Complex kinetics, high frequency oscillations and temperature compensation in the electro-oxidation of ethylene glycol on platinum

Despite the fact that the majority of the catalytic electro-oxidation of small organic molecules presents oscillatory kinetics under certain conditions, there are few systematic studies concerning the influence of experimental parameters on the oscillatory dynamics. Of the studies available, most are devoted to C1 molecules and just some scattered data are available for C2 molecules. We present in this work a comprehensive study of the electro-oxidation of ethylene glycol on polycrystalline platinum surfaces and in alkaline media. The system was studied by means of electrochemical impedance spectroscopy, cyclic voltammetry, and chronoamperometry, and the impact of parameters such as applied current, ethylene glycol concentration, and temperature were investigated. As in the case of other parent systems, the instabilities in this system were associated with a hidden negative differential resistance, as identified by impedance data. Very rich and robust dynamics were observed, including the presence of harmonic and mixed mode oscillations and chaotic states, in some parameter region. Oscillation frequencies of about 16 Hz characterized the fastest oscillations ever reported for the electro-oxidation of small organic molecules. Those high frequencies were strongly influenced by the electrolyte pH and far less affected by the EG concentration. The system was regularly dependent on temperature under voltammetric conditions but rather independent within the oscillatory regime.

Rapid and sensitive measurements of nitrate ester explosives using microchip electrophoresis with electrochemical detection

This article describes an effective microchip protocol based on electrophoretic-separation and electrochemical detection for highly sensitive and rapid measurements of nitrate ester explosives, including ethylene glycol dinitrate (EGDN), pentaerythritol tetranitrate (PETN), propylene glycol dinitrate (PGDN) and glyceryl trinitrate (nitroglycerin, NG). Factors influencing the separation and detection processes were examined and optimized. Under the optimal separation conditions obtained using a 15 mM borate buffer (pH 9.2) containing 20 mM SDS, and applying a separation voltage of 1500 V, the four nitrate ester explosives were separated within less than 3 min. The glassy-carbon amperometric detector (operated at -0.9 V vs. Ag/AgCl) offers convenient cathodic detection down to the picogram level, with detection limits of 0.5 ppm and 0.3 ppm for PGDN and for NG, respectively, along with good repeatability (RSD of 1.8-2.3%; n = 6) and linearity (over the 10-60 ppm range). Such effective microchip operation offers great promise for field screening of nitrate ester explosives and for supporting various counter-terrorism surveillance activities.

Direct Solid-Phase Optical Measurements in Flow Systems: A Review

Measurements based on absorption, reflectance, or luminescence of molecular species or complex ions can be carried out directly on a solid support simultaneously to the retention of the analyte. The use of this strategy in flow-based systems is advantageous in view of the reproducible handling of solutions in retention and elution steps of the analyte. This approach can be exploited to increase sensitivity, minimize reagent consumption as well as waste generation, improve selectivity or for simultaneous determination based on selective retention or differences in sorption rates of the analytes. This review focuses on the main characteristics of direct solid-phase measurements in flow systems, including the discussion of advantages and limitations and practical guidelines to the successful implementation of this approach. Selected applications in diverse fields, such as pharmaceutical, food, and environmental analysis are discussed.

A critical evaluation of a flow-cell based on a liquid core waveguide for chemiluminescence measurements

Liquid-core waveguides (LCWs), devices that constrain the emitted radiation minimizing losses during the transport, are an alternative to maximize the amount of detected radiation in luminescence. In this work, the performance of a LCW flow-cell was critically evaluated for chemiluminescence measurements, by using as model the oxidation of luminol by hydrogen peroxide or hypochlorite. An analytical procedure for hypochlorite determination was also developed, with linear response in the range 0.2-3.8 mg/L (2.7-51 mu mol/L), a detection limit estimated as 8 mu g/L (0.64 mu mol/L) at the 99.7% confidence level and luminol consumption of 50 mu g/determination. The coefficients of variation were 3.3% and 1.6% for 0.4 and 1.9 mg/L CIO(-), respectively, with a sampling rate of 164 determinations/h. The procedure was applied to the analysis of Dakin`s solution samples, yielding results in agreement with those obtained by iodometric titration at the 95% confidence level. Copyright (c) 2008 John Wiley & Sons, Ltd.

A critical evaluation of a long pathlength cell for flow-based spectrophotometric measurements

Coupling of a flow cell based on a liquid core waveguide (LCW) to flow systems for spectro photometric measurements was critically evaluated. Flow-based systems with and without chemical reactions were exploited to estimate the increase in analytical signal in comparison to those obtained with a conventional I cm cell under different experimental conditions. The Schlieren effect associated to intense concentration gradients in the sample zone was investigated with model solutions that do not absorb visible electromagnetic radiation. The effect of radiation scattering was lower than the expected by considering the increase in the optical path, being the magnitude of the perturbation up to 40% higher for the 100-cm LCW cell. Several alternatives for compensation of the Schlieren effect were experimentally investigated. The potentiality of the LCW for turbidimetric measurements and coupling to monosegmented flow analysis was also evaluated. (C) 2008 Elsevier B.V. All rights reserved.

Experimental chronic low-frequency resistance training produces skeletal muscle hypertrophy in the absence of muscle damage and metabolic stress markers

Volitional animal resistance training constitutes an important approach to modeling human resistance training. However, the lack of standardization protocol poses a frequent impediment to the production of skeletal muscle hypertrophy and the study of related physiological variables (i.e., cellular damage/inflammation or metabolic stress). Therefore, the purposes of the present study were: (1) to test whether a long-term and low frequency experimental resistance training program is capable of producing absolute increases in muscle mass; (2) to examine whether cellular damage/inflammation or metabolic stress is involved in the process of hypertrophy. In order to test this hypothesis, animals were assigned to a sedentary control (C, n = 8) or a resistance trained group (RT, n = 7). Trained rats performed 2 exercise sessions per week (16 repetitions per day) during 12 weeks. Our results demonstrated that the resistance training strategy employed was capable of producing absolute mass gain in both soleus and plantaris muscles (12%, p<0.05). Furthermore, muscle tumor necrosis factor (TNF-alpha) protein expression (soleus muscle) was reduced by 24% (p<0.01) in trained group when compared to sedentary one. Finally, serum creatine kinase (CK) activity and serum lactate concentrations were not affected in either group. Such information may have practical applications if reproduced in situations where skeletal muscle hypertrophy is desired but high mechanical stimuli of skeletal muscle and inflammation are not. Copyright (C) 2010 John Wiley & Sons, Ltd.

Influence of high- and low-carbohydrate diet following glycogen-depleting exercise on heart rate variability and plasma catecholamines

The purpose of this study was to investigate the effects of a short-term low-or high-carbohydrate (CHO) diet consumed after exercise on sympathetic nervous system activity. Twelve healthy males underwent a progressive incremental test; a control measurement of plasma catecholamines and heart rate variability (HRV); an exercise protocol to reduce endogenous CHO stores; a low-or high-CHO diet (counterbalanced order) consumed for 2 days, beginning immediately after the exercise protocol; and a second resting plasma catecholamine and HRV measurement. The exercise and diet protocols and the second round of measurements were performed again after a 1-week washout period. The mean (+/- SD) values of the standard deviation of R-R intervals were similar between conditions (control, 899.0 +/- 146.1 ms; low-CHO diet, 876.8 +/- 115.8 ms; and high-CHO diet, 878.7 +/- 127.7 ms). The absolute high-and low-frequency (HF and LF, respectively) densities of the HRV power spectrum were also not different between conditions. However, normalized HF and LF (i.e., relative to the total power spectrum) were lower and higher, respectively, in the low-CHO diet than in the control diet (mean +/- SD, 17 +/- 9 normalized units (NU) and 83 +/- 9 NU vs. 27 +/- 11 NU and 73 +/- 17 NU, respectively; p < 0.05). The LF/HF ratio was higher with the low-CHO diet than with the control diet (mean +/- SD, 7.2 +/- 6.2 and 4.2 +/- 3.2, respectively; p < 0.05). The mean values of plasma catecholamines were not different between diets. These results suggest that the autonomic control of the heart rate was modified after a short-term low-CHO diet, but plasma catecholamine levels were not altered.

Relative frequency of knowledge of results and task complexity in the motor skill acqusition

The aim of this study was to investigate the effects of knowledge of results (KR) frequency and task complexity on motor skill acquisition. The task consisted of throwing a bocha ball to place it as close as possible to the target ball. 120 students ages 11 to 73 years were assigned to one of eight experimental groups according to knowledge of results frequency (25, 50, 75, and 100%) and task complexity (simple and complex). Subjects performed 90 trials in the acquisition phase and 10 trials in the transfer test. The results showed that knowledge of results given at a frequency of 25% resulted in an inferior absolute error than 50% and inferior variable error than 50, 75, and 100 I frequencies, but no effect of task complexity was found.

Three-layer piezoelectrets from fluorinated ethylene-propylene (FEP) copolymer films

A process for preparing three-layer piezoelectrets from fluorinated ethylene-propylene (FEP) copolymer films is introduced. Samples are made from commercial FEP films by means of laser cutting, laser bonding, electrode evaporation, and high-field poling. The observed dielectric-resonance spectra demonstrate the piezoelectricity of the FEP sandwiches. Piezoelectric d (33) coefficients up to a few hundred pC/N are achieved. Charging at elevated temperatures can increase the thermal stability of the piezoelectrets. Isothermal experiments for approximately 15 min demonstrate that samples charged at 140A degrees C keep their piezoelectric activity up to at least 120A degrees C and retain 70% of their initial d (33) even at 130A degrees C. Acoustical measurements show a relatively flat frequency response in the range between 300 Hz and 20 kHz.

Digital frequency relaying based on the modified least mean square method

This research presents a method for frequency estimation in power systems using an adaptive filter based on the Least Mean Square Algorithm (LMS). In order to analyze a power system, three-phase voltages were converted into a complex signal applying the alpha beta-transform and the results were used in an adaptive filtering algorithm. Although the use of the complex LMS algorithm is described in the literature, this paper deals with some practical aspects of the algorithm implementation. In order to reduce computing time, a coefficient generator was implemented. For the algorithm validation, a computing simulation of a power system was carried Out using the ATP software. Many different situations were Simulated for the performance analysis of the proposed methodology. The results were compared to a commercial relay for validation, showing the advantages of the new method. (C) 2009 Elsevier Ltd. All rights reserved.

Redundancy and Observability Analysis of Conventional and PMU Measurements

This letter shows that the matrix can be used for redundancy and observability analysis of metering systems composed of PMU measurements and conventional measurements (power and voltage magnitude measurements). The matrix is obtained via triangular factorization of the Jacobian matrix. Observability analysis and restoration is carried out during the triangular factorization of the Jacobian matrix, and the redundancy analysis is made exploring the matrix structure. As a consequence, the matrix can be used for metering system planning considering conventional and PMU measurements. These features of the matrix will be outlined and illustrated by numerical examples.

Noise reduction in biomedical speech signal processing based on time and frequency Kalman filtering combined with spectral subtraction

The goal of this paper is to study and propose a new technique for noise reduction used during the reconstruction of speech signals, particularly for biomedical applications. The proposed method is based on Kalman filtering in the time domain combined with spectral subtraction. Comparison with discrete Kalman filter in the frequency domain shows better performance of the proposed technique. The performance is evaluated by using the segmental signal-to-noise ratio and the Itakura-Saito`s distance. Results have shown that Kalman`s filter in time combined with spectral subtraction is more robust and efficient, improving the Itakura-Saito`s distance by up to four times. (C) 2007 Elsevier Ltd. All rights reserved.

Evaluation of flow patterns and elongated bubble characteristics during the flow boiling of halocarbon refrigerants in a micro-scale channel

In the present study, quasi-diabatic two-phase flow pattern visualizations and measurements of elongated bubble velocity, frequency and length were performed. The tests were run for R134a and R245fa evaporating in a stainless steel tube with diameter of 2.32 mm, mass velocities ranging from 50 to 600 kg/m(2) s and saturation temperatures of 22 degrees C, 31 degrees C and 41 degrees C. The tube was heated by applying a direct DC current to its surface. Images from a high-speed video-camera (8000 frames/s) obtained through a transparent tube just downstream the heated sections were used to identify the following flow patterns: bubbly, elongated bubbles, churn and annular flows. The visualized flow patterns were compared against the predictions provided by Barnea et al. (1983) [1], Felcar et al. (2007) [10], Revellin and Thome (2007) [3] and Ong and Thome (2009) [11]. From this comparison, it was found that the methods proposed by Felcar et al. (2007) [10] and Ong and Thome (2009) [1] predicted relatively well the present database. Additionally, elongated bubble velocities, frequencies and lengths were determined based on the analysis of high-speed videos. Results suggested that the elongated bubble velocity depends on mass velocity, vapor quality and saturation temperature. The bubble velocity increases with increasing mass velocity and vapor quality and decreases with increasing saturation temperature. Additionally, bubble velocity was correlated as linear functions of the two-phase superficial velocity. (C) 2010 Elsevier Inc. All rights reserved.

Positioning of Deadeners for Vibration Reduction in Vehicle Roof Using Embedded Sensitivity

The noise, vibration and harshness (NVH) performance of passenger vehicles strongly depends on the fluid-structure interaction between the air in the vehicle cavity and the sheet metal structure of the vehicle. Most of the noise and vibration problems related to this interaction come from resonance peaks of the sheet metal, which are excited by external forces (road, engine, and wind). A reduction in these resonance peaks can be achieved by applying bitumen damping layers, also called deadeners, in the sheet metal. The problem is where these deadeners shall be fixed, which is usually done in a trial-and-error basis. In this work, one proposes the use of embedded sensitivity to locate the deadeners in the sheet metal of the vehicle, more specifically in the vehicle roof. Experimental frequency response functions (FRFs) of the roof are obtained and the data are processed by adopting the embedded sensitivity method, thus obtaining the sensitivity of the resonance peaks on the local increase in damping due to the deadeners. As a result, by examining the sensitivity functions, one can find the optimum location of the deadeners that maximize their effect in reducing the resonance peaks of interest. After locating the deadeners in the optimum positions, it was possible to verify a strong reduction in resonance peaks of the vehicle roof, thus showing the efficiency of the procedure. The main advantage of this procedure is that it only requires FRF measurements of the vehicle in its original state not needing any previous modification of the vehicle structure to find the sensitivity functions. [DOI: 10.1115/1.4000769]

PERMEABILITY MEASUREMENTS OF BRAZILIAN PINUS ELLIOTTII

The liquid and gas phase permeability, of Brazilian Pinus elliotii was studied with a custom built gas and liquid flow rate analysis chamber. The longitudinal gas phase permeability is shown to be six times greater than the radial permeability. There is no statistically significant difference between the longitudinal permeability of water versus wood preservative. Scanning Electron Microscopy (SEM) images confirm that the reported permeability properties arc due to the wood itself rather than to blocked pores or other artifacts of the sample cutting process. Wood composition analysis shows that the samples of Pinus elliotii grown in Brazil are similar to other species of Pinus grown in tropical climates. Specifically, the Pinus elliotti in this study is composed of 17% extractives, 0,27% ashes, 21% hemicellulose, 45% cellulose and 30% lignin. Results arc discussed in the context of the continued search for effective wood preservatives for use in tropical climates.