916 resultados para Hanging meniscus rotating disk voltammetry


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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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Procion red HE-3B (RR120) is an example of dye currently used in affinity purification. A method is described for determining trace amounts of RR120 dye contaminant in human serum albumin by cathodic stripping voltammetry. The method is based on a measure of a well-defined peak at -0.58 V, obtained when samples of HSA protein (0.01-2% w/v) containing dye concentrations are submitted to a heating time of 330 min at 80degreesC in NaOH, pH 12.0 and the samples are removed to a solution containing Britton-Robinson buffer, pH 4.0. Using an optimum accumulation potential and tune of 0 V and 240 s, respectively, linear calibration curves were obtained from 1.0 X 10(-9) to 1.0 X 10(-8) mol 1(-1) for RR120 dye. Leakage/hydrolysis of reactive red 120 from an agarose support (e.g. at pH 2 or 12) can also be conveniently determined at very low levels (sub-mug ml(-1)) by means of cathodic stripping voltammetry, which involves adsorptive accumulation of the dye onto the hanging mercury-drop electrode. (C) 2002 Elsevier B.V. B.V. All rights reserved.

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Ceftazidime is hydrolysed only slowly at pH 10 at room temperature. This is indicated by a small cathodic stripping voltammetric peak obtained at pH 10 at a hanging mercury drop electrode at about -0.6 V which corresponds to the reduction of the hydrolysis product. This peak is enhanced more than tenfold by the addition of poly-L-lysine (PLL) to the electrolyte solution. The optimum accumulation potential is between 0 and -0.1 V: the size of the peak decreases steadily, however, as the accumulation potential is moved to more negative potentials and is about one-sixth the size for accumulation at -0.4 V. Existing knowledge of the organic chemistry of cephalosporins indicates that the accumulation must involve an aminolysis reaction of the unprotonated PLL with the beta-lactam ring of the ceftazidime. The limit of detection (3 sigma) in standard solutions was calculated to be 1 x 10(-10) mol l(-1). The detection limit in buffer solution containing 1% of urine was calculated to be 5 x 10(-9) mol l(-1), i.e. 5 x 10(-6) mol l(-1) in the urine. (C) 1999 Elsevier B.V. B.V. AU rights reserved.

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Purpose: To compare 2 methods used to determine the disk position based on sagittal magnetic resonance images. Patients and Methods: A cross-sectional study of patients with the signs and symptoms of temporomandibular disorders was conducted. The patients' ages and gender distributions were collected. The disk position diagnosis from the clinical examination was considered the primary outcome. Three observers evaluated the presence of anterior displacement on magnetic resonance images according to 2 criteria: method 1 (12-o'clock position) and method 2 (location of the intermediate zone). To assess the intraobserver variability of the 2 methods, the examiners evaluated the same magnetic resonance images at the beginning of the study (time 1) and 40 days later (time 2). The intraobserver agreement was assessed using the observed agreement and the kappa statistic. McNemar's test was used to assess the differences between each method and the clinical examination findings (P < .05). The accuracy, sensitivity, specificity, and positive and negative predictive values were calculated by comparing the diagnosis from each method with that from the clinical examination (considered the reference standard). Results: The final sample was composed of 20 subjects with a mean age of 33.0 +/- 33.7 years; 3 were men (15%) and 17 were women (85%). A statistically significant difference between the 2 methods was found. Method 1 yielded a greater percentage of anterior displaced disks (52.5%). The agreement between the clinical diagnosis and method 1 was lower (70.0%) than that between the clinical diagnosis and method 2 (87.5%). No statistically significant difference was found between the clinical diagnosis and method 2. Conclusion: The disk position should be judged according to the intermediate zone criterion. (C) 2012 American Association of Oral and Maxillofacial Surgeons J Oral Maxillofac Surg 70:1534-1539, 2012

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The oxygen reduction reaction (ORR) was studied in KOH electrolyte on carbon supported epsilon-manganese dioxide (epsilon-MnO2/C). The epsilon-MnO2/C catalyst was prepared via thermal decomposition of manganese nitrate and carbon powder (Vulcan XC-72) mixtures. X-ray powder diffraction (XRD) measurements were performed in order to determine the crystalline structure of the resulting composite, while energy dispersive X-ray analysis (EDX) was used to evaluate the chemical composition of the synthesized material. The electrochemical studies were conducted using cyclic voltammetry (CV) and quasi-steady state polarization measurements carried out with an ultra thin layer rotating ring/disk electrode (RRDE) configuration. The electrocatalytic results obtained for 20% (w/w) Pt/C (E-TEK Inc., USA) and alpha-MnO2/C for the ORR, considered as one of the most active manganese oxide based catalyst for the ORR in alkaline media, were included for comparison. The RRDE results revealed that the ORR on the MnO2 catalysts proceeds preferentially through the complete 4e(-) reduction pathway via a 2 plus 2e(-) reduction process involving hydrogen peroxide as an intermediate. A benchmark close to the performance of 20% (w/w) Pt/C (E-TEK Inc., USA) was observed for the epsilon-MnO2/C material in the kinetic control region, superior to the performance of alpha-MnO2/C, but a higher amount of HO2- was obtained when epsilon-MnO2/C was used as catalyst. The higher production of hydrogen peroxide on epsilon-MnO2/C was related to the presence of structural defects, typical of this oxide, while the better catalytic performance in the kinetic control region compared to alpha-MnO2/C was related with the higher electrochemical activity for the proton insertion kinetics, which is a structure sensitive process. (C) 2012 Elsevier Ltd. All rights reserved.

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The use of rotating ring–disk electrodes as generator-collector systems has so far been limited to the detection of Faradaic currents at the ring. As opposed to other generator-collector configurations, non-Faradaic detection has not yet been carried out with rotating ring–disk electrodes. In this study, a.c. perturbation based detection for measurement of the ring impedance is introduced. By using a conducting polymer-modified disk electrode in combination with a bare gold ring as a model, it is shown that the measured ring capacitance correlates with the polarization of the polymer film, most probably due to counter-ion exchange. A method of calculating the ring capacitance based on a small-signal sinusoid perturbation is described and the most important instrumental limitations are identified.

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The ESS-Bilbao facility, hosted by the University of the Basque Country (UPV/EHU), envisages the operation of a high-current proton accelerator delivering beams with energies up to 50 MeV. The time-averaged proton current will be 2.25 mA, delivered by 1.5 ms proton pulses with a repetition rate of 20 Hz. This beam will feed a neutron source based upon the Be (p,n) reaction, which will enable the provision of relevant neutron experimentation capabilities. The neutron source baseline concept consists in a rotating beryllium target cooled by water. The target structure will comprise a rotatable disk made of 6061-T6 aluminium alloy holding 20 beryllium plates. Heat dissipation from the target relies upon a distribution of coolant-flow channels. The practical implementation of such a concept is here described with emphasis put on the beryllium plates thermo-mechanical optimization, the chosen coolant distribution system as well as the mechanical behavior of the assembly.

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Tese de doutoramento, Química (Química Física), Universidade de Lisboa, Faculdade de Ciências, 2016

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The cathodic and anodic characteristics of freshly polished and pre-reduced UNS S32550 (ASTM A479) super duplex stainless steel in a filtered and conductivity-adjusted seawater have been investigated under controlled flow conditions. A rotating cylinder electrode was used together with both steady and non-steady-state voltammetry and a potential step current transient technique to investigate the electrode reactions in the fully characterized electrolyte. Both oxygen reduction and hydrogen evolution were highly irreversible and the material exhibited excellent passivation and repassivation kinetics. Relative corrosion rates were derived and the corrosion mechanism of the alloy was found to be completely independent of the mass-transfer effects, which can contribute to flow-induced corrosion.

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Origin of hydrodynamic turbulence in rotating shear flows is investigated. The particular emphasis is on flows whose angular velocities decrease but specific angular momenta increase with increasing radial coordinate. Such flows are Rayleigh stable, but must be turbulent in order to explain observed data. Such a mismatch between the linear theory and observations/experiments is more severe when any hydromagnetic/magnetohydrodynamic instability and the corresponding turbulence therein is ruled out. The present work explores the effect of stochastic noise on such hydrodynamic flows. We focus on a small section of such a flow which is essentially a plane shear flow supplemented by the Coriolis effect. This also mimics a small section of an astrophysical accretion disk. It is found that such stochastically driven flows exhibit large temporal and spatial correlations of perturbation velocities, and hence large energy dissipations, that presumably generate instability. A range of angular velocity profiles (for the steady flow), starting with the constant angular momentum to that of the constant circular velocity are explored. It is shown that the growth and roughness exponents calculated from the contour (envelope) of the perturbed flows are all identical, revealing a unique universality class for the stochastically forced hydrodynamics of rotating shear flows. This work, to the best of our knowledge, is the first attempt to understand origin of instability and turbulence in the three-dimensional Rayleigh stable rotating shear flows by introducing additive stochastic noise to the underlying linearized governing equations. This has important implications in resolving the turbulence problem in astrophysical hydrodynamic flows such as accretion disks.

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Origin of hydrodynamic turbulence in rotating shear flows is investigated. The particular emphasis is on flows whose angular velocities decrease but specific angular momenta increase with increasing radial coordinate. Such flows are Rayleigh stable, but must be turbulent in order to explain observed data. Such a mismatch between the linear theory and observations/experiments is more severe when any hydromagnetic/magnetohydrodynamic instability and the corresponding turbulence therein is ruled out. The present work explores the effect of stochastic noise on such hydrodynamic flows. We focus on a small section of such a flow which is essentially a plane shear flow supplemented by the Coriolis effect. This also mimics a small section of an astrophysical accretion disk. It is found that such stochastically driven flows exhibit large temporal and spatial correlations of perturbation velocities, and hence large energy dissipations, that presumably generate instability. A range of angular velocity profiles (for the steady flow), starting with the constant angular momentum to that of the constant circular velocity are explored. It is shown that the growth and roughness exponents calculated from the contour (envelope) of the perturbed flows are all identical, revealing a unique universality class for the stochastically forced hydrodynamics of rotating shear flows. This work, to the best of our knowledge, is the first attempt to understand origin of instability and turbulence in the three-dimensional Rayleigh stable rotating shear flows by introducing additive stochastic noise to the underlying linearized governing equations. This has important implications in resolving the turbulence problem in astrophysical hydrodynamic flows such as accretion disks.

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A novel voltammetric method for simultaneous determination of the glucocorticoid residues prednisone, prednisolone, and dexamethasone was developed. All three compounds were reduced at a mercury electrode in a Britton-Robinson buffer (pH 3.78), and well-defined voltammetric waves were observed. However, the voltammograms of these three compounds overlapped seriously and showed nonlinear character, and thus, it was difficult to analyze the compounds individually in their mixtures. In this work, two chemometrics methods, principal component regression (PCR) and partial least squares (PLS), were applied to resolve the overlapped voltammograms, and the calibration models were established for simultaneous determination of these compounds. Under the optimum experimental conditions, the limits of detection (LOD) were 5.6, 8.3, and 16.8 µg l-1 for prednisone, prednisolone, and dexamethasone, respectively. The proposed method was also applied for the determination of these glucocorticoid residues in the rabbit plasma and human urine samples with satisfactory results.

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Established Monte Carlo user codes BEAMnrc and DOSXYZnrc permit the accurate and straightforward simulation of radiotherapy experiments and treatments delivered from multiple beam angles. However, when an electronic portal imaging detector (EPID) is included in these simulations, treatment delivery from non-zero beam angles becomes problematic. This study introduces CTCombine, a purpose-built code for rotating selected CT data volumes, converting CT numbers to mass densities, combining the results with model EPIDs and writing output in a form which can easily be read and used by the dose calculation code DOSXYZnrc. The geometric and dosimetric accuracy of CTCombine’s output has been assessed by simulating simple and complex treatments applied to a rotated planar phantom and a rotated humanoid phantom and comparing the resulting virtual EPID images with the images acquired using experimental measurements and independent simulations of equivalent phantoms. It is expected that CTCombine will be useful for Monte Carlo studies of EPID dosimetry as well as other EPID imaging applications.