developed other tests with this effluent to monitor a larger number of decontamination parameters (Turbidity, Total Solids, Color, Conductivity, Total Organic Carbon (TOC) and metals (barium, chromium, lithium, manganese and Zinc), comparing the efficiency of this type of electrochemical treatment (EO or electrocoagulation) using a flow cell. In this assay was compared to electro streaming. In the case of the OE, Ti/IrO2-TaO5 was used as the anode, however, the electrocoagulation process, aluminum electrodes were used; applying current densities of 10, 20 and 30 mA/cm2 in the presence and absence of NaCl as an electrolyte. The results showed that EO using Ti/IrO2–TaO5 was anode as efficient when Cl- was present in the effluent. In contrast, the electrocoagulation flow reduces the dissolved organic matter in the effluent, under certain experimental conditions.

Aplicação de tratamentos eletroquímicos integrados para remediação de solos e águas contaminadas com petróleo e pesticidas

Electrochemical technologies have been proposed as a promising alternative for the treatment of effluents and contaminated soils. Therefore, the objective of this work was to study the treatment of contaminated soils and wastewaters using electrochemical technologies. Thus, the study regarding the scale-up of the electrochemical system with continuous flow treatment of wastewater of the petrochemical industry was investigated using platinum electrodes supported on titanium (Ti / Pt), and boron-doped diamond (BDD). The results clearly showed that under the operating conditions studied and electrocatalytic materials employed, the better removal efficiency was achieved with BDD electrode reducing the chemical oxygen demand (COD) from 2746 mg L-1 to 200 mg L-1 in 5 h consuming 56.2 kWh m-3 . The decontamination of soils and effluents by petrochemical products was evaluated by studying the effects of electrokinetic remediation for removal of total petroleum hydrocarbons (HTP) from contaminated soil with diesel. The efficiency of this process was dependent on the electrolyte used Na2SO4 (96.46%), citric acid (81.36%) and NaOH (68.03%) for 15 days. Furthermore, the effluent after treatment of the soil was treated by electrochemical oxidation, achieving a good elimination of the organic polluting load dissolved. Depending on the physical behavior of wastewater contaminated with oil (emulsified state); atrazine emulsified effluents were investigated. The main characteristics of the effluent produced during the washing of contaminated soil were studied, being dependent on the surfactant dosage used; which determined its electrolytic treatment with BDD. The electrochemical oxidation of emulsified effluent of atrazine was efficient, but the key to the treatment is reducing the size of micelles.

Aplicação da oxidação eletroquímica no tratamento de efluentes contendo corantes reativos utilizando Ti/Pt e Ti/Pt-SnSb

The textile effluents are a complex mixture of many pollutants that contain high organic loads, severe color and toxic compounds. The high concentration of the textile effluent may cause increased chemical demand (COD) and biochemical (BOD) of oxygen, elevated temperature, acidity or alkalinity, causing damage and environmental problems. In addition to representing a serious threat to human health such effluent is also quite toxic to most aquatic organisms. And for this reason, one must meet the concentration limits for emission sources and sewage system. This study aimed to investigate the performance of electrochemical treatment of a textile effluent for the removal of color, turbidity, dissolved oxygen (DO) and dissolved organic matter by investigating the influence of experimental parameters such as the electrocatalyst materials (Ti/Pt and Ti/Pt-SnSb) and current density in order to compare their efficiency, energy consumption and cost. The dye Novacron Blue CD (NB) was employed in synthetic solution, while the dyes Remazol Yellow 3RS (RY 3RS) Remazol Red RR Gran (RR-RR Gran) and Navy Blue CL-R (NB CL-R) were used to generate simulated textile effluent laboratory. The results showed that the application of electrochemical oxidation process favors the elimination of color effectively independent the electrocatalytic material and current used, as well as treated effluent. However, the influence of electrocatalytic material was crucial to reduction of the organic matter in all cases.

Estudo comparativo dos processos eletroquímicos oxidativos avançados (PEOAs) no tratamento de efluentes contendo corantes orgânicos de difícil degradação

Organic dyes have been widely used in various branches of dyeing industries. These compounds are known to be very toxic, mutagenic, cancinogenic only cause aesthetic pollution and irreversible damage to aquatic ecosystems and human health. Are recalcitrant contaminants due to its high stability and resistance to photobleaching and bio. Given this context, the search for technologies that can minimize the effects of such pollutants is required. In recent decades the Electrochemical Oxidation Process Advanced (PEOAs) based on the generation of strongly oxidizing species (radicals ●OH) offer promising approaches for the prevention of problems caused by industrial effluents. This study analyzed the degradation and mineralization of textile dyes and the study of a real effluent in order to assess the feasibility of PEOAs: Electro-Fenton (EF), Photo Electro-Fenton (PEF) and anodic oxidation (AO), and these methods still was studied the Solar Fotoelectro-Fenton (SPEF) in a pre-pilot plant, in order to study the electrochemical treatment on an industrial scale. In the study has compared the effect of PEOAs in the removal of color, TOC and decay kinetics of degradation of the compounds, and also for using the Congo Red (CR) SPEF studies were performed mineralization current efficiency (MCE). The best results are given to the treatment of the PEF for all the studied dyes. From the results it was possible to choose the PEF as the most effective and promising for application of treatment when compared to other methods of treatment, and prove from SPEF that the process can be used in industrial scales, since this method PEF has been improved and solar irradiation replaced the UVA lamp.

Estudo comparativo dos processos eletroquímicos oxidativos avançados (PEOAs) no tratamento de efluentes contendo corantes orgânicos de difícil degradação

Organic dyes have been widely used in various branches of dyeing industries. These compounds are known to be very toxic, mutagenic, cancinogenic only cause aesthetic pollution and irreversible damage to aquatic ecosystems and human health. Are recalcitrant contaminants due to its high stability and resistance to photobleaching and bio. Given this context, the search for technologies that can minimize the effects of such pollutants is required. In recent decades the Electrochemical Oxidation Process Advanced (PEOAs) based on the generation of strongly oxidizing species (radicals ●OH) offer promising approaches for the prevention of problems caused by industrial effluents. This study analyzed the degradation and mineralization of textile dyes and the study of a real effluent in order to assess the feasibility of PEOAs: Electro-Fenton (EF), Photo Electro-Fenton (PEF) and anodic oxidation (AO), and these methods still was studied the Solar Fotoelectro-Fenton (SPEF) in a pre-pilot plant, in order to study the electrochemical treatment on an industrial scale. In the study has compared the effect of PEOAs in the removal of color, TOC and decay kinetics of degradation of the compounds, and also for using the Congo Red (CR) SPEF studies were performed mineralization current efficiency (MCE). The best results are given to the treatment of the PEF for all the studied dyes. From the results it was possible to choose the PEF as the most effective and promising for application of treatment when compared to other methods of treatment, and prove from SPEF that the process can be used in industrial scales, since this method PEF has been improved and solar irradiation replaced the UVA lamp.

Estudo da produção eletroquímica de espécies de cloro ativo para tratamento de efluentes sintéticos

The treatment of wastewater is essential to human health. One of the most important steps is the disinfection treatment which uses chlorine to eliminate bacteria as required by environmental agencies. However, the identification of potentially toxic byproducts generated by this method, such as trihalomethanes, has stimulated the development of new alternative disinfection technologies. Among them, heterogeneous photocatalysis, TiO2 photocatalysis and electrochemical disinfection are considered suitable alternatives to the chlorination method. Thus, the present dissertation analyzes the evolution of active chlorine species in a synthetic NaCl solution and it is tested to treat a synthetic solution of the dye Reactive Blue 19 using boron-doped diamond (BDD) and ruthenium oxide (Ti/Ru0.3Ti0.7O2) as anodes. The indirect electrochemical process was discussed in terms of mineralization of the total organic load and percentage of color removal in order to evaluate the applicability of electrochemical technology. Electrochemical experiments were carried out with different current densities (25, 50 and 75 mA.cm-2) during 120 minutes. On the other hand, other important parameter in this study was the influence of the proportion sp3/sp2 on BDD anode on the performance of the evolution of active chlorine species which was investigated by electrolytic techniques (linear polarization), with the intention of determining the related training oxidizing species and consumption energy to chemical or electrochemical reactions. From the results, it can be noted that the BDD electrode showed better efficiency throughout the electrochemical process.

Estudo da produção eletroquímica de espécies de cloro ativo para tratamento de efluentes sintéticos

The treatment of wastewater is essential to human health. One of the most important steps is the disinfection treatment which uses chlorine to eliminate bacteria as required by environmental agencies. However, the identification of potentially toxic byproducts generated by this method, such as trihalomethanes, has stimulated the development of new alternative disinfection technologies. Among them, heterogeneous photocatalysis, TiO2 photocatalysis and electrochemical disinfection are considered suitable alternatives to the chlorination method. Thus, the present dissertation analyzes the evolution of active chlorine species in a synthetic NaCl solution and it is tested to treat a synthetic solution of the dye Reactive Blue 19 using boron-doped diamond (BDD) and ruthenium oxide (Ti/Ru0.3Ti0.7O2) as anodes. The indirect electrochemical process was discussed in terms of mineralization of the total organic load and percentage of color removal in order to evaluate the applicability of electrochemical technology. Electrochemical experiments were carried out with different current densities (25, 50 and 75 mA.cm-2) during 120 minutes. On the other hand, other important parameter in this study was the influence of the proportion sp3/sp2 on BDD anode on the performance of the evolution of active chlorine species which was investigated by electrolytic techniques (linear polarization), with the intention of determining the related training oxidizing species and consumption energy to chemical or electrochemical reactions. From the results, it can be noted that the BDD electrode showed better efficiency throughout the electrochemical process.

Modelagem eletroquímica e do distúrbio ácido-básico em atletas de karatê participantes do campeonato mundial WKO 2014

The objective of this study was to analyze the electrochemical and acid-base disorders in high performance athletes during the World Karate Championship hosted by the WKO (World Karate Organization) in 2014. In this study 19 male athletes were analyzed (age 34 ± 8), black belts and with over 5 years of experience in the sport. Capillary blood samples from the digital pulp of the finger were collected in three stages: rest, 5 minutes after and 10 minutes after fighting (kumite). The sample was analyzed using blood gas analyzer GEM Premier 3000, using the parameters pH, Na+, K+, Ca2+, lactate e HCO3−. The values related to acid-base disturbance presented statistical differences (p <0.05) in most of the collected moments. The lactate levels found were 2.77 ± 0.97mmol / L in rest, 6.57 ± 2.1 for 5 minutes after and 4.06 ± 1.55 for 10 minutes after combat. The samples collected for the electrolytic markers showed no statistical differences in their values (p <0.05). Through the data collected, we conjecture that the sport can be characterized as a high-intensity exercise and with a predominance of the glycolytic system. The analysis of acid-base disturbance is an efficient method to assist in the control of training loads.

Desenvolvimento de uma célula a combustível de glicerol direto em meio alcalino

Dissertação (mestrado)—Universidade de Brasília, Instituto de Química, Programa de Pós-Graduação em Química, 2015.

Desenvolvimento de uma célula a combustível de glicerol direto em meio alcalino

Dissertação (mestrado)—Universidade de Brasília, Instituto de Química, Programa de Pós-Graduação em Química, 2015.