Triphenylmethane dyes, an alternative for mediated electronic transfer systems in glucose oxidase biofuel cells

The bioelectrochemical behavior of three triphenylmethane (TPM) dyes commonly used as pH indicators, and their application in mediated electron transfer systems for glucose oxidase bioanodes in biofuel cells was investigated. Bromophenol Blue, Bromothymol Blue, Bromocresol Green were compared bio-electrochemically against two widely used mediators, benzoquinone and ferrocene carboxy aldehyde. Biochemical studies were performed in terms of enzymatic oxidation, enzyme affinity, catalytic efficiency and co-factor regeneration. The different features of the TPM dyes as mediators are determined by the characteristics in the oxidation/reduction processes studied electrochemically. The reversibility of the oxidation/reduction processes was also established through the dependence of the voltammetric peaks with the sweep rates. All three dyes showed good performances compared to the FA and BQ when evaluated in a half enzymatic fuel cell. Potentiodynamic and power response experiments showed maxima power densities of 32.8 mu W cm(-2) for ferrocene carboxy aldehyde followed by similar values obtained for TPM dyes around 30 mu W cm(-2) using glucose and mediator concentrations of 10 mmol L(-1) and 1.0 mmol L(-1), respectively. Since no mediator consumption was observed during the bioelectrochemical process, and also good redox re-cycled processes were achieved, the use of triphenylmethane dyes is considered to be promising compared to other mediated systems used with glucose oxiclase bioanodes and/or biofuel cells. (C) 2011 Elsevier Inc. All rights reserved.

Stabilizing Nonstationary Electrochemical Time Series

Electrochemical systems are ideal working-horses for studying oscillatory dynamics. Experimentally obtained time series, however, are usually associated with a spontaneous drift in some uncontrollable parameter that triggers transitions among different oscillatory patterns, despite the fact that all controllable parameters are kept constant. Herein we present an empirical method to stabilize experimental potential time series. The method consists of applying a negative galvanodynamic sweep to compensate the spontaneous drift and was tested for the oscillatory electro-oxidation of methanol on platinum. For a wide range of applied currents, the base system presents spontaneous transitions from quasi-harmonic to mixed mode oscillations. Temporal patterns were stabilized by galvanodynamic sweeps at different rates. The procedure resulted in a considerable increase in the number of oscillatory cycles from 5 to 20 times, depending on the specific temporal pattern. The spontaneous drift has been associated with uncompensated oscillations, in which the coverage of some adsorbed species are not reestablished after one cycle; i.e., there is a net accumulation and/or depletion of adsorbed species during oscillations. We interpreted the rate of the galvanodynamic sweep in terms of the time scales of the poisoning processes that underlies the uncompensated oscillations and thus the spontaneous slow drift.

Electrodeposition and characterization of undoped and nitrogen-doped ZnSe films

Semiconducting films of (n-type) ZnSe and (p-type) nitrogen-doped ZnSe were electrodeposited by a linear-sweep voltammetric technique on to a substrate of fluorine-tin oxide (FM) glass ceramics. The films were characterized by scanning electron microscopy, energy-dispersive X-ray analysis and grazing-incidence X-ray diffraction. The results indicated that the material was deposited uniformly over the substrate, forming clusters when the Zn content of the bath was 0.1 mol L(-1) and a film when it was 0.2 or 0.3 mol L(-1). The effectiveness of doping the films with nitrogen by adding ammonium sulfate to the deposition solution was assessed by measuring the film-electrolyte interface capacitance (C) at various applied potentials (E(ap)) and plotting Mott-Schottky curves (C(-2) vs E(ap)), whose slope sign was used to identify p-type ZnSe. (C) 2009 Elsevier B.V. All rights reserved.

Spatiotemporal Pattern Formation in the Oscillatory Electro-Oxidation of Sulfide on a Platinum Disk

Spatiotemporal pattern formation in the electrocatalytic oxidation of sulfide on a platinum disk is investigated using electrochemical methods and a charge-coupled device (CCD) camera simultaneously. The system is characterized by different oscillatory regions spread over a wide potential range. An additional series resistor and a large electrode area facilitate observation of multiple regions of kinetic instabilities along the current/potential curve. Spatiotemporal patterns on the working electrode, such as fronts, pulses, spirals, twinkling eyes, labyrinthine stripes, and alternating synchronized deposition and dissolution, are observed at different operating conditions of series resistance and sweep rate.

Deposition of selenium thin layers on gold surfaces from sulphuric acid media: Studies using electrochemical quartz crystal microbalance, cyclic voltammetry and AFM

In this paper we report here new considerations about the relationship between the mass and charge variations (m/z relationship) in underpotential deposition (UPD), bulk deposition and also in the H(2)Se formation reaction. Nanogravimetric experiments were able to show the adsorption of H(2)SeO(3) on the AuO surface prior to the voltammetric sweep and that, after the AuO reduction, 0.40 monolayer of H(2)SeO(3) remains adsorbed on the newly reduced Au surface, which was enough to gives rise to the UPD layer. The UPD results indicate that the maximum coverage with Se(ads) on polycrystalline gold surface corresponds to approximately 0.40 monolayer, in good agreement with charge density results. The cyclic voltammetry experiments demonstrated that the amount of bulk Se obtained during the potential scan to approximately 2 Se monolayers, which was further confirmed by electrochemical quartz crystal microbalance (EQCM) measurements that pointed out a mass variation corresponding of 3 monolayers of Se. In addition, the Se thin films were obtained by chronoamperometric experiments, where the Au electrode was polarized at +0.10V during different times in 1.0 M H(2)SO(4) + 1.0 mM SeO(2). The topologic aspects of the electrodeposits were observed in Atomic Force Microscope (AFM) measurements. Finally, in highly negative potential polarizations, the H(2)Se formation was analyzed by voltammetric and nanogravimetric measurements. These finding brings a new light on the selenium electrodeposition and point up to a proposed electrochemical model for molecule controlled surface engineering. (c) 2009 Elsevier Ltd. All rights reserved.

Development of an Analytical Methodology for Quantification of Strong Acid in Diesel Oil

Many factors can affect the quality of diesel oil, in particular the degradation processes that are directly related to some organosulfur compounds. During the degradation process, these compounds are oxidized into their corresponding sulfonic acids, generating a strong acid content during the process. p-Toluene sulfonic acid analysis was performed using the linear sweep voltammetry technique with a platinum ultramicroelectrode in aqueous solution containing 3 mol L(-1) potassium chloride. An extraction step was introduced prior to the voltammetric detection in order to avoid the adsorption of organic molecules, which inhibit the electrochemical response. The extraction step promoted the transference of sulfonic acid from the diesel oil to an aqueous phase. The method was accurate and reproducible, with detection and quantification limits of 5 ppm and 15 ppm, respectively. Recovery of sulfonic acid was around 90%.

Nanogravimetric study of the complex voltammetric response in the electro-oxidation of methanol on platinum

Instead of a time-invariant voltammetric profile, many electrochemical systems display a cycle-dependent current-potential response. This phenomenon has been referred to as complex voltammetric response and it has been observed during the electro-oxidation of several molecules such as methanol, ethanol, propanol and hydrogen. There are currently two explanations for the surface mechanism underlying this behavior. In one scenario, the complex voltammogram would result from the specific kinetic pathway taken during the forward sweep. In the other explanation, the phenomenon is discussed in terms of the interplay among the surface roughening and subsequent relaxation, and the ohmic drop coupled to a negative differential resistance. We report in this paper a nanogravimetric investigation of the complex voltammetric response in the electro-oxidation of methanol on platinum electrode in both acidic and alkaline media. Different periodic patterns composed of intercalated small and large hysteresis cycles were observed as a function of the applied voltage and the series resistance between the working electrode and the potentiostat. Independently, nanogravimetric results indicated no detectable difference in the delta-frequency versus voltage profile between small and large hysteresis cycles. These findings were interpreted as experimental evidence of the secondary, if any, role played by the very electrochemical reaction on the emergence of complex voltammetric response. (C) 2009 Elsevier Ltd. All rights reserved.

Estudo paramétrico da recuperação de óleo no processo de drenagem gravitacional com injeção de CO2

The gas injection has become the most important IOR process in the United States. Furthermore, the year 2006 marks the first time the gas injection IOR production has surpassed that of steam injection. In Brazil, the installation of a petrochemical complex in the Northeast of Brazil (Bahia State) offers opportunities for the injection of gases in the fields located in the Recôncavo Basin. Field-scale gas injection applications have almost always been associated with design and operational difficulties. The mobility ratio, which controls the volumetric sweep, between the injected gas and displaced oil bank in gas processes, is typically unfavorable due to the relatively low viscosity of the injected gas. Furthermore, the difference between their densities results in severe gravity segregation of fluids in the reservoirs, consequently leading to poor control in the volumetric sweep. Nowadays, from the above applications of gas injection, the WAG process is most popular. However, in attempting to solve the mobility problems, the WAG process gives rise to other problems associated with increased water saturation in the reservoir including diminished gas injectivity and increased competition to the flow of oil. The low field performance of WAG floods with oil recoveries in the range of 5-10% is a clear indication of these problems. In order to find na effective alternative to WAG, the Gas Assisted Gravity Drainage (GAGD) was developed. This process is designed to take advantage of gravity force to allow vertical segregation between the injected CO2 and reservoir crude oil due to their density difference. This process consists of placing horizontal producers near the bottom of the pay zone and injecting gás through existing vertical wells in field. Homogeneous models were used in this work which can be extrapolated to commercial application for fields located in the Northeast of Brazil. The simulations were performed in a CMG simulator, the STARS 2007.11, where some parameters and their interactions were analyzed. The results have shown that the CO2 injection in GAGD process increased significantly the rate and the final recovery of oil

Análise da trajetória de poços horizontais em reservatório de óleo pesado

The application of thermal methods, to increase the recovery of heavy oil in mature fields through drainage with multilateral and horizontal wells, has been thoroughly studied, theorically, experimentally, testing new tools and methods. The continuous injection of steam, through a steam injector well and a horizontal producer well in order to improve horizontal sweep of the fluid reservoir, it is an efficient method. Starting from an heterogeneous model, geologically characterized, modeling geostatistics, set history and identification of the best path of permeability, with seismic 3D, has been dubbed a studying model. It was studied horizontal wells in various directions in relation to the steam and the channel of higher permeability, in eight different depths. Into in the same area were studied, the sensitivity of the trajectories of horizontal wells, according to the depth of navigation. With the purpose of obtaining the highest output of oil to a particular flow, quality, temperature and time for the injection of steam. The wells studied showed a significant improvement in the cumulative oil recovery in one of the paths by promoting an alternative to application in mature fields or under development fields with heavy oil

Avaliação da espécie vegetal Croton cajucara Benth como inibidor de biocorrosão em aço carbono Aisi 1020

Actually in the oil industry biotechnological approaches represent a challenge. In that, attention to metal structures affected by electrochemical corrosive processes, as well as by the interference of microorganisms (biocorrosion) which affect the kinetics of the environment / metal interface. Regarding to economical and environmental impacts reduction let to the use of natural products as an alternative to toxic synthetic inhibitors. This study aims the employment of green chemistry by evaluating the stem bark extracts (EHC, hydroalcoholic extract) and leaves (ECF, chloroform extract) of plant species Croton cajucara Benth as a corrosion inhibitor. In addition the effectiveness of corrosion inhibition of bioactive trans-clerodane dehydrocrotonin (DCTN) isolated from the stem bark of this Croton was also evaluated. For this purpose, carbon steel AISI 1020 was immersed in saline media (3,5 % NaCl) in the presence and absence of a microorganism recovered from a pipeline oil sample. Corrosion inhibition efficiency and its mechanisms were investigated by linear sweep voltammetry and electrochemical impedance. Culture-dependent and molecular biology techniques were used to characterize and identify bacterial species present in oil samples. The tested natural products EHC, ECF and DCTN (DMSO as solvent) in abiotic environment presented respectively, corrosion inhibition efficiencies of 57.6% (500 ppm), 86.1% (500 ppm) and 54.5% (62.5 ppm). Adsorption phenomena showed that EHC best fit Frumkin isotherm and ECF to Temkin isotherm. EHC extract (250 ppm) dissolved in a polar microemulsion system (MES-EHC) showed significant maximum inhibition efficiency (93.8%) fitting Langmuir isotherm. In the presence of the isolated Pseudomonas sp, EHC and ECF were able to form eco-compatible organic films with anti-corrosive properties

Efeitos do plantio direto e da consorciação soja-milho sobre inimigos naturais e pragas

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Structure and viscoelastic behavior of pharmaceutical biocompatible anionic microemulsions containing the antitumoral drug compound doxorubicin

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Investigation on dielectric response of PMN ceramics around paraelectric-ferroelectric diffuse phase transition

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Differential pulse voltammetric determination of nitrite with gold ultramicroelectrode

The application of disk shaped gold ultramicroelectrode for nitrite determination with and without addition of supporting electrolyte was studied using the differential pulse voltammetric method. The well-defined peak for nitrite oxidation near 0.8V (vs. Ag/AgCl reference electrode) was used to obtain analytical plots in the concentration range from 0.1 to 0.6 mmol L-1 and from 10.0 to 50.0 mu mol.L-1. The calculated detection limit was 0.65 mu mol.L-1 in purified water, in the absence of supporting electrolyte, with relative standard deviation of 1.36% (n=6) for analyzing 10.0 mu mol L-1 nitrite solutions, and accuracy of 100.9 %, based on recovery studies. The application of this analytical method to mineral and river water samples of natural pH also showed improved sensitivity when compared with the linear sweep voltammetric method previously reported.

Determination of lead in the absence of supporting electrolyte using carbon fiber ultramicroelectrode without mercury film

The determination of lead ions directly in water, for application in analysis of samples of environmental interest, was studied by electroanalytical techniques. Linear sweep anodic stripping voltammetry with a carbon fiber disk ultramicroelectrode (7.0 mu m in diameter), without mercury film, has been used for lead determination, by standard addition, in purified water in the absence of supporting electrolyte. The response was linear in the range from 10.0 to 50.0 mu g L-1, with a detection limit of 0.8 mu g L-1, for 300 s preconcentration time, at -1.2 V and 1.0 V s(-1) scan rate. The reliability of the analytical procedure was evaluated by precision using relative standard deviations (5.6%, for three repetitive stripping current measurements of solution with 10.0 mu g L-1 lead ions) and by the accuracy with recovery experiments (mean of 110.8%) for the same concentration.