Análise por injeção em fluxo com detecção amperométrica de múltiplos pulsos: potencialidades e aplicações

The potentialities and applications of the Multiple Pulse Amperometric detection (MPA) coupled with Flow Injection Analysis (FIA) are evaluated. Important aspects as cleaning and activation of electrode surface, indirect and simultaneous analysis of electroactive compounds and the use of the internal standard method for quantifications utilizing FIA-MPA are presented. The main parameters concerning the detection of electroactive analytes by multiple pulse amperometric detection in flowing solutions were also discussed. In addition, aspects such as flow rate, sample volume, application time of the potential pulses and instrumentation necessary for implementing of the method were also addressed.

Especiação química de arsênio inorgânico no estuário da Laguna dos Patos (RS, Brasil)

This study optimized and validated a method to perform chemical speciation of inorganic arsenic in water samples collected under the Monitoring Program of the Port of Rio Grande-RS in July and October 2010 from the Laguna dos Patos Estuary (RS, Brazil). The flow injection hydride generation atomic absorption spectrometry technique was employed, allowing quantification of As3+ and As5+ present in estuarine water samples. Data interpretation for results generated using the improved method for analyzing water samples collected from Laguna dos Patos Estuary was done by main components analysis.

Desenvolvimento de um sistema de análise por injeção em fluxo utilizando materiais alternativos de baixo custo para fins didáticos

This work describes a simple and inexpensive flow injection analysis system in which gravity force provides fluid propulsion while needles for insulin administration or metallic wires act as electrodes for amperometric detection. The proposed system was able to demonstrate the influence of several operational parameters on the transient signals. Moreover, this system was successfully used to evaluate both the stoichiometry of Cu2+-EDTA complex and the effect of pH on the kinetics of the reaction between ferricyanide and ascorbic acid. Therefore, the proposed system can be regarded as an efficient and accessible didactic tool for the teaching of FIA principles.

Amperometric biosensor for ascorbic acid

A L-ascorbic acid biosensor based on ascorbate oxidase has been developed. The enzyme was extracted from the mesocarp of cucumber (Cucumis sativus) by using 0.05 mol L-1 phosphate buffer, pH 5.8 containing 0.5 mol L-1 NaCl. After the dialysis versus phosphate buffer 0.05 mol L-1 pH 5.8, the enzyme was immobilized onto nylon net through glutaraldehyde covalent bond. The membrane was coupled to an O2 electrode and the yielding reaction monitored by oxygen depletion at -600 mV using flow injection analysis optimized to 0.1 mol L-1 phosphate buffer pH 5.8, as the carrier solution and flow-rate of 0.5 mL min-1. The ascorbic acid calibration curve was linear from 1.2x10-4 to 1.0x10-3 mol L-1. The evaluation of biosensor lifetime leads to 500 injections. Commercial pharmaceutical samples were analyzed with the proposed method and the results were compared with those obtained by high-performance liquid chromatography (HPLC).

Immobilization of glucose oxidase enzyme (GOD) in large pore ordered mesoporous cage-like FDU-1 silica

Large pore ordered mesoporous silica FDU-1 with three-dimensional (3D) face-centered cubic, Fm3m arrangement of rnesopores, was synthesized under strong acid media using B-50-6600 poly(ethylene oxide)-poly(butylene oxide)-poly(ethylene oxide) triblock copolymer (EO(39)BO(47)EO(39)), tetraethyl orthosilicate (TEOS) and trimethyl-benzene (TMB). Large pore FDU-1 silica was obtained by using the following gel composition 1TEOS:0.00735B50-6600:0.00735TMB:6HCl:155H(2)O. The pristine material exhibited a BET specific surface area of 684 m(2) g(-1), total pore volume of 0.89 cm(3) g(-1), external surface area of 49 m(2) g(-1) and microporous volume of 0.09 cm(3) g(-1). The enzyme activity was determined by the Flow Injection Analysis-Chemiluminescence (FIA-CL) method. For GOD immobilized on the FDU-1 silica, GOD supernatant and GOD solution, the FIA-CL results were 9.0, 18.6 and 34.0 U, respectively. The value obtained for the activity of the GOD solution with FIA-CL method is in agreement with the 35 U, obtained by spectrophotometry. (C) 2011 Elsevier B.V. All rights reserved.

Development of impedimetric and optical calcium biosensor by using modified gold electrode with porcine S100A12 protein

We describe the development of a label free method to analyze the interactions between Ca(2+) and the porcine S100A12 protein immobilized on polyvinyl butyral (PVB). The modified gold electrodes were characterized using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM) and surface plasmon resonance (SPR) techniques. SEM analyses of PVB and PVB-S100A12 showed a heterogeneous distribution of PVB spherules on gold surface. EIS and CV measurements have shown that redox probe reactions on the modified gold electrodes were partially blocked due the adsorption of PVB-S100A12, and confirm the existence of a positive response of the immobilized S100Al2 to the presence of calcium ions. The biosensor exhibited a wide linear response to Ca(2+) concentrations ranging from 12.5 to 200 mM. The PVB-S100A12 seems to be bound to the gold electrode surface by physical adsorption: we observed an increase of 1184.32 m degrees in the SPR angle after the adsorption of the protein on the PVB surface (in an indication that 9.84 ng of S100A12 are adsorbed per mm(2) of the Au-PVB electrode), followed by a further increase of 581.66 m degrees after attachment of the Ca(2+) ions. In addition, no SPR response is obtained for non-specific ions. These studies might be useful as a platform for the design of new reusable and sensitive biosensing devices that could find use in the clinical applications. (C) 2010 Elsevier B.V. All rights reserved.

Amperometric detection of benzoyl peroxide in pharmaceutical preparations using carbon paste electrodes with peroxidases naturally immobilized on coconut fibers

This paper describes the applications of anew carbon paste electrode containing fibers of coconut (Cocus nucifera L) fruit, which are very rich in peroxidase enzymes naturally immobilized on its structure. The new sensor was applied for the amperometric quantification of benzoyl peroxide in facial creams and dermatological shampoos. The amperometric measurements were performed in 0.1 mol L(-1) phosphate buffer (pH 5.2), at 0.0 V (versus Ag/AgCl). On these conditions, benzoyl peroxide was rapidly determined in the 5.0-55 mu mol L(-1), with a detection limit of 2.5 mu mol L(-1) (s/n = 3), response time of 4.1 s (90% of the steady state) and sensitivity limit of 0.33 A mol L(-1) cm(-2). The amperometric results are in good agreement with those obtained by spectrophotometric technique, used as a standard method. (C) 2009 Elsevier B.V. All rights reserved.

Quantification of N-acetylcysteine in pharmaceuticals using cobalt phthalocyanine modified graphite electrodes

Flow injection analysis (FIA) with amperometric detection was employed for the quantification of N-acetylcysteine (NAC) in pharmaceutical formulations, utilizing an ordinary pyrolytic graphite (OPG) electrode modified with cobalt phthalocyanine (CoPc). Cyclic voltammetry was used in preliminary studies to establish the best conditions for NAC analysis. In FIA-amperometric experiments the OPG-CoPc electrode exhibited sharp and reproducible current peaks over a wide linear working range (5.0 x 10(-5)-1.0 x 10(-3) mol L(-1)) in 0.1 mol L(-1) NaOH solution. High sensitivity (130 mA mol(-1) cm(2)) and a low detection limit (9.0 x 10(-7) mol L(-1)) were achieved using the sensor. The repeatability (R.S.D.%) for 13 successive flow injections of a solution containing 5.0 x 10(-4) mol L(-1) NAC was 1.1%. The new procedure was applied in analyses of commercial pharmaceutical products and the results were in excellent agreement with those obtained using the official titrimetric method. The proposed amperometric method is highly suitable for quality control analyses of NAC in pharmaceuticals since it is rapid, precise and requires much less work than the recommended titrimetric method. (C) 2010 Elsevier B.V. All rights reserved.

Análise paramétrica da simulação composicional do processo de Drenagem Gravitacional Assistida por Gás (GAGD)

In Brazil and around the world, oil companies are looking for, and expected development of new technologies and processes that can increase the oil recovery factor in mature reservoirs, in a simple and inexpensive way. So, the latest research has developed a new process called Gas Assisted Gravity Drainage (GAGD) which was classified as a gas injection IOR. The process, which is undergoing pilot testing in the field, is being extensively studied through physical scale models and core-floods laboratory, due to high oil recoveries in relation to other gas injection IOR. This process consists of injecting gas at the top of a reservoir through horizontal or vertical injector wells and displacing the oil, taking advantage of natural gravity segregation of fluids, to a horizontal producer well placed at the bottom of the reservoir. To study this process it was modeled a homogeneous reservoir and a model of multi-component fluid with characteristics similar to light oil Brazilian fields through a compositional simulator, to optimize the operational parameters. The model of the process was simulated in GEM (CMG, 2009.10). The operational parameters studied were the gas injection rate, the type of gas injection, the location of the injector and production well. We also studied the presence of water drive in the process. The results showed that the maximum vertical spacing between the two wells, caused the maximum recovery of oil in GAGD. Also, it was found that the largest flow injection, it obtained the largest recovery factors. This parameter controls the speed of the front of the gas injected and determined if the gravitational force dominates or not the process in the recovery of oil. Natural gas had better performance than CO2 and that the presence of aquifer in the reservoir was less influential in the process. In economic analysis found that by injecting natural gas is obtained more economically beneficial than CO2

Modelagem e previsão da perda de injetividade em poços canhoneados

Waterflooding is a technique largely applied in the oil industry. The injected water displaces oil to the producer wells and avoid reservoir pressure decline. However, suspended particles in the injected water may cause plugging of pore throats causing formation damage (permeability reduction) and injectivity decline during waterflooding. When injectivity decline occurs it is necessary to increase the injection pressure in order to maintain water flow injection. Therefore, a reliable prediction of injectivity decline is essential in waterflooding projects. In this dissertation, a simulator based on the traditional porous medium filtration model (including deep bed filtration and external filter cake formation) was developed and applied to predict injectivity decline in perforated wells (this prediction was made from history data). Experimental modeling and injectivity decline in open-hole wells is also discussed. The injectivity of modeling showed good agreement with field data, which can be used to support plan stimulation injection wells

Estudo de sistemas multicomponentes no processo de injeção cíclica de vapor

In Brazilian Northeast there are reservoirs with heavy oil, which use steam flooding as a recovery method. This process allows to reduce oil viscosity, increasing its mobility and consequently its oil recovery. Steam injection is a thermal method and can occurs in continues or cyclic form. Cyclic steam stimulation (CSS) can be repeated several times. Each cycle consisting of three stages: steam injection, soaking time and production phase. CSS becomes less efficient with an increase of number of cycles. Thus, this work aims to study the influence of compositional models in cyclic steam injection and the effects of some parameters, such like: flow injection, steam quality and temperature of steam injected, analyzing the influence of pseudocomponents numbers on oil rate, cumulative oil, oil recovery and simulation time. In the situations analyzed was compared the model of fluid of three phases and three components known as Blackoil . Simulations were done using commercial software (CMG), it was analyzed a homogeneous reservoir with characteristics similar to those found in Brazilian Northeast. It was observed that an increase of components number, increase the time spent in simulation. As for analyzed parameters, it appears that the steam rate, and steam quality has influence on cumulative oil and oil recovery. The number of components did not a lot influenced on oil recovery, however it has influenced on gas production

Estudo paramétrico do processo de injeção de solventes em poços horizontais para reservatórios de óleos pesados

The world has many types of oil that have a range of values of density and viscosity, these are characteristics to identify whether an oil is light, heavy or even ultraheavy. The occurrence of heavy oil has increased significantly and pointing to a need for greater investment in the exploitation of deposits and therefore new methods to recover that oil. There are economic forecasts that by 2025, the heavy oil will be the main source of fossil energy in the world. One such method is the use of solvent vaporized VAPEX which is known as a recovery method which consists of two horizontal wells parallel to each other, with a gun and another producer, which uses as an injection solvent that is vaporized in order to reduce the viscosity of oil or bitumen, facilitating the flow to the producing well. This method was proposed by Dr. Roger Butler, in 1991. The importance of this study is to analyze how the influence some operational reservoir and parameters are important in the process VAPEX, such as accumulation of oil produced in the recovery factor in flow injection and production rate. Parameters such as flow injection, spacing between wells, type of solvent to be injected, vertical permeability and oil viscosity were addressed in this study. The results showed that the oil viscosity is the parameter that showed statistically significant influence, then the choice of Heptane solvent to be injected showed a greater recovery of oil compared to other solvents chosen, considering the spacing between the wells was shown that for a greater distance between the wells to produce more oil

Estudo de modelos composicionais de óleo na injeção contínua de vapor

The objective of the thermal recovery is to heat the resevoir and the oil in it to increase its recovery. In the Potiguar river basin there are located several heavy oil reservoirs whose primary recovery energy provides us with a little oil flow, which makes these reservoirs great candidates for application of a method of recovery advanced of the oil, especially the thermal. The steam injection can occur on a cyclical or continuous manner. The continuous steam injection occurs through injection wells, which in its vicinity form a zone of steam that expands itself, having as a consequence the displace of the oil with viscosity and mobility improved towards the producing wells. Another possible mechanism of displacement of oil in reservoirs subjected to continuous injection of steam is the distillation of oil by steam, which at high temperatures; their lighter fractions can be vaporized by changing the composition of the oil produced, of the oil residual or to shatter in the amount of oil produced. In this context, this paper aims to study the influence of compositional models in the continuous injection of steam through in the analysis of some parameters such as flow injection steam and temperature of injection. Were made various leading comparative analysis taking the various models of fluid, varying from a good elementary, with 03 pseudocomponents to a modeling of fluids with increasing numbers of pseudocomponents. A commercial numerical simulator was used for the study from a homogeneous reservoir model with similar features to those found in northeastern Brazil. Some conclusions as the increasing of the simulation time with increasing number of pseudocomponents, the significant influence of flow injection on cumulative production of oil and little influence of the number of pseudocomponents in the flows and cumulative production of oil were found

Estudo dos parâmetros operacionais do processo de combustão in situ em reservatório de petróleo pesado

The occurrence of heavy oil reservoirs have increased substantially and, due to the high viscosity characteristic of this type of oil, conventional recovery methods can not be applied. Thermal methods have been studied for the recovery of this type of oil, with a main objective to reduce its viscosity, by increasing the reservoir temperature, favoring the mobility of the oil and allowing an increasing in the productivity rate of the fields. In situ combustion (ISC) is a thermal recovery method in which heat is produced inside the reservoir by the combustion of part of the oil with injected oxygen, contrasting with the injection of fluid that is heated in the surface for subsequent injection, which leads to loss heat during the trajectory to the reservoir. The ISC is a favorable method for recovery of heavy oil, but it is still difficult to be field implemented. This work had as an objective the parametric analysis of ISC process applied to a semi-synthetic reservoir with characteristics of the Brazilian Northeast reservoirs using vertical production and vertical injection wells, as the air flow injection and the wells completions. For the analysis, was used a commercial program for simulation of oil reservoirs using thermal processes, called Steam, Thermal and Advanced Processes Reservoir Simulator (STARS) from Computer Modelling Group (CMG). From the results it was possible to analyze the efficiency of the ISC process in heavy oil reservoirs by increasing the reservoir temperature, providing a large decrease in oil viscosity, increasing its mobility inside the reservoir, as well as the improvement in the quality of this oil and therefore increasing significantly its recovered fraction. Among the analyzed parameters, the flow rate of air injection was the one which had greater influence in ISC, obtaining higher recovery factor the higher is the flow rate of injection, due to the greater amount of oxygen while ensuring the maintenance of the combustion front

Studies of the Electrochemical Degradation of Acetaminophen Using a Real-Time Biomimetic Sensor

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