Development of an electrochemical sensor for potassium ions based on KSr(2)Nb(5)O(15) modified electrode

In the work described by this paper, we studied the development of a selective potassium ion sensor constituted of a carbon paste electrode modified (CPEM) with a novel KSr(2)Nb(2)O(15). The material KSr(2)Nb(2)O(15) is an oxide with the tetragonal tungsten bronze structure (TTB) type are in forefront both in the area of research as well as in industrial applications. The sensor response to potassium ions was linear in the concentration range 1.26 x 10(-5) at 1.62 x 10(-3) mol L(-1) (E (mV) = 32.7 + 51.1 log [K(+)]). The sensor based KSr(2)Nb(2)O(15), of the TTB-type presented very good potentiometric response, with a slope of 51.1 mV/dec (at 25 degrees C) and detection limit for the potassium ions of 7.27 x 10(-5) mol.L(-1)

An electrochemical sensor for dipyrone determination based on nickel-salen film modified electrode

An amperometric dipyrone sensor based on a polymeric nickel-salen (salen = N,N'-ethylenebis(salicydeneiminato)) film coated platinum electrode was developed. The sensor was constructed by electropolymerization of nickel-salen complex at a platinum electrode in acetonitrile/tetrabuthylamonium perchlorate by cyclic voltammetry. After cycling the modified electrode in a 0.50 mol L-1 KCl solution, the estimated surface concentration was found to be equal to 1.29 x 10(-9) mol cm(-2). This is a typical behavior of an electrode surface immobilized with a redox couple that can usually be considered as a reversible single-electron reduction/oxidation of the nickel(II)/nickel(III) couple. A plot of the anodic current versus the dipyrone concentration for chronoamperometry (potential fixed = +0.50 V) at the sensor was linear in the 4.7 x 10(-6) to 1.1 x 10(-4) mol L-1 concentration range and the concentration limit was 1.2 x 10(-6) mol L-1. The proposed electrode is useful for the quality control and routine analysis of dipyrone in pharmaceutical formulations.

Electrochemical evaluation of the a carbon-paste electrode modified with spinel manganese(IV) oxide under flow conditions for amperometric determination of lithium

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

Immobilization of streptavidin in sol-gel films: Application on the diagnosis of hepatitis C virus

Recent advances have accelerated the development of biosensors for the analysis of specific gene sequences. In this kind of biosensor, a DNA probe is immobilized on a transducer and the hybridization with the target DNA is monitored by suitable methodology. In the present work, the streptavidin (STA) was encapsulated in thin films siloxane-poly(propylene oxide) hybrids prepared by sol-gel method and deposited on the graphite electrode surface by dip-coating process. Biotinylated 18-mer probes were immobilized through STA and a novel amperometric DNA biosensor for the detection and genotyping of the hepatitis C virus (genotypes 1, 2A/C, 2B and 3) is described. The HCV RNA from serum was submitted to reverse transcriptase-linked polymerase chain reaction (RT-PCR) and biotin-labeled cDNA was obtained. Thus, the cDNA was hybridized to the target-specific oligonucleotide probe immobilized on the graphite electrode surface and following the avidin-peroxidase conjugate was added. The enzymatic response was investigated by constant potential amperometry at -0.45 V versus Ag/AgCl using H2O2 and KI solutions. HCV RNA negative and positive controls and positive samples of sera patients were analyzed and the results were compared to commercial kit. The proposed methodology appeared to be suitable and convenient tool for streptavidin immobilization and diagnose of HCV disease. (c) 2006 Elsevier B.V. All rights reserved.

Waveshapes of continuing currents and properties of M-components in natural positive cloud-to-ground lightning

This work analyses the waveshapes of continuing currents and parameters of M-components in positive cloud-to-ground (CG) flashes through high-speed GPS synchronized videos. The dataset is composed of only long continuing currents (with duration longer than 40 ms) and was selected from more than 800 flashes recorded in Sao Jose dos Campos (45.864 degrees W, 23.215 degrees S) and Uruguaiana (29.806 degrees W, 57.005 degrees S) in Southeast and South of Brazil, respectively, during 2003 to 2007 summers. The videos are compared with data obtained by the Brazilian Lightning Location System (BrasilDAT) in order to determine the polarity of each flash and select only positive cases. There are only two studies of waveshapes of continuing currents in the literature. One is based on direct current measurements of triggered lightning, in which four different types of waveshapes were observed; and the other is based on measurements of luminosity variations in high-speed videos of CG negative lightning, in which besides the four types above mentioned two additional types were observed. The present work is an extension of the latter, using the same method but now applied to obtain the waveshapes of positive CG lightning. As far as the authors know, this is the first report on M-components in positive continuing currents. We also have used the luminosity-versus-time graphs to observe their occurrence and measure some parameters (duration, elapsed time and time between two successive M-components), whose statistics are presented and compared in detail to the data for negative flashes. We have plotted a histogram of the M-components elapsed time over the total duration of the continuing current for positive flashes, which presented an exponential decay (correlation coefficient: 0.83), similar to what has been observed for negative flashes. (C) 2008 Elsevier B.V. All rights reserved.

Positive leader characteristics from high-speed video observations

Based on analyses of high-speed video recordings of cloud-to-ground lightning in Brazil and the USA, the characteristics of positive cloud-to-ground (+CG) leaders are presented. The high frame rates permitted the average, 2-dimensional speeds of development along the paths of the channels to be resolved with good accuracy. The values range from 0.3 to 6.0 x 10(5) ms(-1) with a mean of 2.7 x 10(5) ms(-1). Contrary to what is usually assumed, downward +CG leader speeds are similar to downward -CG leader speeds. Our observations also show that the speeds tend to increase by a factor of 1.1 to 6.5 as they approach the ground. The presence of short duration, recoil leaders (RLs) during the development of positive leaders reveal a highly branched structure that is not usually recorded when using conventional photographic and video cameras. The existence of the RLs may help to explain observations of UHF-VHF radiation during the development of +CG flashes.

A method for plotting the complementary root locus using the root-locus (positive gain) rules

The root-locus method is a well-known and commonly used tool in control system analysis and design. It is an important topic in introductory undergraduate engineering control disciplines. Although complementary root locus (plant with negative gain) is not as common as root locus (plant with positive gain) and in many introductory textbooks for control systems is not presented, it has been shown a valuable tool in control system design. This paper shows that complementary root locus can be plotted using only the well-known construction rules to plot root locus. It can offer for the students a better comprehension on this subject. These results present a procedure to avoid problems that appear in root-locus plots for plants with the same number of poles and zeros.

Mitigation of symmetry condition in positive realness for adaptive control

Feasibility of nonlinear and adaptive control methodologies in multivariable linear time-invariant systems with state-space realization (A, B, C) is apparently limited by the standard strictly positive realness conditions that imply that the product CB must be positive definite symmetric. This paper expands the applicability of the strictly positive realness conditions used for the proofs of stability of adaptive control or control with uncertainty by showing that the not necessarily symmetric CB is only required to have a diagonal Jordan form and positive eigenvalues. The paper also shows that under the new condition any minimum-phase systems can be made strictly positive real via constant output feedback. The paper illustrates the usefulness of these extended properties with an adaptive control example. (C) 2006 Elsevier Ltd. All rights reserved.

LMI-based algorithm for strictly positive real systems with static output feedback

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

Stripping voltammetry of mercury(II) with a chemically modified carbon paste electrode containing silica gel functionalized with 2,5-dimercapto-1,3,4-thiadiazole

The accumulation voltammetry of mercury(II) was investigated at a carbon paste electrode chemically modified with silica gel functionalized with 2,5-dimercapto-1,3,4-thiadiazole (DTTPSG-CPE). The repetitive cyclic voltammogram of mercury(II) solution in the potential range -0.2 to +0.8 V (vs. Ag/AgCl), (0.02 mol L-1 KNO3; nu=20 mV s(-1)) show two peaks one at about 0.0 V and other at 0.31 V. However, the cathodic wave peak, around 0.0 V, is irregular and changes its form in each cycle. This peak at about 0.0 V is the reduction current for mercury(II) accumulated in the DTTPSG-CPE. The anodic wave peak at 0.31 V is well-defined and does not change during the cycles. The resultant material was characterized by cyclic and differential pulse anodic stripping voltammetry performed with the electrode in differents supporting electrolytes. The mercury response was evaluated with respect to pH, electrode composition, preconcentration time, mercury concentration, cleaning solution, possible interferences and other variables. The precision for six determinations (n=6) of 0.05 and 0.20 mg (L)-(1) Hg(II) was 2.8 and 2.2% (relative standard deviation), respectively. The method was satisfactory and used to determine the concentration of mercury(II) in natural waters contaminated by this metal.

Voltammetric determination of total iron in fuel ethanol using a 1,10 fenantroline/nafion carbon paste-modified electrode

This work presents a methodology for iron determination in fuel ethanol using a modified carbon paste electrode with 1.10 fenantroline/nafion. The electrochemical parameters were optimized for the proposed system and the voltammetric technique of square wave was employed for iron determination. An accumulation time of 5 minutes, such as a 100 mV of pulse magnitude (E(sw)) and frequency (f) of 25 Hz were used as optimized experimental conditions. The modified carbon paste electrode presented linear dependence of amperometric signal with iron concentration in a work range from 6.0x10(-6) until 2.0x10(-5) mol L(-1) of iron, exhibiting a linear correlation coefficient of 0.9884, a detection limit of 2.4 x10(-6) mol L(-1) (n = 3) and amperometric sensibility of 4.5x10(5) mu A/mol L(-1). Analytical curve method was used for iron determination at a commercial fuel sample. Flame atomic absorption spectroscopy was employed as comparative technique.

Voltammetric Behavior of a Modified Electrode With Azide Copper Octa(3-Aminopropyl)Octasilsesquioxane Composite in the Oxidation of Ascorbic Acid

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

Determination of N-Acetylcysteine by Cyclic Voltammetry Using Modified Carbon Paste Electrode with Copper Nitroprusside Adsorbed on the 3-Aminopropylsilica

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

Positive end-expiratory pressure in acute respiratory distress syndrome: should the 'open lung strategy' be replaced by a 'protective lung strategy'?

In patients with acute respiratory distress syndrome, positive end-expiratory pressure is associated with alveolar recruitment and lung hyperinflation despite the administration of a low tidal volume. The best positive end-expiratory pressure should correspond to the best compromise between recruitment and distension, a condition that coincides with the best respiratory elastance.

Different nutritional-state indicators of HIV-positive individuals undergoing antiretroviral therapy

This study aimed at learning about the nutritional profile of HIV-positive individuals undergoing antiretroviral therapy and at comparing the performance of nutritional-state indicators. A transversal study was performed on 94 patients attending the Tropical Diseases Outpatient Hospital of Botucatu Medical School (FMB)-UNESP. The body mass index (BMI) and the classification by Papini-Berto (PB) were used to evaluate nutritional state, aiming at detecting malnutrition and obesity. The waist-to-hips ratio (W/HR) and waist circumference (WC) were adopted for identification of abdominal obesity and lipodystrophy. According to BMI, most of the individuals were eutrophic, followed by 30.9% overweight and 6.4% malnourished. By using the PB classification, the frequency of malnourished increased (22.3%). The analysis of the PB classification in relation to BMI indicated that the former presented high sensitivity and good specificity for malnutrition diagnosis, namely 100% and 83%, respectively. The prevalence of abdominal obesity was 7.44% according to WC, and a higher prevalence (38.3%) was observed when taking W/HR into account. There was significant positive association between nutritional diagnosis according to PB and T CD4(+) lymphocyte. The results support the use of PB classification for malnutrition detection as well as that of BMI and W/HR for overweight and fat redistribution.