Ethanol electro-oxidation on carbon-supported Pt-Ru, Pt-Rh and Pt-Ru-Rh nanoparticles

This work investigates the effects of carbon-supported Pt, Pt-Ru, Pt-Rh and Pt-Ru-Rh alloy electrocatalysts oil the yields of CO2 and acetic acid as electro-oxidation products of ethanol. Electronic and structural features of these metal alloys were studied by in situ X-ray absorption spectroscopy (XAS). The electrochemical activity was investigated by polarization experiments and the reaction intermediates and products were analyzed by in situ Fourier Transform Infra-Red Spectroscopy (FTIR). Electrochemical stripping of CO. which is one of the adsorbed intermediates, presented a faster oxidation kinetics on the Pt-Ru electrocatalyst, and similar rates of reaction on Pt-Rh and Pt. The electrochemical current of ethanol oxidation showed a higher value and the onset potential was less positive oil Pt-Ru. However, in situ FTIR spectra evidenced that the CO2/acetic acid ratio is higher for the materials with Rh, mainly at lower potentials. These results indicate that the Ru atoms act mainly by providing oxygenated species for the oxidation of ethanol intermediates, and point out ail important role of Rh on the C-C bond dissociation. (C) 2007 Elsevier Ltd. All rights reserved.

The electrochemical effect of acid functionalisation of carbon nanotubes to be used in sensors development

The electrochemical behaviour of multi-walled carbon nanotubes was compared with that of glassy carbon, and the differences were investigated by cyclic voltammetry and electrochemical impedance spectroscopy before and after acid pre-treatment. The electrochemical techniques showed that acid functionalisation significantly improves the electrocatalytic properties of carbon nanotubes. These electrocatalytic properties enhance the analytical signal, shift the oxidation peak potential to a less positive value, and the charge-transfers rate increase of both dopamine and K(4)[Fe(CN)(6)]. The functionalisation step and the resulting appearance of edge planes covered with different chemical groups were confirmed by FTIR measurements. Carbon nanotubes after acid pre-treatment are a potentially powerful analytical tool for sensor development. (C) 2010 Elsevier B.V. All rights reserved.

Determination of epinephrine in urine using multi-walled carbon nanotube modified with cobalt phthalocyanine in a paraffin composite electrode

This paper describes the development, electrochemical characterization and utilization of a cobalt phthalocyanine (CoPc), modified multi-walled carbon nanotube (MWCNT), and paraffin composite electrode for the quantitative determination of epinephrine (EP) in human urine samples. The electrochemical profile of the proposed composite electrode was analyzed by differential pulse voltammetry (DPV) that showed a shift of the oxidation peak potential of EP at 175 mV to less positive value, compared with a paraffin/graphite composite electrode without CoPc. DPV experiments in PBS at pH 6.0 were performed to determine EP without any previous step of extraction, clean-up, and derivatization, in the range from 1.33 to 5.50 mu mol L(-1), with a detection limit of 15.6 nmol L(-1) (2.86) of EP in electrolyte prepared with purified water. The lifetime of the proposed sensors was at least over 1000 determinations with 1.7 and 3.1 repeatability and reproducibility relative standard deviations, respectively. Human urine samples without any purification step were successfully analyzed under the standard addition method using paraffin/MWCNT/CoPc composite electrode. (C) 2010 Elsevier B.V. All rights reserved.

Anodic stripping voltammetric determination of copper(II) using a functionalized carbon nanotubes paste electrode modified with crosslinked chitosan

The development and application of a functionalized carbon nanotubes paste electrode (CNPE) modified with crosslinked chitosan for determination of Cu(II) in industrial wastewater, natural water and human urine samples by linear scan anodic stripping voltammetry (LSASV) are described. Different electrodes were constructed using chitosan and chitosan crosslinked with glutaraldehyde (CTS-GA) and epichlorohydrin (CTS-ECH). The best voltammetric response for Cu(II) was obtained with a paste composition of 65% (m/m) of functionalized carbon nanotubes, 15% (m/m) of CTS-ECH, and 20% (m/m) of mineral oil using a solution of 0.05 mol L(-1) KNO(3) with pH adjusted to 2.25 with HNO(3), an accumulation potential of 0.3V vs. Ag/AgCl (3.0 mol L(-1) KCl) for 300 s and a scan rate of 100 mV s(-1). Under these optimal experimental conditions, the voltammetric response was linearly dependent on the Cu(II) concentration in the range from 7.90 x 10(-8) to 1.60 x 10(-5) mol L(-1) with a detection limit of 1.00 x 10(-8) mol L(-1). The samples analyses were evaluated using the proposed sensor and a good recovery of Cu(II) was obtained with results in the range from 98.0% to 104%. The analysis of industrial wastewater, natural water and human urine samples obtained using the proposed CNPE modified with CTS-ECH electrode and those obtained using a comparative method are in agreement at the 95% confidence level. (C) 2009 Elsevier B. V. All rights reserved.

A comparative study of the electrogeneration of hydrogen peroxide using Vulcan and Printex carbon supports

A comparative study of two different conductive carbon-black pigments, Vulcan XC-72 R and Printex L6, for the electrogeneration of hydrogen peroxide (H(2)O(2)) by reducing dissolved oxygen in an alkaline solution was performed. The materials were physically characterized by X-ray diffraction (XRD), Fourier transform infrared attenuated total reflection (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS). XRD shows the presence of SO(2) and ATR-FTIR technique indicates a difference in NO and SO(2) functional groups between the two carbon pigments. XPS indicated presence of SO and NO and more oxygenated acid species on Printex L6. A rotating ring-disk electrode was used for electrochemical analysis of the oxygen reduction reaction (ORR). The results showed that the Printex L6 was better than Vulcan XC-72 R for H(2)O(2) production. Results also indicate that the number of electrons transferred in the ORR for Printex L6 and Vulcan XC-72 R were 2.2 and 2.9, respectively, while the percentages of H(2)O(2) formed were 88% and 51%. Scanning electrochemistry microscopy images confirmed the higher amount of H(2)O(2) formed in the Printex L6 pigment. Printex L6 was shown to be a more promising for H(2)O(2) production than Vulcan XC-72 R, while the latter was shown to have more potential for fuel cells. (C) 2011 Elsevier Ltd. All rights reserved.

Voltammetric determination of isoprenaline in pharmaceutical preparations using a copper(II) hexacyanoferrate(III) modified carbon paste electrode

The electroanalytical determination of isoprenaline in pharmaceutical preparations of a homemade carbon paste electrode modified with copper(II) hexacyanoferrate(III) (CuHCF) was studied by cyclic voltammetry. Several parameters were studied for the optimization of the sensor such as electrode composition, electrolytic solution, pH effect, potential scan rate and interferences in potential. The optimum conditions were found in an electrode composition (in mass) of 15% CuHCF, 60% graphite and 25% mineral oil in 0.5 mol l(-1) acetate buffer solution at pH 6.0. The analytical curve for isoprenaline was linear in the concentration range from 1.96 x 10(-4) to 1.07 x 10(-3) mol l(-1) with a detection limit of 8.0 x 10(-5) mol l(-1). The relative standard deviation was 1.2% for 1.96 x 10(-4) mol l(-1) isoprenaline solution (n=5). The procedure was successfully applied to the determination of isoprenaline in pharmaceutical preparations; the CuHCF modified carbon paste electrode gave comparable results to those results obtained using a UV spectrophotometric method. (C) 2004 Elsevier B.V. All rights reserved.

Sensor for cysteine based on oxovanadium(IV) complex of Salen modified carbon paste electrode

The electrochemical behavior of a carbon paste electrode modified (CPEM) with N,N′-ethylenebis(salicylideneiminato)oxovanadium(IV) complex ([(VO)-O-IV(Salen)]) was investigated as a new sensor for cysteine. Cyclic voltammetry at the modified electrode in 0.1 mol L-1 KCl Solution (pH 5.0) showed a single-electron reduction/oxidation of the Couple VO3+/VO2+. The CPEM with [VO(Salen)] presented good electrochemical stability in a wide pH range (4.0-10.0) and an ability to electrooxidate cysteine at 0.65 V versus SCE. These results demonstrate the viability of the use of this modified electrode as an amperometric sensor for cysteine determination. © 2004 Elsevier B.V. All rights reserved.

Short-term temporal changes of soil carbon losses after tillage described by a first-order decay model

Tillage stimulates soil carbon (C) losses by increasing aeration, changing temperature and moisture conditions, and thus favoring microbial decomposition. In addition, soil aggregate disruption by tillage exposes once protected organic matter to decomposition. We propose a model to explain carbon dioxide (CO2) emission after tillage as a function of the no-till emission plus a correction due to the tillage disturbance. The model assumes that C in the readily decomposable organic matter follows a first-order reaction kinetics equation as: dC(sail)(t)/dt = -kC(soil)(t) and that soil C-CO2 emission is proportional to the C decay rate in soil, where C-soil(t) is the available labile soil C (g m(-2)) at any time (t). Emissions are modeled in terms soil C available to decomposition in the tilled and non-tilled plots, and a relationship is derived between no-till (F-NT) and tilled (F-Gamma) fluxes, which is: F-T = a1F(NT)e(-a2t), where t is time after tillage. Predicted and observed fluxes showed good agreement based on determination coefficient (R-2), index of agreement and model efficiency, with R-2 as high as 0.97. The two parameters included in the model are related to the difference between the decay constant (k factor) of tilled and no-till plots (a(2)) and also to the amount of labile carbon added to the readily decomposable soil organic matter due to tillage (a,). These two parameters were estimated in the model ranging from 1.27 and 2.60 (a(1)) and - 1.52 x 10(-2) and 2.2 x 10(-2) day(-1) (a(2)). The advantage is that temporal variability of tillage-induced emissions can be described by only one analytical function that includes the no-till emission plus an exponential term modulated by tillage and environmentally dependent parameters. (C) 2008 Elsevier B.V. All rights reserved.

Hepatoprotective treatment attenuates oxidative damages induced by carbon tetrachloride in rats

The present study evaluated the hepatoprotective effect of an N-acetyl or-methionine + choline chloride + caffeine + thiamine hydrochloride + nicotinamide + pyridoxine hydrochloride compound at doses of 0.2, 0.6 and 1.0 mL/kg of b.w., and the assessment was done by the investigation of serum-enzymatic activity, metabolic functions of the liver and histophatological changes in female Wistar rats, which were subjected to experimental intoxication with CCl4. One hundred and nineteen rats were randomly distributed into 17 groups, performing five different treatments, being evaluated seven animals per treatment in four periods: 2, 4, 6 and 8 days after CCl4-induced intoxication. Treated rats with the hepatoprotective medicine (HM) presented a significant reduction in infiltration of inflammatory cells, steatosis, necrosis and liver congestion when compared to non-treated rats (control). Beside these results, the treatment showed a positive effect on circulatory alterations in the intoxicated animals, with reduction of spleen and renal congestion, as well as, promotion of a significant improvement in ALT, AST, LDH, ALP, GGT enzymatic serum activity reduction and in recovering liver function regarding the metabolism of urea, triglycerides and glucose. These findings indicate therapeutic usefulness of the compound when administered at dose 0.6 and 1.0 mL/kg of b.w. in female Wistar rats. (C) 2010 Elsevier GmbH. All rights reserved.

Carbon, nitrogen and phosphorus mineralization in two soils amended with distillery yeast

The possibility of using yeast from alcohol distilleries as a source of nutrients in soil was investigated. The following treatments were used: no fertilization (control), 0.5% (w/w) yeast, 1% (w/w) yeast, and NPK. The decomposition of yeast was monitored for 90 days in two soils. The CO, production and the microbial biomass were increased by art average of 1- to 3-fold by yeast incorporation compared to control. Protease activity also was enhanced 3- to 8-fold in the soils supplemented with yeast compared to control. The phosphatase activities were higher than control only during the first days. While nitrate contents increased in all treatments compared to control, available P only increased in the soils amended with 1%, yeast or NPK by 45-119% and 309-489%, respectively. These results indicate that there exists an excellent potential for the use of yeast in the soil as a source of nitrate and available P for plant nutrition. (C) 2003 Elsevier Ltd. All rights reserved.

Screening Botryosphaeria species for lipases: Production of lipase by Botryosphaeria ribis EC-01 grown on soybean oil and other carbon sources

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Study of the carbon dioxide chemical fixation-activation by guanidines

Fixation of CO2 is one of the most important priorities of the scientific community dedicated to reduce global warming. In this work, we propose new methods for the fixation of CO2 using the guanidine bases tetramethylguanidine (TMG) and 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]-pyrimidine (TBD). In order to understand the reactions occurring during the CO2 fixation and release processes, we employed several experimental methods, including solution and solid-state NMR, FTIR, and coupled TGA-FTIR. Quantum mechanical NMR calculations were also carried out. Based on the results obtained, we concluded that CO2 fixation with both TMG and TBD guanidines is a kinetically reversible process, and the corresponding fixation products have proved to be useful as transcarboxylating compounds. Afterward, CO2 thermal releasing from this fixation product with TBD was found to be an interesting process for CO2 capture and isolation purposes. (C) 2008 Elsevier Ltd. All rights reserved.

Electrochemical characterization of the paste carbon modified electrode with KSr2Ni0.75Nb4.25O15-delta solid in catalytic oxidation of the dipyrone

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

Selectivity of the cyclic carbonate formation by fixation of carbon dioxide into epoxides catalyzed by Lewis bases

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

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)