A time-dependent, two-step binding mode of the nitro dye flavianic acid to trypsin in acid media

Synthetic dyes bind to proteins causing selective coprecipitation of the complexes in acid aqueous solution by a process of reversible denaturation that can be used as an alternative method for protein fractionation. The events that occur before precipitation were investigated by equilibrium dialysis using bovine trypsin and flavianic acid as a model able to cause coprecipitation. A two-step mode of interaction was found to be dependent on the incubation periods allowed for binding, with pronounced binding occurring after 42 h of incubation. The first step seems to involve hydration effects and conformational changes induced by binding of the first dye molecule, following rapid denaturation due to the binding of six additional flavianate anions to the macromolecule.

Deposition of selenium thin layers on gold surfaces from sulphuric acid media: Studies using electrochemical quartz crystal microbalance, cyclic voltammetry and AFM

In this paper we report here new considerations about the relationship between the mass and charge variations (m/z relationship) in underpotential deposition (UPD), bulk deposition and also in the H(2)Se formation reaction. Nanogravimetric experiments were able to show the adsorption of H(2)SeO(3) on the AuO surface prior to the voltammetric sweep and that, after the AuO reduction, 0.40 monolayer of H(2)SeO(3) remains adsorbed on the newly reduced Au surface, which was enough to gives rise to the UPD layer. The UPD results indicate that the maximum coverage with Se(ads) on polycrystalline gold surface corresponds to approximately 0.40 monolayer, in good agreement with charge density results. The cyclic voltammetry experiments demonstrated that the amount of bulk Se obtained during the potential scan to approximately 2 Se monolayers, which was further confirmed by electrochemical quartz crystal microbalance (EQCM) measurements that pointed out a mass variation corresponding of 3 monolayers of Se. In addition, the Se thin films were obtained by chronoamperometric experiments, where the Au electrode was polarized at +0.10V during different times in 1.0 M H(2)SO(4) + 1.0 mM SeO(2). The topologic aspects of the electrodeposits were observed in Atomic Force Microscope (AFM) measurements. Finally, in highly negative potential polarizations, the H(2)Se formation was analyzed by voltammetric and nanogravimetric measurements. These finding brings a new light on the selenium electrodeposition and point up to a proposed electrochemical model for molecule controlled surface engineering. (c) 2009 Elsevier Ltd. All rights reserved.

Effect of the catalyst composition in the Pt-x(Ru-Ir)(1-x)/C system on the electro-oxidation of methanol in acid media

The effect of variations in the composition for ternary catalysts of the type Pt-x(Ru-Ir)(1-x)/C on the methanol oxidation reaction in acid media for x values of 0.25, 0.50 and 0.75 is reported. The catalysts were prepared by the sol-gel method and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), atomic absorption spectroscopy (AAS) and energy dispersive X-ray (EDX) analyses. The nanometric character (2.8-3.2 nm) of the sol-gel deposits was demonstrated by XRD and TEM while EDX and AAS analyses showed that the metallic ratio in the compounds was very near to the expected one. Cyclic voltammograms for methanol oxidation revealed that the reaction onset occur at less positive potentials in all the ternary catalysts tested here when compared to a Pt-0.75-Ru-0.25/C (E-Tek) commercial composite. Steady-state polarization experiments (Tafel plots) showed that the Pt-0.25(Ru-Ir)(0.75)/C catalyst is the more active one for methanol oxidation as revealed by the shift of the reaction onset towards lower potentials. In addition, constant potential electrolyses suggest that the addition of Ru and Ir to Pt decreases the poisoning effect of the strongly adsorbed species generated during methanol oxidation. Consequently, the Pt-0.25 (Ru-Ir)(0.75)/C Composite catalyst is a very promising one for practical applications. (c) 2007 Elsevier B.V. All rights reserved.

Carbon supported electrocatalysts prepared by the sol-gel method and their utilization for the oxidation of methanol in acid media

One of the key objectives in fuel-cell technology is to improve the performance of the anode catalyst for the alcohol oxidation and reduce Pt loading. Here, we show the use of six different electrocatalysts synthesized by the sol -gel method on carbon powder to promote the oxidation of methanol in acid media. The catalysts Pt-PbO(x) and Pt-(RuO(2)-PbO(x)) with 10% of catalyst load exhibited significantly enhanced catalytic activity toward the methanol oxidation reaction as compared to Pt-(RuO(2))/C and Pt/C electrodes. Cyclic voltammetry studies showed that the electrocatalysts Pt-PbO(x)/C and Pt-(RuO(2)-PbO(x))/C started the oxidation process at extremely low potentials and that they represent a good novelty to oxidize methanol. Furthermore, quasi-stationary polarization experiments and cronoamperometry studies showed the good performance of the Pt-PbO(x), Pt-(RuO(2)-PbO(x))/C and Pt-(RuO(2)-IrO(2))/C catalysts during the oxidation process. Thus, the addition of metallic Pt and PbO(x) onto high-area carbon powder, by the sol -gel route, constitutes an interesting way to prepare anodes with high catalytic activity for further applications in direct methanol fuel cell systems.

The influence of different co-catalysts in Pt-based ternary and quaternary electro-catalysts on the electro-oxidation of methanol and ethanol in acid media

One of the key objectives in fuel cell technology is to reduce Pt loading by the improvement of its catalytic activity towards alcohol oxidation. Here, a sol-gel based method was used to prepare ternary and quaternary carbon supported nanoparticles by combining Pt-Ru with Mo, Ta, Pb, Rh or Ir, which were used as electro-catalysts for the methanol and ethanol oxidation reactions in acid medium. Structural characterization performed by XRD measurements revealed that crystalline structures with crystallites ranging from 2.8 to 4.1 nm in size and with different alloy degrees were produced. Tantalum and lead deposited as a heterogeneous mixture of oxides with different valences resulting in materials with complex structures. The catalysts activities were evaluated by cyclic voltammetry and by Tafel plots and the results showed that the activity towards methanol oxidation was highly dependent of the alloy degree, while for ethanol the presence of a metal capable to promote the break of C-C bond, such as Rh, was necessary for a good performance. Additionally, the catalysts containing of TaOx or PbOx resulted in the best materials due to different effects: the hi-functional mechanism promoted by TaOx and a better dispersion of the catalysts constituents promoted by PbOx. (C) 2012 Elsevier B.V. All rights reserved.

Platinum–rhodium–tin/carbon electrocatalysts for ethanol oxidation in acid media: effect of the precursor addition order and the amount of tin

Carbon-supported Pt x –Rh y –Sn z catalysts (x:y:z = 3:1:4, 6:2:4, 9:3:4) are prepared by Pt, Rh, and Sn precursors reduction in different addition order. The materials are characterized by X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy techniques and are evaluated for the electrooxidation of ethanol in acidic media by cyclic voltammetry, chronoamperometry, and anode potentiostatic polarization. The influence of both the order in which the precursors are added and the composition of metals in the catalysts on the electrocatalytic activity and physico-chemical characteristics of Pt x –Rh y –Sn z /C catalysts is evaluated. Oxidized Rh species prevail on the surface of catalysts synthesized by simultaneous co-precipitation, thus demonstrating the influence of synthesis method on the oxidation state of catalysts. Furthermore, high amounts of Sn in composites synthesized by co-precipitation result in very active catalysts at low potentials (bifunctional effect), while medium Sn load is needed for sequentially deposited catalysts when the electronic effect is most important (high potentials), since more exposed Pt and Rh sites are needed on the catalyst surface to alcohol oxidation. The Pt3–Rh1–Sn4/C catalyst prepared by co-precipitation is the most active at potentials lower than 0.55 V (related to bifunctional effect), while the Pt6–Rh2–Sn4/C catalyst, prepared by sequential precipitation (first Rh and, after drying, Pt + Sn), is the most active above 0.55 V.

Adsorption of Pb(2+), Cu(2+) and Cd(2+) in FDU-1 silica and FDU-1 silica modified with humic acid

Ordered mesoporous silica with cubic structure, type FDU-1, was synthesized under strong acid media using B-50-6600 poly(ethylene oxide)-poly(butilene oxide)-poly(ethylene oxide) triblock copolymer (EO(39)BO(47)EO(39)) and tetraethyl orthosilicate (TEOS). Humic acid (HA) was modified to the synthesis process at a concentration of 1.5 mmol per gram of SiO(2). Thermogravimetry, small angle X-ray diffraction, nitrogen adsorption and high resolution transmission electron microscopy were used to characterize the samples. The pristine FDU-1 and FDU-1 with incorporated 1.5 mmol of HA were tested for adsorption of Pb(2+), Cu(2+) and Cd(2+) in aqueous solution. Incorporation of humic acid into the FDU-1 silica afforded an adsorbent with strong affinity for Cd(2+), Cu(2+) and Pb(2+) from single ion solutions. Adsorption of Cu(2+) was significantly enhanced after incorporation of humic acid, a fact that can be explained by the formation of complexes with carboxylic and phenolic groups at low concentrations of the metal cation. The results demonstrated the potential applicability of FDU-1 with incorporated HA in the removal of low concentrations of heavy metal cations from aqueous solution, such as wastewaters, after usual precipitation of metal hydroxides in alkaline medium and proper pH conditioning in the range between 6 and 7. (C) 2007 Elsevier Inc. All rights reserved.

Determinação espectrofotométrica de hexametilenotetramina (HMT) em medicamentos, utilizando ácido cromotrópico e forno de micro-ondas

This paper proposes a methodology for spectrophotometric determination of hexamethylenetetramine (HMT) by using chromotropic acid in a phosphoric acid media employing a domestic microwave oven as a source of heating. The reddish-purple soluble product is quantitatively formed after 30 s of irradiation and obeys the Beer´s law in the range between 0.1-1.2 mg L-1 HMT (r = 0.99925). The method was applied successfully in commercial pharmaceutical preparations containing dyes in their composition. The results showed that the method proposed is feasible for simplicity, speed, low cost, precision and accuracy when compared with United States Pharmacopeia official method.

Determinação eletroquímica da capacidade antioxidante de sucos de frutas industrializados usando o CRAC assay

Fruits juices are natural sources of several compounds that present antioxidant action. Together with the fruits, they contribute with almost 40% of the antioxidant capacity in a healthy diet avoiding and preventing diseases deriving from oxidative stress. The present study determined the antioxidant capacity of seven samples of industrialized fruits juices applying CRAC (Ceric Reducing/Antioxidant Capacity) assay, a new electrochemistry assay that evaluates, by means of chronoamperometric measurements, the ability of a sample in reducing species Ce4+ in acid media. At the end of the assay was obtained the following classification: cashew > guava > grape > mango > apple > orange > passion fruit.

Temperature effects on the oscillatory electro-oxidation of methanol on platinum

We report in this paper the effect of temperature on the oscillatory electro-oxidation of methanol on polycrystalline platinum in aqueous sulfuric acid media. Potential oscillations were studied under galvanostatic control and at four temperatures ranging from 5 to 35 degrees C. For a given temperature, the departure from thermodynamic equilibrium does not affect the oscillation period and results in a slight increase of the oscillation amplitude. Apparent activation energies were also evaluated in voltammetric and chronoamperometric experiments and were compared to those obtained under oscillatory conditions. In any case, the apparent activation energies values fell into the region between 50 and 70 kJ mol(-1). Specifically under oscillatory conditions an apparent activation energy of 60 +/- 3 kJ mol(-1) and a temperature coefficient q(10) of about 2.3 were observed. The present findings extend our recently published report (J. Phys. Chem. A, 2008, 112, 4617) on the temperature effect on the oscillatory electro-oxidation of formic acid. We found that, despite the fact that both studies were carried out under similar conditions, unlike the case of formic acid, only conventional, Arrhenius, dynamics was observed for methanol.

The role of the steps in the cleavage of the C-C bond during ethanol oxidation on platinum electrodes

Ethanol oxidation has been studied on stepped platinum single crystal electrodes in acid media using electrochemical and Fourier transform infrared (FTIR) techniques. The electrodes used belong to two different series of stepped surfaces: those having (111) terraces with (100) monoatomic steps and those with (111) terraces with (110) monoatomic steps. The behaviors of the two series of stepped surfaces for the oxidation of ethanol are very different. On the one hand, the presence of (100) steps on the (111) terraces provides no significant enhancement of the activity of the surfaces. On the other hand, (110) steps have a double effect on the ethanol oxidation reaction. At potentials below 0.7 V, the step catalyzes the C-C bond cleavage and also the oxidation of the adsorbed CO species formed. At higher potentials, the step is not only able to break the C-C bond, but also to catalyze the oxidation of ethanol to acetic acid and acetaldehyde. The highest catalytic activity from voltammetry for ethanol oxidation was obtained with the Pt(554) electrode.

Morphological and electrochemical investigation of RuO(2)-Ta(2)O(5) oxide films prepared by the Pechini-Adams method

Preparation methods can profoundly affect the structural and electrochemical properties of electrocatalytic coatings. In this investigation, RuO(2)-Ta(2)O(5) thin films containing between 10 and 90 at.% Ru were prepared by the Pechini-Adams method. These coatings were electrochemically and physically characterized by cyclic voltammetry, scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). The composition and morphology of the oxide were investigated before and after accelerated life tests (ALT) by EDX and SEM. SEM results indicate typical mud-flat-cracking morphology for the majority of the films. High resolution SEMs reveal that pure oxide phases exhibit nanoporosity while binary compositions display a very compact structure. EDX analyses reveal considerable amounts of Ru in the coating even after total deactivation. XRD indicated a rutile-type structure for RuO(2) and orthorhombic structure for Ta(2)O(5). XPS data demonstrate that the binding energy of Ta is affected by Ru addition in the thin films, but the binding energy of Ru is not likewise influenced by Ta. The stability of the electrodes was evaluated by ALT performed at 750 mA cm(-2) in 80 degrees C 0.5 mol dm(-3) H(2)SO(4). The performance of electrodes prepared by the Pechini-Adams method is 100% better than that of electrodes prepared by standard thermal decomposition.

Kinetic measurements during transient film growth on zinc

Quimica Nova, Vol. 32, Nº2

Ozonólise das ligninas organossolve e kraft eucalipto. Parte II: cinética nos meios ácido e básico

Organosolv and kraft lignins were treated with ozone both in basic and acid media and the reaction was studied kinetically. In contrast to reported studies, ozone was more efective in basic medium. Kraft lignin was degraded faster than organosolv lignin in both media but in the basic medium the rate of reaction was very much faster than in the acid one: for kraft lignin, the observed degradation was 93% for 2 min of reaction in the basic medium and 56% for 10 min of reaction in the acid medium; for organosolv lignin, 47% and 25%, respectively, in the same times. Higher phenolic hydroxyl groups contents increase the reaction rate.

Determinação eletroquímica da capacidade antioxidante de sucos de frutas industrializados usando o CRAC assay

Fruits juices are natural sources of several compounds that present antioxidant action. Together with the fruits, they contribute with almost 40% of the antioxidant capacity in a healthy diet avoiding and preventing diseases deriving from oxidative stress. The present study determined the antioxidant capacity of seven samples of industrialized fruits juices applying CRAC (Ceric Reducing/Antioxidant Capacity) assay, a new electrochemistry assay that evaluates, by means of chronoamperometric measurements, the ability of a sample in reducing species Ce4+ in acid media. At the end of the assay was obtained the following classification: cashew > guava > grape > mango > apple > orange > passion fruit.