Surface structure effects on the electrochemical oxidation of ethanol on platinum single crystal electrodes

Ethanol oxidation has been studied on Pt(111), Pt(100) and Pt(110) electrodes in order to investigate the effect of the surface structure and adsorbing anions using electrochemical and FTIR techniques. The results indicate that the surface structure and anion adsorption affect significantly the reactivity of the electrode. Thus, the main product of the oxidation of ethanol on the Pt(111) electrode is acetic acid, and acetaldehyde is formed as secondary product. Moreover, the amount of CO formed is very small, and probably associated with the defects present on the electrode surface. For that reason, the amount of CO(2) is also small. This electrode has the highest catalytic activity for the formation of acetic acid in perchloric acid. However, the formation of acetic acid is inhibited by the presence of specifically adsorbed anions, such as (bi) sulfate or acetate, which is the result of the formation of acetic acid. On the other hand, CO is readily formed at low potentials on the Pt(100) electrode, blocking completely the surface. Between 0.65 and 0.80 V, the CO layer is oxidized and the production of acetaldehyde and acetic acid is detected. The Pt(110) electrode displays the highest catalytic activity for the splitting of the C-C bond. Reactions giving rise to CO formation, from either ethanol or acetaldehyde, occur at high rate at any potential. On the other hand, the oxidation of acetaldehyde to acetic acid has probably the lower reaction rate of the three basal planes.

Autocatalysis in the open circuit interaction of alcohol molecules with oxidized Pt surfaces

We studied the open circuit interaction of methanol and ethanol with oxidized platinum electrodes using in situ infrared spectroscopy. For methanol, it was found that formic acid is the main species formed in the initial region of the transient and that the steep decrease of the open circuit potential coincides with an explosive increase in the CO(2) production, which is followed by an increase in the coverage of adsorbed CO. For ethanol, acetaldehyde was the main product detected and only traces of dissolved CO(2) and adsorbed CO were found after the steep potential decay. In both cases, the transients were interpreted in terms of (a) the emergence of sub-surface oxygen in the beginning of the transient, where the oxide content is high, and (b) the autocatalytic production of free platinum sites for lower oxide content during the steep decay of the open circuit potential.

Flow injection analysis of paracetamol using a biomimetic sensor as a sensitive and selective amperometric detector

This work describes the coupling of a biomimetic sensor to a flow injection system for the sensitive determination of paracetamol. The sensor was prepared as previously described in the literature (M. D. P. T. Sotomayor, A. Sigoli, M. R. V. Lanza, A. A. Tanaka and L. T. Kubota, J. Braz. Chem. Soc., 2008, 19, 734) by modifying a glassy carbon electrode surface with a Nafion (R) membrane doped with iron tetrapyridinoporphyrazine (FeTPyPz), a biomimetic catalyst of the P450 enzyme. The performance of the sensor for paracetamol detection was investigated and optimized in a flow injection system (FIA) using a wall jet electrochemical cell. Under optimized conditions a wide linear response range (1.0 x 10(-5) to 5.0 x 10(-2) mol L(-1)) was obtained, with a sensitivity of 2579 (+/- 129) mu A L mu mol(-1). The detection and quantification limits of the sensor for paracetamol in the FIA system were 1.0 and 3.5 mu mol L(-1), respectively. The analytical frequency was 51 samples h(-1), and over a period of five days (320 determinations) the biosensor maintained practically the same response. The system was successfully applied to paracetamol quantification in seven pharmaceutical formulations and in water samples from six rivers in Sao Paulo State, Brazil.

Dual contactless conductivity and amperometric detection on hybrid PDMS/glass electrophoresis microchips

A new approach for the integration of dual contactless conductivity and amperometric detection with an electrophoresis microchip system is presented. The PDMS layer with the embedded channels was reversibly sealed to a thin glass substrate (400 mu m), on top of which a palladium electrode had been previously fabricated enabling end-channel amperometric detection. The thin glass substrate served also as a physical wall between the separation channel and the sensing copper electrodes for contactless conductivity detection. The latter were not integrated in the microfluidic device, but fabricated on an independent plastic substrate allowing a simpler and more cost-effective fabrication of the chip. PDMS/glass chips with merely contactless conductivity detection were first characterized in terms of sensitivity, efficiency and reproducibility. The separation efficiency of this system was found to be similar or slightly superior to other systems reported in the literature. The simultaneous determination of ionic and electroactive species was illustrated by the separation of peroxynitrite degradation products, i.e. NO(3)(-) (non-electroactive) and NO(2)(-) (electroactive), using hybrid PDMS/glass chips with dual contactless conductivity and amperometric detection. While both ions were detected by contactless conductivity detection with good efficiency, NO(2)(-) was also simultaneously detected amperometrically with a significant enhancement in sensitivity compared to contactless conductivity detection.

Rapid prototyping of polymeric electrophoresis microchips with integrated copper electrodes for contactless conductivity detection

A simple and easy approach to produce polymeric microchips with integrated copper electrodes for capacitively coupled contactless conductivity detection (CD) is described. Copper electrodes were fabricated using a printed circuit board (PCB) as an inexpensive thin-layer of metal. The electrode layout was first drawn and laser printed on a wax paper sheet. The toner layer deposited on the paper sheet was thermally transferred to the PCB surface working as a mask for wet chemical etching of the copper layer. After the etching step, the toner was removed with an acetonitrile-dampened cotton. A poly(ethylene terephthalate) (PET) film coated with a thin thermo-sensitive adhesive layer was used to laminate the PCB plate providing an insulator layer of the electrodes to perform CID measurements. Electrophoresis microchannels were fabricated in poly(dimethylsiloxane) (PDMS) by soft lithography and reversibly sealed against the PET film. These hybrid PDMS/PET chips exhibited a stable electroosmotic mobility of 4.25 +/- 0.04 x 10(-4) V cm(-2) s(-1), at pH 6.1, over fifty runs. Efficiencies ranging from 1127 to 1690 theoretical plates were obtained for inorganic cations.

A flow-based procedure with solenoid micro-pumps for the spectrophotometric determination of uric acid in urine

The determination of uric acid in urine shows clinical importance, once it can be related to human organism dysfunctions, such as gout. An analytical procedure employing a multicommuted flow system was developed for the determination of uric acid in urine samples. Cu(II) ions are reduced by uric acid to Cu(I) that can be quantified by spectrophotometry in the presence of 2,2`-biquinoline 4,4`-dicarboxylic acid (BCA). The analytical response was linear between 10 and 100 mu mol L(-1) uric acid with a detection limit of 3.0 mu mol L(-1) (99.7% confidence level). Coefficient of variation of 1.2% and sampling rate of 150 determinations per hour were achieved. Per determination, 32 mu g of CuSO(4) and 200 mu g of BCA were consumed, generating 2.0 mL of waste. Recoveries from 91 to 112% were estimated and the results for 7 urine samples agreed with those obtained by the commercially available enzymatic kit for determination of uric acid. The procedure required 100-fold dilution of urine samples, minimizing sample consumption and interfering effects. In order to avoid the manual dilution step, on-line sample dilution was achieved by a simple system reconfiguration attaining a sampling rate of 95 h(-1). (C) 2009 Elsevier B.V. All rights reserved.

Exploiting pi-acceptors for the determination of thyroid hormones (T3 and T4) using a single interface flow system

A fully automated methodology was developed for the determination of the thyroid hormones levothyroxine (T4) and liothyronine (T3). The proposed method exploits the formation of highly coloured charge-transfer (CT) complexes between these compounds, acting as electron donors, and pi-acceptors such as chloranilic acid (CIA) and 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ). For automation of the analytical procedure a simple, fast and versatile single interface flow system (SIFA)was implemented guaranteeing a simplified performance optimisation, low maintenance and a cost-effective operation. Moreover, the single reaction interface assured a convenient and straightforward approach for implementing job`s method of continuous variations used to establish the stoichiometry of the formed CT complexes. Linear calibration plots for levothyroxine and liothyronine concentrations ranging from 5.0 x 10(-5) to 2.5 x 10(-4) mol L(-1) and 1.0 x 10(-5) to 1.0 x 10(-4) mol L(-1), respectively, were obtained, with good precision (R.S.D. <4.6% and <3.9%) and with a determination frequency of 26 h(-1) for both drugs. The results obtained for pharmaceutical formulations were statistically comparable to the declared hormone amount with relative deviations lower than 2.1%. The accuracy was confirmed by carrying out recovery studies, which furnished recovery values ranging from 96.3% to 103.7% for levothyroxine and 100.1% for liothyronine. (C) 2009 Elsevier B.V. All rights reserved.

DFT and electrochemical studies on nortriptyline oxidation sites

A study on the possible sites of oxidation and epoxidation of nortriptyline was performed using electrochemical and quantum chemical methods; these sites are involved in the biological responses (for example, hepatotoxicity) of nortriptyline and other similar antidepressants. Quantum chemical studies and electrochemical experiments demonstrated that the oxidation and epoxidation sites are located on the apolar region of nortriptyline, which will useful for understanding the molecule`s activity. Also, for the determination of the compound in biological fluids or in pharmaceutical formulations, we propose a useful analytical methodology using a graphite-polyurethane composite electrode, which exhibited the best performance when compared with boron-doped diamond or glassy carbon surfaces.

Microstructural characterization of as-cast Cr-B alloys

Accurate knowledge of several Me-B (Me - Metal) phase diagrams are important to evaluate higher order systems such as Me-Si-B ternaries. This work presents results of microstructural characterization of as-cast Cr-B alloys which are significant to assess the liquid compositions associated to most of the invariant reactions of this system. Alloys of different compositions were prepared by arc melting pure Cr and B pressed powder mixtures under argon atmosphere in a water-cooled copper crucible with non-consumable tungsten electrode and titanium getter. The phases were identified by scanning electron microscopy (SEM), using back-scattered electron (BSE) image mode and X-ray diffraction (XRD). In general, a good agreement was found between our data and those from the currently accepted Cr-B phase diagram. (c) 2006 Elsevier Inc. All rights reserved.

Microstructural characterization of as-cast Cr-Si alloys

This work presents results of microstructural characterization of as-cast Cr-Si alloys. The alloys were prepared by arc melting pure Cr (min. 99.996%) and Si (min. 99.998%) powder mixtures under argon atmosphere in a water-cooled copper crucible with nonconsumable tungsten electrode and titanium getter. The phases were identified by scanning electron microscopy (SEM), using the back-scattered electron (BSE) image mode and X-ray diffraction (XRD). The results confirm the currently accepted Cr-Si phase diagram in terms of the invariant reactions and solid phases present in this system. Small corrections are proposed for the compositions of the liquid phase in the following reactions: (i) L double left right arrow Cr-ss+Cr3Si, from 15 to 16 at.% Si; (ii) L+alpha Cr5Si3 double left right arrow CrSi, from 51 at.% Si to slightly above 53 at.% Si; (iii) L double left right arrow CrSi+CrSi2, from 56 to slightly above 57 at.% Si; (iv) L double left right arrow CrSi2+Si, from 82 to slightly above 85 at.% Si. (c) 2006 Elsevier Inc. All rights reserved.

Enzymatic Hydrolysis of Chemithermomechanically Pretreated Sugarcane Bagasse and Samples with Reduced Initial Lignin Content

Chemithermomechanical (CTM) processing was used to pretreat sugarcane bagasse with the aim of increasing cell wall accessibility to hydrolytic enzymes. Yields of the pretreated samples were in the range of 75-94%. Disk refining and alkaline-CTM and alkaline/sulfite-CTM pretreatments yielded pretreated materials with 21.7, 17.8, and 15.3% of lignin, respectively. Hemicellulose content was also decreased to some extent. Fibers of the pretreated materials presented some external fibrillation, fiber curling, increased swelling, and high water retention capacity. Cellulose conversion of the alkaline-CTM- and alkaline/sulfite-CTM-pretreated samples reached 50 and 85%, respectively, after 96 h of enzymatic hydrolysis. Two samples with low initial lignin content were also evaluated after the mildest alkaline-CTM pretreatment. One sample was a partially delignified mill-processed bagasse. The other was a sugarcane hybrid selected in a breeding program. Samples with lower initial lignin content were hydrolyzed considerably faster in the first 24 h of enzymatic digestion. For example, enzymatic hydrolysis of the sample with the lowest initial lignin content (14.2%) reached 64% cellulose conversion after only 24 h of hydrolysis when compared with the 30% observed for the mill-processed bagasse containing an initial lignin content of 24.4%. (C) 2011 American Institute of Chemical Engineers Biotechnol. Prog., 27: 395-401, 2011

A novel electrocatalyst support with proton conductive properties for polymer electrolyte membrane fuel cell applications

The objective of this study is to graft the Surface of carbon black, by chemically introducing polymeric chains (Nafion (R) like) with proton-conducting properties. This procedure aims for a better interaction of the proton-conducting phase with the metallic catalyst particles, as well as hinders posterior support particle agglomeration. Also loss of active surface call be prevented. The proton conduction between the active electrocatalyst site and the Nafion (R) ionomer membrane should be enhanced, thus diminishing the ohmic drop ill the polymer electrolyte membrane fuel cell (PEMFC). PtRu nanoparticles were supported on different carbon materials by the impregnation method and direct reduction with ethylene glycol and characterized using amongst others FTIR, XRD and TEM. The screen printing technique was used to produce membrane electrode assemblies (MEA) for single cell tests in H(2)/air(PEMFC) and methanol operation (DMFC). In the PEMFC experiments, PtRu supported on grafted carbon shows 550 mW cm(-2) gmetal(-1) power density, which represents at least 78% improvement in performance, compared to the power density of commercial PtRu/C ETEK. The DMFC results of the grafted electrocatalyst achieve around 100% improvement. The polarization Curves results clearly show that the main Cause of the observed effect is the reduction in ohmic drop, caused by the grafted polymer. (C) 2009 Elsevier B.V. All rights reserved.

Lumbar Epidural Anesthesia in the Treatment of Discal Lombosciatalgia: A Comparative Clinical Study between Methylprednisolone and Methylprednisolone with Levobupivacaine

Sousa FAEF, Colhado OCG - Lumbar Epidural Anesthesia in the Treatment of Discal Lombosciatalgia: A Comparative Clinical Study between Methylprednisolone and Methylprednisolone with Levobupivacaine. Background and objectives: Lumbar epidural technique has been used in the treatment of lombosciatalgia since 1953. In most cases, methylprednisolone is used along with a local anesthetic, and it is not known whether the isolated use of methylprednisolone is equally effective in relieving symptoms. The objective of this study was to compare the efficacy of two different solutions - methylprednisolone with saline and methylprednisolone with levobupivacaine injected in the epidural space to heal lombosciatalgia secondary to lumbar herniated disk. Methods: Sixty individuals ASA I and II, of both genders, ages 18 to 65 years participated in this randomized, double-blind study over a period of one year. They underwent interlaminar lumbar epidural analgesia without radioscopic control to heal a lombosciatalgia and they were divided into two groups: G-M (methylprednisolone + saline) and G-M + L (methylprednisolone + levobupivacaine + saline) both at a volume of 10 mL. Diagnosis was based on history, physical exam, and imaging exam (MRI). The Visual Analogue Scale (VAS) was applied in a total of two blockades, 15 days apart. Results: A reduction in pain severity was observed in the methylprednisolone-levobupivacaine group, but without statistical significance. Conclusions: The analgesic efficacy of the G-M + L solution was superior to that of the G-M solution in the treatment of discal lombosciatalgia regarding the shorter time to onset of analgesia, but this was not significant at the time of discharge, and both solutions were effective in the treatment of discal lombosciatalgia.

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.

Finite element homogenization technique for the characterization of d(15) shear piezoelectric macro-fibre composites

A finite element homogenization method for a shear actuated d(15) macro-fibre composite (MFC) made of seven layers (Kapton, acrylic, electrode, piezoceramic fibre and epoxy composite, electrode, acrylic, Kapton) is proposed and used for the characterization of its effective material properties. The methodology is first validated for the MFC active layer only, made of piezoceramic fibre and epoxy, through comparison with previously published analytical results. Then, the methodology is applied to the seven-layer MFC. It is shown that the packaging reduces significantly the shear stiffness of the piezoceramic material and, thus, leads to significantly smaller effective electromechanical coupling coefficient k(15) and piezoelectric stress constant e(15) when compared to the piezoceramic fibre properties. However, it is found that the piezoelectric charge constant d(15) is less affected by the softer layers required by the MFC packaging.