An electrochemical gas sensor based on paper supported room temperature ionic liquids

A sensitive and fast-responding membrane-free amperometric gas sensor is described, consisting of a small filter paper foil soaked with a room temperature ionic liquid (RTIL), upon which three electrodes are screen printed with carbon ink, using a suitable mask. It takes advantage of the high electrical conductivity and negligible vapour pressure of RTILs as well as their easy immobilization into a porous and inexpensive supporting material such as paper. Moreover, thanks to a careful control of the preparation procedure, a very close contact between the RTIL and electrode material can be achieved so as to allow gaseous analytes to undergo charge transfer just as soon as they reach the three-phase sites where the electrode material, paper supported RTIL and gas phase meet. Thus, the adverse effect on recorded currents of slow steps such as analyte diffusion and dissolution in a solvent is avoided. To evaluate the performance of this device, it was used as a wall-jet amperometric detector for flow injection analysis of 1-butanethiol vapours, adopted as the model gaseous analyte, present in headspace samples in equilibrium with aqueous solutions at controlled concentrations. With this purpose, the RTIL soaked paper electrochemical detector (RTIL-PED) was assembled by using 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide as the wicking RTIL and printing the working electrode with carbon ink doped with cobalt(II) phthalocyanine, to profit from its ability to electrocatalyze thiol oxidation. The results obtained were quite satisfactory (detection limit: 0.5 mu M; dynamic range: 2-200 mu M, both referring to solution concentrations; correlation coefficient: 0.998; repeatability: +/- 7% RSD; long-term stability: 9%), thus suggesting the possible use of this device for manifold applications.

Reliability, Validity and Classification Accuracy of the South Oaks Gambling Screen in a Brazilian Sample

The purpose of this study was to examine the reliability, validity and classification accuracy of the South Oaks Gambling Screen (SOGS) in a sample of the Brazilian population. Participants in this study were drawn from three sources: 71 men and women from the general population interviewed at a metropolitan train station; 116 men and women encountered at a bingo venue; and 54 men and women undergoing treatment for gambling. The SOGS and a DSM-IV-based instrument were applied by trained researchers. The internal consistency of the SOGS was 0.75 according to the Cronbach`s alpha model, and construct validity was good. A significant difference among groups was demonstrated by ANOVA (F ((2.238)) = 221.3, P < 0.001). The SOGS items and DSM-IV symptoms were highly correlated (r = 0.854, P < 0.01). The SOGS also presented satisfactory psychometric properties: sensitivity (100), specificity (74.7), positive predictive rate (60.7), negative predictive rate (100) and misclassification rate (0.18). However, a cut-off score of eight improved classification accuracy and reduced the rate of false positives: sensitivity (95.4), specificity (89.8), positive predictive rate (78.5), negative predictive rate (98) and misclassification rate (0.09). Thus, the SOGS was found to be reliable and valid in the Brazilian population.

Determination of Tetracycline in Environmental Water Samples at a Graphite-Polyurethane Composite Electrode

A bare graphite-polyurethane composite was evaluated in the tetracycline (TC) determination in natural water samples. Using differential pulse voltammetry (DPV), a linear response was observed in the range of 4.00-40.0 mu mol L-1 with limit of detection of 2.80 mu mol L-1, without the need of surface renewing between successive runs. During the tetracycline determination in water samples, recoveries between 92.6 and 100% were found. The results for TC determination in water samples after a pre-concentration stage agreed with spiked value at a 95% confidence level according to student t-test.

Use of Gas Diffusion Electrode for the In Situ Generation of Hydrogen Peroxide in an Electrochemical Flow-By Reactor

Hydrogen peroxide is a powerful oxidant that finds application in several areas, but most particularly in the treatment of industrial wastewaters. The aim of the present study was to investigate the effects of applied potential and electrolyte flow conditions on the in situ generation of hydrogen peroxide in an electrochemical flow-by reactor with a gas diffusion electrode (GDE). The electrolyses were performed in an aqueous acidic medium using a GDE constructed with conductive black graphite and polytetrafluoroethylene (80:20 w/w). Under laminar flow conditions (flow rate = 50 L/h), hydrogen peroxide was formed in a maximum yield of 414 mg/L after 2 h at -2.25 V vs Pt //Ag/AgCl (global rate constant = 3.1 mg/(L min); energy consumption = 22.1 kWh/kg). Under turbulent flow (300 L/h), the maximum yield obtained was 294 mg/L after 2 h at -1.75 V vs Pt//Ag/AgCl (global rate constant = 2.5 mg/ (L min); energy consumption = 30.1 kWh/kg).

A comparative study of the electrochemical oxidation of the herbicide tebuthiuron using boron-doped diamond electrode

The thiadiazolylurea derivative tebuthiuron (TBH) is commonly used as an herbicide even though it is highly toxic to humans. While various processes have been proposed for the removal of organic contaminants of this type from wastewater, electrochemical degradation has shown particular promise. The aim of the present study was to investigate the electrochemical degradation of TBH using anodes comprising boron-doped (5000 and 30000 ppm) diamond (BDD) films deposited onto Ti substrates operated at current densities in the range 10-200 mA cm(-2). Both anodes removed TBH following a similar pseudo first-order reaction kinetics with k(ap)p close to 3.2 x 10(-2) min(-1). The maximum mineralization efficiency obtained was 80%. High-pressure liquid chromatography with UV-VIS detection established that both anodes degraded TBH via similar intermediates. Ion chromatography revealed that increasing concentrations of nitrate ions (up to 0.9 ppm) were formed with increasing current density, while the formation of nitrite ions was observed with both anodes at current densities >= 150 mA cm(-2). The BDD film prepared at the lower doping level (5000 ppm) was more efficient in degrading TBH than its more highly doped counterpart. This unexpected finding may be explained in terms of the quantity of impurities incorporated into the diamond lattice during chemical vapor deposition. (C) 2012 Elsevier Ltd. All rights reserved.

ARE TWO ITEMS SUFFICIENT TO SCREEN FOR DEPRESSION WITHIN THE HOSPITAL CONTEXT?

Objective: to determine the ability of the reduced form of a screening instrument, the Patient Health Questionnaire-2 (PHQ-2), to assess the presence of depressive disorders in patients admitted to a general hospital. Method: A sample of 227 patients admitted to the clinical wards of a Brazilian general university hospital were assessed with Module A of the Diagnostic Structured Interview for the DSM-IV (SCID-IV) and filled out the PHQ-9 and PHQ-2. Results: The PHQ-2 demonstrated an area under the ROC curve of 0.89 (p < 0.0001), with a cutoff point of three or more being the one that best equilibrated the sensitivity (0.86) and specificity (0.75) values. The agreement index between the PHQ-2 and module A of SCID-W was 78.4% and the Kappa value was 0.51. Regarding reliability, the Cronbach alpha value obtained was 0.64 and the intraclass correlation coefficient was 0.52. Conclusion: PHQ-2 proved to be an instrument with good psychometric properties comparable to those of PHQ-9, being superior to the latter regarding the rate of false-positive results. In addition, it is a brief instrument that elicits little resistance on the part of the patient, being inexpensive and requiring little time, thus being of important help to the treatment teams for the detection of depressive disorder, being suitable for incorporation into hospital admission protocols and thus possibly favoring more immediate interventions. (Int'l J. Psychiatry in Medicine 2012;44:141-148)

Development and Evaluation of a Pseudoreference Pt//Ag/AgCl Electrode for Electrochemical Systems

The use of standard reference electrodes, such as Ag/AgCl or saturated calomel electrodes, in potentiometric and amperometric studies involving miniaturized electrochemical systems, or those operating under positive hydraulic pressure, is often impractical. Placement of the reference electrode in the direct vicinity of the working electrode is often prohibited by the dimensions or layout of the electrochemical cell, while the alternative strategy of locating the reference electrode in a separate compartment often leads to electrolyte leakage and contamination of the system. In the present study, we have investigated the functionality of a pseudoreference electrode comprising a platinum wire, one end of which was maintained in intimate contact with the internal solution of an Ag/AgCl reference electrode while the other was connected, via a BNC connector, to a platinum probe located within the electrochemical cell. Linear and cyclic voltammetric studies, involving both aqueous and nonaqueous electrolytes, were carried out using the pseudoreference electrode and an electrochemical cup-type cell with three electrodes or an electrochemical flow reactor. In all cases, the functionality of the Pt//Ag/AgCl system was similar to that of a conventional Ag/AgCl reference electrode. Variations in the electrolyte did not alter the potential or voltammetric profile recorded when using the pseudoreference system, although peak currents were generally improved and potential values shifted by approximately +350 mV in comparison with the Ag/AgCl electrode, therefore, the system pseudoreference can be applied in any electrochemical system due to the constant potential difference. It is concluded that the pseudoreference electrode can be used with advantage to obtain potentiometric and amperometric measurements in both simple and complex electrochemical systems.

Hydrogen peroxide monitoring in Fenton reaction by using a ruthenium oxide hexacyanoferrate/multiwalled carbon nanotubes modified electrode

A novel amperometric sensor based on the incorporation of ruthenium oxide hexacyanoferrate (RuOHCF) into multiwalled carbon nanotubes (MWCNTs) immobilized on a glassy carbon electrode is described. Cyclic voltammetry experiments indicated that the cathodic reduction of hydrogen peroxide at the RuOHCF/MWCNTs100/GC modified electrode is facilitated, occurring at 0.0 V vs. Ag/AgCl/KCl(sat). Following the optimization of the experimental conditions, the proposed sensor presented excellent analytical properties for hydrogen peroxide determination, with a low limit of detection (4.7 mu mol L-1), a large dynamic concentration range (0.1-10 mmol L-1) and a sensitivity of 1280 mu A mmol(-1) L cm(-2). The usefulness of the RuOHCF/MWCNTs100/GC electrochemical sensor was confirmed by monitoring the consumption of hydrogen peroxide during the degradation of phenol by the Fenton reaction. (C) 2012 Elsevier B.V. All rights reserved.

Is the poly (methylene blue)-modified glassy carbon electrode an adequate electrode for the simple detection of thiols and amino acid-based molecules?

This paper describes the preparation, characterization, and use of poly (methylene blue) (PMB)-modified glassy carbon electrodes (GCE) (GCE-PMB) in the detection of the thiols L-cysteine (L-CySH) and N-acetyl cysteine (Acy), and the herbicide glyphosate (GLYP) in pH 5.3 aqueous solution. The polymer film prepared by electropolymerization showed different characteristics such as robustness, stability, and redox properties satisfactorily. The surface coverage concentration (Gamma) of PMB was found to be 7.90 x 10(-9) - mol cm(-2). Moreover, we observed strong adhesion of the polymer film to the electrode surface. The results using GCE-PMB as a sensor indicated that this modified electrode exhibited electrocatalytic activity toward the detection of thiols and glyphosate in 0.1 mol L-1 KO (pH 5.3). Meanwhile, strong adsorption of the analytes on the GCE-PMB electrodes was also observed. Otherwise, using a low concentration (1 x 10(-4) mol L-1) of L-cysteine and N-acetyl cysteine and 8.9 x 10(-6) mol L-1 of glyphosate, separately, it was possible to observe a well-defined electrochemical response, thus providing an opportunity to further understand the applicability of PMB as a sensor for amino acid-based molecules. (C) 2012 Elsevier B.V. All rights reserved.

Comparison between the C5 or C6-Cz electrode assembly and C3 or C4-Cz assembly for transcranial electric motor activation of muscular response of the contralateral facial nerve

We used an assembly of electrodes C3 and C4-Cz in order to activate the motor cortical area of the corticobulbar tract to elucidate the motor-evoked potential of the contralateral mentalis muscle. We compared this setup to that of an assembly with electrodes C5 or C6-Cz using a train of electrical pulses and a single electrical pulse. This analysis was made in 23 consecutive patients who underwent several varied surgeries and were prospectively operated on at Santa Paula Hospital between January and June 2011. The results showed that the assembly with C5 or C6-Cz produced a multisynaptic motor-evoked potential in the contralateral mentalis muscle in 86.9 % of the patients, whereas 82.6 % of patients stimulated at points C3 or C4-Cz presented the same response. However, both assemblies showed similar behavior with the use of a single electrical pulse for peripheral contralateral nerve stimulation. We concluded that the C5 or C6-Cz assembly was similar to C3 or C4-Cz in obtaining a multisynaptic response in the contralateral mentalis muscle, although it required less intensive stimulation than the C3 or C4- Cz assembly.

Ear and electrode effects reduce within-group variability in middle latency response amplitude measures

Objectives: To establish normative amplitude values for relative difference measurements of the middle latency response (MLR) in normal-hearing pediatrics and to determine if these measurements provided a significant reduction of within-group variability when compared to raw, absolute amplitude measures. A relative amplitude difference is defined in the present paper as the difference in Na-Pa amplitude between two electrodes (e.g. vertical bar Na-Pa at C3 minus Na-Pa at C4 vertical bar, or electrode effects) or between two ears (e.g. vertical bar Na-Pa on left ear stimulation minus Na-Pa on right ear stimulation vertical bar, or ear effects). In contrast, an absolute amplitude is defined as a single Na-Pa measurement made at one electrode for stimulation of one ear (e.g. Na-Pa measured at C3 on left ear stimulation). Design: Cross-sectional study. Study sample: 155 pediatrics with normal peripheral and central hearing, and no history of psychological, neurological, or learning disability issues. Results: Within-group variability was significantly smaller for relative differences when compared to absolute amplitude measures. Electrode effects showed significantly less variability than ear effects. Normative values for ear and electrode effects were reported. Conclusions: Relative differences may provide better utility in the clinical diagnosis of central auditory pathology in pediatrics when compared to absolute amplitude measures because these difference measures show significantly lower variability when examined across subjects.

ELECTROCHEMICAL OXIDATION OF THE HERBICIDE TEBUTHIURON USING DSA (R)-TYPE ELECTRODE

ELECTROCHEMICAL OXIDATION OF THE HERBICIDE TEBUTHIURON USING DSA (R)-TYPE ELECTRODE. Tebuthiuron (TBH) is a herbicide widely used in different cultures and known for its toxic effects. Electrochemical methods are promising for removing pollutants such as pesticides. This study showed the degradation of TBH using a DSA (R) anode operated at current densities of 50 to 200 mA cm(-2). Removal presented pseudo-first order kinetics while high-pressure liquid chromatography (UV detection) showed two peaks, ascribed to degradation intermediates. The maximum percentage of total organic carbon removed was 12.9%. Ion chromatography revealed that higher concentrations of nitrate and nitrite ions formed with increasing current density.

Flow injection analysis of free glycerol in biodiesel using a copper electrode as an amperometric detector

The main goal of this work was to develop a simple analytical method for quantification of glycerol based on the electrocatalytic oxidation of glycerol on the copper surface adapted in a flow injection system. Under optimal experimental conditions, the peak current response increases linearly with glycerol concentration over the range 60-3200 mg kg(-1) (equivalent to 3-160 mg L(-1) in solution). The repeatability of the electrode response in the flow injection analysis (FIA) configuration was evaluated as 5% (n = 10), and the detection limit of the method was estimated to be 5 mg kg(-1) in biodiesel (equivalent to 250 mu g L(-1) in solution) (S/N = 3). The sample throughput under optimised conditions was estimated to be 90 h(-1). Different types of biodiesel samples (B100), as in the types of vegetable oils or animal fats used to produce the fuels, were analysed (seven samples). The only sample pre-treatment used was an extraction of glycerol from the biodiesel sample containing a ratio of 5 mL of water to 250 mg of biodiesel. The proposed method improves the analytical parameters obtained by other electroanalytical methods for quantification of glycerol in biodiesel samples, and its accuracy was evaluated using a spike-and-recovery assay, where all the biodiesel samples used obtained admissible values according to the Association of Official Analytical Chemists. Crown Copyright (C) 2011 Published by Elsevier Ltd. All rights reserved.

EVALUATION OF THE POTENTIALITIES OF A CARBON NANOTUBES/SILICONE RUBBER COMPOSITE ELECTRODE IN THE DETERMINATION OF HYDROCHLOROTHIAZIDE

A multiwall carbon nanotube/silicone rubber (MWCNT/SR) composite electrode has been used for the determination of hydrochlorothiazide (HCTZ) in pharmaceutical formulations by differential pulse voltammetry (DPV). The electro-oxidation process was evaluated by cyclic voltammetry, from which it was observed that HCTZ presents an irreversible oxidation peak at 0.82 V vs. saturated calomel electrode (SCE) in the potential range from 0.5 to 1.1 V, in Britton-Robinson buffer pH 7.0 at MWCNT/SR. HCTZ was determined by DPV using a MWCNT/SR 70% (MWCNT, m/m) composite electrode after the optimization of the experimental parameters. The linear range was from 5.0 to 70.0 mu mol L-1, with a limit of detection (LOD) of 2.6 mu mol L-1. The HCTZ was determined in pharmaceutical formulations using the proposed composite electrode and the results agreed with those from the official high performance liquid chromatography (HPLC) method within 95% confidence level, according to the t-Student test.

Intervention Based Exclusively on Stage- Matched Printed EducationalMaterials Regarding Healthy Eating Does Not Result in Changes to Adolescents' Dietary Behavior

Purpose. To assess the impact of a six-month stage-based intervention on fruit and vegetable intake, regarding perceived benefits and barriers, and self-efficacy among adolescents. Design. Randomized treatment-control, pre-post design. Subjects/ Setting. Schools were randomized between control and experimental groups. 860 adolescents from ten public schools in Bras ' ilia, Federal District, Brazil were evaluated at baseline; 771 (81%) completed the study. Intervention. Experimental group received monthly magazines and newsletters aimed at promotion of healthy eating. Measures. Self-reported fruit and vegetable intake, stages of change, self-efficacy and decisional balance scores were evaluated at baseline and post-intervention in both groups. Analysis. The effectiveness of the intervention was evaluated using the analysis of covariance model (ANCOVA) and repeated measurement analysis by means of weighted least squares. Comparison between the proportions of adolescents who advanced through the stages during the intervention was performed using the Mantel-Haenszel chi-square test. Results. After adjusting for sex and age, study variables showed no modifications through the proposed intervention. There was no statistical difference in participant mobility in the intervention and control groups between the stages of change, throughout the study. Conclusion. A nutritional intervention based exclusively on distribution of stage-matched printed educational materials was insufficient to change adolescents' dietary behavior.