Eletrocatálise das reações de oxidação de hidrogênio e de redução de oxigênio

This work discusses the electrocatalytic processes taking place in the polymer electrolyte fuel cell electrodes, specifically the hydrogen oxidation reaction (HOR) and the oxygen reduction reaction (ORR), because these are clear examples of electrochemical reactions favored by the use of electrocatalysts. Since the gaseous reactants are very little soluble in the electrolyte, the use of special electrodes, named gas diffusion electrodes, is required to promote easy and continuous access of reactant gases to the electrocatalytic sites. Besides this, other important aspects such as the use of spectroscopic techniques and of theoretical models to improve the knowledge of the electrocatalytic systems are shortly discussed.

Estudo da degradação de ranitidina via H2O2 eletrogerado/Fenton em um reator eletroquímico com eletrodos de difusão gasosa

The study of the electrochemical degradation of the ranitidine was developed using an electrochemical reactor with a gas diffusion electrode (GDE) as cathode. The electrolysis experiments was performed at constant current (1 < A < 10) and flow rate of 200 L h-1. The process of drug degradation, chemical/electrochemical and electro-Fenton ways, using electrochemical reactor showed best efficiency at current values of > 4 A. The process reached a production of 630 mg L-1 of the H2O2 at 7 A. The ranitidine concentrations was reduced in 99.9% (HPLC) and chemical oxygen demand (COD) was reduced in 86.7% by electro-Fenton.

Avaliação da degradação do diclofenaco sódico utilizando H2O2/fenton em reator eletroquímico

This paper describes a degradation study of the anti-inflammatory sodium diclofenac in aqueous medium using an electro-chemical flow reactor with a gas diffusion electrode as cathode. Two degradation processes were compared: by H2O2 electro-generated and H2O2 electro-generated/Fe(II). Concentration of sodium diclofenac was determined during the experiments by HPLC. The changes in chemical oxigen demand (COD) were also evaluated. Under the specific reaction conditions, 350 mg L-1 of H2O2 was electro-generated and 99.2% of sodium diclofenac was degradated, with 27.4% COD reduction. At the same conditions, but using Fe(II), drug degradation was 99.4% and the COD reduction was 63.2%.

Degradação eletroquímica do cloranfenicol em reator de fluxo

This paper reports a study of electrochemical degradation of the chloramphenicol antibiotic in aqueous medium using a flow-by reactor with DSA® anode. The process efficiency was monitored by chloramphenicol concentration analysis with liquid chromatography (HPLC) during the experiments. Analysis of Total Organic Carbon (TOC) was performed to estimate the degradation degree and Ion Chromatography (IC) was performed to determinate inorganic ions formed during the eletrochemical degradation process. In electrochemical flow-by reactor, 52% of chloramphenicol was degraded, with 12% TOC reduction. IC analysis showed the production of chloride ions (25 mg L-1), nitrate ions (6 mg L-1) and nitrite ions (4.5 mg L-1).

Degradação de corantes têxteis e remediação de resíduos de tingimento por processos Fenton, foto-Fenton e eletro-Fenton

In this work the degradation of textile dyes were evaluated, using Fenton, photo-Fenton and electro-Fenton processes. Under optimized conditions Fenton and photo-Fenton processes showed high decolorization capacity of the model dyes. The electro-Fenton process was carried out in an undivided electrochemical reactor (1000 mL) equipped with a carbon-felt cathode (253 cm²) and a platinum gauze anode (6 cm²). Under optimal conditions (J: 1.6 mA cm-2, Na2SO4: 0.075 mol L-1, pH: 3) H2O2 concentration of about 60 mg L-1 was observed. The addition of Fe2+ (15 mg L-1) induces Fenton reactions that permit almost total decolorization of textile dyes.

CÉLULAS SOLARES SENSIBILIZADAS POR CORANTES NATURAIS: UM EXPERIMENTO INTRODUTÓRIO SOBRE ENERGIA RENOVÁVEL PARA ALUNOS DE GRADUAÇÃO

An interesting practical experiment about the preparation of dye–sensitized solar cells (DSSC) using natural dyes were carried out by the undergraduate students in the chemistry course at UNICAMP . Natural dyes were extracted from blueberries (Vaccinium myrtillus L.), jabuticabas (Myrciaria cauliflora), raw and cooked beets (Beta vulgaris L.), and annattos (Bixa orellana L.), which were used to sensitize TiO2 films that composed the photoanode in the DSSC. A polymer electrolyte containing an iodide/triiodide redox couple was used in lieu of the use of liquid solutions to prevent any leakage in the devices. A maximum solar-to-electric energy conversion of 0.26 ± 0.02% was obtained for the solar cell prepared with annatto extracts. This experiment was an effective way to illustrate to the undergraduate students how to apply some of the chemical concepts that they learned during their chemistry course to produce electric energy from a clean and renewable energy source. Teachers could also exploit the basics of the electronic transitions in inorganic and organic compounds (e.g., metal-to-ligand charge transfer and ϖ-ϖ* transitions), thermodynamics (e.g., Gibbs free energy), acid–base reactions in the oxide solid surface and electrolyte, and band theory (i.e., the importance of the Fermi level energy).

Geração eletroquímica do hidreto de selênio em sistema de injeção em fluxo com detecção por espectrometria de absorção atômica com chama Ar-Glp

This paper presents a system for electrochemical hydride generation using flow-injection and atomic absorption spectrometry to determine selenium in biological materials. The electrolytic cell was constructed by assembling two reservoirs, one for the sample and the other for the electrolytic solution separated by a Nafion membrane. Each compartment had a Pt electrode. The sample and electrolyte flow-rates, acidic media, and applied current were adjusted to attain the best analytical performance and ensure the membrane lifetime. The atomisation system used a T quartz tube in an air-LPG flame. The composition of the flame, the observation height, and the argon flow rate used to carry the hydrides were critically investigated. The system allowed to perform thirty determinations per hour with a detection limit of 10 mug L-1 of Se. Relative standard deviations were in general lower than 1.5% for a solution containing 20.0 and 34.0 mug L-1 of Se in a typical sample digest. Accuracy was assessed analysing the certified materials: rice flour (NIST-1568) from National Institute of Standard and Technology and dried fish (MA-A-2), whole animal blood (A-2/1974) from the International Atomic Energy Agency.

Influence of the medium (strongly acid or basic) over the electrochemical properties of the nitrate selective electrode

A nitrate selective electrode was prepared for use in an aggresive medium (high acidic or basic concentration). It is demonstrated that the depending E graph with respect to pNO3- has not a Nernstian response in concentration acidic range upper 0.1 mol/L H2SO4. The observed behaviour is supposed to be due to the formation of a dimeric anion HN2O6-.

Electrochemical study and dependence of 'transition state' in Co(II) and Ni(II) complexes with some antibiotics and cephalothin

Electrode kinetics and study of 'transition state' with applied potential in case of [M - antibiotics - cephalothin] system were reported at pH = 7.30 ± 0.01 at suitable supporting electrolyte at 25.0ºC. The M = Co or Ni and antibiotics were doxycycline, chlortetracycline, oxytetracycline, tetracycline, minocycline, amoxicillin and chloramphenicol used as primary ligands and cephalothin as secondary ligand. Kinetic parameters viz. transfer coefficient (a), degree of irreversibility (l), diffusion coefficient (D) and rate constant (k) were determined. The values of a and k varied from 0.41 to 0.59 and 2.60 X 10-3 cm s-1 to 9.67 X 10-3 cm s-1 in case of [Co - antibiotics - cephalothin] system. In case of [Ni - antibiotics - cephalothin], a and k varied from 0.41 to 0.58 and 2.34 X 10-3 cm s-1 to 9.19 X 10-3 cm s-1 respectively confirmed that transition state behaves between oxidant and reductant response to applied potential and it adjusts it self in such a way that the same is located midway between dropping mercury electrode and solution interface. The values of rate constant confirmed the quasireversible nature of electrode processes. The stability constants (logb) of complexes were also determined.

Application of response surface methodology to study the biological removal of nitrogen from effluent of cattle slaughterhouse in a sequencing batch reactor

The aim of this study was to evaluate the efficiency of a sequencing batch reactor (SBR) on biological removal of nitrogen from cattle slaughterhouse wastewater by nitrification/denitrification processes. The effects of initial concentration of ammoniacal nitrogen were investigated at 100; 150 and 200 mg L-1 and air flow rate at 0.125; 0.375 and 0.625 L min¹ Lreactor-1 on the nitrogen compounds removal, by a Central Composite Rotational Design (CCRD) configuration. There were variations from 9.2 to 94.9%, 4.0 to 19.6% and 20.8 to 92.0% in the conversion of ammoniacal nitrogen to nitrate and nitrite concentration and removal of total nitrogen, respectively. The increase of air flow rate and decrease of the initial concentration of ammoniacal nitrogen resulted in higher efficiencies of total nitrogen removal, as well as the conversion of ammoniacal nitrogen to nitrate. During the pre-established intervals of this study, the removal and conversion efficiencies of nitrogen compounds above 85% were achieved in air flow rate variations from 0.375 to 0.725 L min-1 Lreactor-1 and initial concentration of ammoniacal nitrogen from 80 to 200 mg L-1. On denitrification process, we obtained efficiencies from 91.5 to 96.9% on the removal of nitrite/nitrate and from 78.3 to 87.9% on the removal of organic matter.

Instabilities in electrochemical systems with a rotating disc electrode

Polarization curves experimentally obtained in the electro-dissolution of iron in a 1 M H2SO4 solution using a rotating disc as the working electrode present a current instability region within the range of applied voltage in which the current is controlled by mass transport in the electrolyte. According to the literature (Barcia et. al., 1992) the electro-dissolution process leads to the existence of a viscosity gradient in the interface metal-solution, which leads to a velocity field quantitatively different form the one developed in uniform viscosity conditions and may affect the stability of the hydrodynamic field. The purpose of this work is to investigate whether a steady viscosity profile, depending on the distance to the electrode surface, affects the stability properties of the classic velocity field near a rotating disc. Two classes of perturbations are considered: perturbations monotonically varying along the radial direction, and perturbations periodically modulated along the radial direction. The results show that the hydrodynamic field is always stable with respect to the first class of perturbations and that the neutral stability curves are modified by the presence of a viscosity gradient in the second case, in the sense of reducing the critical Reynolds number beyond which perturbations are amplified. This result supports the hypothesis that the current oscillations observed in the polarization curve may originate from a hydrodynamic instability.

Preserved xenogenic amniotic membrane as a patch on the repair of superficial corneal ulcers in rabbits

The aim of this study was to evaluate the effects of canine amniotic membrane, previously preserved in glycerin, used as a patch on the repair of experimentally-made superficial corneal ulcers and to compare corneal epithelization between the treated and non-treated groups. Xenogeneic amniotic membranes were collected aseptically and preserved in 99% glycerin at room temperature. Each animal was anesthetized and submitted to superficial corneal keratectomy of the left eye. The treated group received a fragment of canine amniotic membrane as a patch, while the control group had no treatment. The treated group showed blepharospasm, ocular discharge and conjunctival congestion. The membrane accelerated corneal repair in the beginning of the process, however, it delayed its conclusion (p<0.05). Treated eyes showed greater vessel formation and decreased corneal transparency (p<0.05). The stroma of the control group was thicker than that of the treated group (p<0.05). We suggest that amniotic membrane used in this manner can be applied as a therapy for superficial corneal ulcers in the beginning phases of the repair process.

The institutional configuration of sport policy in Brazil: organization, evolution and dilemmas

Brazil has become the center of the spotlight of the whole world recently, amongst many other reasons, one of them was because it was chosen to host a series of mega sporting events - Pan American Games in 2007, Confederations Football Cup in 2013, Fifa Football World Cup 2014 Games and 2016 Olympic and Paralympic Games in 2016. However, little is known about the country's administrative governmental structure focused on sport policy. The available studies focus their analysis on the sport policies content, but not on the arrangement of its structural decision-making. The main aim of this article is indeed to describe, based on official documentation, the evolution and the current arrangements of the government responsible for the administrative structure for the planning and implementation of sports policies in Brazil. Thus, we tried to list the main problems arising from the organization of the Brazilian sports' management. These problems are: (1) inappropriate institutional structure in terms of human resources and obstacles to participation by other social actors beyond the officials (parliament and members of the Ministry of Sports) in the sports policy; (2) disarticulation between public institutions generating redundancies and conflicts of jurisdiction due to the poor division of labor between bureaucracy agencies; and (3) inadequate planning proved by the lack of organization of some institutions, and by the lack of assessment and continuity of public policies over time. Therefore, we must emphasize those problems from above, and due to these administrative arrangements, Brazilian sports' policy has big challenges in the sport development in this country, which includes the creation of a national "system" for sports and a priority investment in sport education.

Comparative studies of Yersinia pestis outer membrane isolation techniques and their potential use in plague epidemiology

In the present study three techniques for obtaining outer membrane enriched fractions from Yersinia pestis were evaluated. The techniques analysed were: differential solubilization of the cytoplasmic membrane with Sarkosyl or Triton X-100, and centrifugation in sucrose density gradients. The sodium dodecyl-sulfate polyacrylamide gel electrophoresis (SDS-PAGE) of outer membrane isolated by the different methods resulted in similar protein patterns. The measurement of NADH-dehydrogenase and succinate dehydrogenase (inner membrane enzymes) indicated that the outer membrane preparations obtained by the three methods were pure enough for analytical studies. In addition, preliminary evidences on the potential use of outer membrane proteins for the identification of geographic variants of Y. pestis wild isolates are presented.

Analysis of proteins from membrane and soluble fractions of Giardia duodenalis trophozoites of two Brazilian axenic strains

In the present study, we have analyzed by sodium docecyl sulphate - polyacrilamide gel electrophoresis (SDS-PAGE), immunoblotting and Concanavalin A blotting (Con A blotting) proteins of membrane fractions and soluble fractions obtained from Giardia duodenalis trophozoites of two axenic strains isolated in Brazil from a symptomatic (BTU-11) and an asymptomatic patient (BTU-10), as compared to the reference strain Portland 1. Both Brazilian strains showed a complex and homogeneous electrophoretic pattern of proteins, but some differences could be observed. Several glycoproteins were detected, particularly the proteins of 81, 72, 59 kDa and the protein of 62 kDa in the membrane proteins and cytosol, respectively. Many antigenic components were revealed by anti-Giardia rabbit IgG antibodies in the immunoblotting analysis. Among these components, the membrane protein of 32 kDa and the cytosol protein of 30 kDa could be related to giardin, as previously demonstrated.