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5 pags., 2 figs., 2 tabs., The study of non-precious metal catalysts (NPMCs) as alternatives to platinum for oxygen reduction is crucial if the use of fuel cells is to become more widespread. Among NPMCs, pyrolyzed catalysts (Fe-N-C) are particularly promising in both basic and acid media. The characterization of active sites and the understanding of the oxygen reduction reaction (ORR) mechanism are crucial for the design of active Fe-N-C catalysts. In this study, we have tested the involvement of the metal centre in the ORR process at pH 13 for two pyrolyzed iron porphyrins. The pyrolyzed catalysts present a FeN4 active site structure similar to that of the porphyrin precursors. Regarding the mechanism, we have found evidence for the crucial role of the Fe(II) centres. There is a direct relation between the Fe(III)/(II) redox transition of the catalysts and the onset potential of the ORR, showing that the electrogeneration of Fe(II) from Fe(III)OH– controls the catalysis. The poisoning of iron centres with CN− induces a decrease in the ORR activity. However, the onset potential for H2O2 generation remains unchanged. The Tafel plots show two different slopes at high and low overpotentials. Based on these results, we propose two different mechanisms, both dependent on the redox potential of the catalysts and the FeO2 binding energy., This work was supported by Fondecyt Regular Projects 1161117,1181037. Fondecyt Postdoctoral Projects 3170330, 3180509, and Conicyt Scholar ships 1160955,21160212

In this study, the corrosion inhibition properties of nanocontainer-type layered double hydroxide (LDH) are evaluated on iron that is immersed in a 3.5% NaCl aqueous solution. LDH ZnAl-NO3 was synthesized via coprecipitation. The material presents satisfactory crystallinity with a Zn/Al ratio of 2:1. Methyl orange (MO) has been added into the synthesis process by exchange with nitrate ions and/or by adsorption of MO onto LDH surfaces (LDH-MO). Iron was immersed in solutions with various concentrations of LDH and LDH-MO ranged 1–6 gl−1, and the corrosion inhibition properties were investigated using linear sweep votammetry, electrochemical impedance spectroscopy (EIS), and SEM. Based on pitting potential studies, LDH has demonstrated inhibition of the pitting corrosion process, and the optimal concentration was identified as 2 gl−1. The presence of MO in LDH provides excellent anticorrosive properties with a mixed inhibition mechanism. The corrosion potential of LDH-MO presents more noble values and exchange current densities that are one order of magnitude less than those of the bare iron after 72 h of immersion in a 3.5% NaCl aqueous solution. EIS results corroborated that the corrosion resistance increased when 2 gl−1 of LDH-MO was in solution. SEM images support the anticorrosive behaviour of the LDH-MO.

Peroxydisulfate (PDS, S2O82−)-based advanced oxidation processes have been developed as an alternative to those based on OH, as PDS activation yields a much more stable radical like SO4 − that can maintain the oxidation ability of water treatment systems for longer time. Here, the electrochemical PDS activation has been investigated using reticulated vitreous carbon (RVC) substrate modified with Fe3O4 nanoparticles (NPs) as cathode. The NPs were exhaustively characterized by different surface analysis techniques (TEM, SEM) and Mossbauer spectroscopy. Cyclic voltammetry and linear sweep voltammetry with a rotating disk electrode allowed concluding that the main electrocatalytic role in the cathodic PDS activation to SO4 − corresponded to the Fe(II) active sites continuously promoted upon cathodic polarization. These sites were less catalytic for O2 reduction reaction, although it was still feasible with n = 2.7 electrons as determined from Koutecky-Levich analysis. Both cathodic reactions followed an inner-sphere reaction mechanism. The Fe3O4-modified RVC cathodes were employed to electrolyze Methylene Blue aqueous solutions at pH 3.5, employing different current values and PDS concentrations. Dissolved O2 was purged to impede the competitive cathodic H2O2 production and Fenton’s reaction. The occurrence of dye adsorption/electrosorption on the cathode reduced the mass transport limitations, enhancing the reaction between SO4 − and organic molecules. The best operation conditions to reach total and fast color removal at 18 min were 2 mM PDS and 10 mA, yielding > 80% TOC abatement at 45 min. Reproducible degradation profiles were found after 5 runs, thereby ensuring the stability of the Fe3O4-modified RVC, with no iron sludge production.

9 pags., 6 figs., 2 tabs., Pyrolyzed non-precious metal catalysts (NPMCs) are promising materials to replace platinum-based catalysts in the cathode of the fuel cells. These catalysts present high catalytic activity both in alkaline and acid media for the oxygen reduction reaction (ORR). These catalysts are essentially heterogeneous as they can present different types of active sites. MNx structures have been proposed as the most active for the ORR, similar to those of the MN4 structures of metal porphyrins and phthalocyanines. Several parameters have been proposed as reactivity descriptors to correlate the structure of these materials with their catalytic activity, such as the amount of MNx and of pyridinic nitrogens in the graphitic structure. In this study, we have explored the metal center redox potential of the catalyst as an overall reactivity descriptor. We have investigated this descriptor for pyrolyzed and intact catalysts for the ORR in acid and basic media. We have found that for all catalysts tested, there is a linear correlation between the redox potential of the catalyst and the catalytic activity expressed as (log i)). The activity increases as the redox potential becomes more positive. The correlation gives a straight line of slope close to +0.12 V/decade which agrees with the theoretical slope proposed in a previous publication assuming the adsorbed M − O follows a Langmuir isotherm and that the redox potential is directly linked to the M − O binding energy. The Tafel plots present two slopes, at low and high overpotentials. Based on these results, we proposed two different mechanisms. The low Tafel slopes of −60 mV appear at potentials where the surface concentration of M(II) active sites is potential dependent (close to the onset potential). At higher overpotentials the surface coverage of M(II) becomes constant and the slope changes to −0.120 V/decade., This work was supported by Fondecyt Regular Projects 1161117,1181037, Fondecyt Postdoctoral Projects 3170330 and 3180509, andConicyt Scholarship 21160955.

In the search for new quinoid compounds endowed with potential anticancer activity, the synthesis of novel heterodimers containing the cytotoxic 7-phenylaminoisoquinolinequinone and 2-phenylaminonaphthoquinone pharmacophores, connected through methylene and ethylene spacers, is reported. The heterodimers were prepared from their respective isoquinoline and naphthoquinones and 4,4&prime, diaminodiphenyl alkenes. The access to the target heterodimers and their corresponding monomers was performed both through oxidative amination reactions assisted by ultrasound and CeCl3&middot, 7H2O catalysis &ldquo, in water&rdquo, This eco-friendly procedure was successfully extended to the one-pot synthesis of homodimers derived from the 7-phenylaminoisoquinolinequinone pharmacophore. The electrochemical properties of the monomers and dimers were determined by cyclic and square wave voltammetry. The number of electrons transferred during the oxidation process, associated to the redox potential EI1/2, was determined by controlled potential coulometry.

Multilayers of polyaniline (PAni) and PAni/nanotubes-TiO2 composite were compared for corrosive protection on carbon steel and welded carbon steel. The layer porosity, morphology and thickness were characterized. PAni coating showed the best protection when a layer of 2 μm was deposited on steel surface. In spite of the good anticorrosive behaviour of PAni, when the layer thickness was increased up to 4.5 μm a decrease in the anticorrosive behaviour is detected due to the development of mechanical tensions which increase the porosity of the film. However, the addition of TiO2 nanotubes to PAni coatings shows an interesting ability to inhibit this undesirable mechanical effect, showing a good anticorrosive behaviour and lower porosity when thickness layer is increased. The morphological and electrochemical tests of the samples showed good resistance against degradation in chloride medium and in the salt spray analysis, promoting improvement of corrosion protection in an aggressive corrosion medium.

Corrosion of zinc in aqueous methanesulfonic acid has been evaluated over a wide range of concentrations of acid (0.5–5 mol dm−3), dissolved zinc (0.5–2 mol dm−3), and electrolyte temperature (22–50 °C). The corrosion rate of zinc, in terms of weight loss and the volume of hydrogen evolved, varied with time and it was found to be highly dependent on the surface state and electrolyte conditions. With an initial active layer of zinc present, the corrosion rate rapidly increased following a decline when the proton concentration in the solution decreased to ca. 0.56 mol dm−3. Organic and inorganic inhibitors were added to the electrolyte to suppress the zinc corrosion in 1 mol dm−3 methanesulfonic acid. The strong adsorption and blocking effects of cationic organic adsorption inhibitors, such as cetyltrimethyl ammonium bromide and butyltriphenyl phosphonium chloride, led to a significant decrease in zinc corrosion over a 10 h immersion period. With the addition of indium and lead ions inhibitors, the zinc surface showed less activity. Zinc corrosion continued to a smaller extent in the presence of these metallic inhibitors during the first few hours, but the metallic layer of the inhibitors did not cover the surface completely resulting in continued hydrogen evolution and making the inhibitors less effective at longer times.

In classical volcano correlations in electrocatalysis, the shape of (log io) plots versus the binding energy of the reactant to active sites, the maximum activity is associated to a situation where the surface coverage of reactant species is equal to 0.5 corresponding to a free energy of adsorption of the reactant equal to zero. When studying electrochemical reactions catalysed by macrocyclic transition metal complexes adsorbed on graphite electrodes, volcano correlations are found when plotting the activity versus the formal potential of the catalyst for several reactions, assuming that the formal potential is somehow related to the free energy of the adsorption of the reacting molecule. In this work we offer an interpretation different from that given in the literature for these correlations for the electrooxidation of hydrazine. The highest catalytic activity is achieved when the formal potential of the catalyst approaches the N2H4/N2 reversible potential. In contrast, if log i (normalized for the actual surface concentrations of Fe(II) active sites at constant potential) is plotted versus the difference between the Fe(II)/(I) formal potential of the catalysts and the standard potential of the N2H4/N2 reaction, the correlation is linear with a slope close to 2RT/F. Keywords: Falling region, Tuning formal potential, Design best catalyst, Surface redox catalysis

An efficient and inexpensive catalyst for the oxygen reduction reaction (ORR) is the key missing component for large-scale development of fuel cells. Bio-inspired tethered electrocatalysts could be the solution to this problematic reaction. Either unsubstituted Fe phthalocyanine (FePc) or Fe hexadecachloro-phthalocyanine (16(Cl)FePc) was anchored to carbon nanotubes (CNTs) via a pyridine axial ligand. The results show that the fifth coordination plays a major role in increasing the catalytic activity of FePc and 16(Cl)FePc for the ORR. The coordination also allows the decoupling of the metal centre from the carbon support, thus changing the geometrical and electronic structure and hindering the production of HO. The pentacoordinated catalysts were stable in acidic pH according to the rotating disk analysis, but the activity of the hexadecachloro compound was not higher than that of the unsubstituted phthalocyanine. Cl atoms reduced the coupling between O and Fe, mismatching the energy of the frontier orbitals and lowering the activity towards the reduction of O.

Reticulated vitreous carbon (RVC) of different porosities (20, 45, 60, 80, and 100 ppi—pores per inch) has been used as a large surface area substrate for preparing 3D-like PbO2 coatings (RVC/PbO2) as well as composite coatings with hydrothermally synthesized titanate nanotubes (RVC/PbO2/TiNT) by galvanostatic electrodeposition from baths containing lead(II) methanesulfonate and methanesulfonic acid. The effect of the RVC porosity on the coating thickness, the electrocatalytic behaviour and the ability to remove the colour and total organic carbon (TOC) from solutions containing the azo dye Methyl Orange has been systematically assessed. As shown from scanning electron micrographs, the greatest thickness (up to 120 μm) was obtained using > 60 ppi, but the β-PbO2 nanocrystallytes mainly grew on the external surface, leaving mostly uncoated inner RVC stripes and ending in planar-like PbO2-based electrodes. In contrast, thinner but perfectly adherent and homogeneous coating of the inner and outer surface was achieved with 20-60 ppi, showing electrodes with an optimal three-dimensionallity. This was especially confirmed by cyclic voltammograms for the composite coatings, as deduced from their highest electroactivity that can be related to enhanced adsorption onto the TiNT clusters and the larger ability to produce active PbO2( O H ). The comparative electro-oxidation of 0.25 × 10−3 mol dm−3 Methyl Orange acidic solutions in 0.05 mol dm−3 Na2SO4 at 0.6 A demonstrated that RVC (45 ppi)/PbO2/TiNT was the optimum material. It allowed the quickest decolourisation, reaching 60% in 2.5 min and > 98% at 45 min, and > 55% TOC abatement at 240 min. The anode presented a perfect surface coverage, with no evidence of RVC degradation. The effect of dye concentration and supporting electrolyte nature was studied, revealing a very positive effect of NaCl.

Following an adapted three-step seed-mediated method, we synthesize colloidal Au thin and long (L > 100 nm) nanorods (NRs) and characterize the metallic nanostructures evolving from the initial Au nanoparticle (NPs) seeds to thiolate-functionalized NRs, using HRTEM and ultraviolet, visible, and near-infrared absorption spectroscopy (UV-vis-NIR). For the long NRs we analyze the role of several solvents and rod concentration on the spectral features of the assembled products, which are further studied with simulated spectra. Superimposed to a broad resonance in the range 700-900 nm, which corresponds to short (L < 100 nm) interacting nanorods, the growth of long nanorods is clearly identified with the emergence of a robust resonance at 960 nm, linked to the three half-wavelength antenna plasmon mode. This mode is enhanced when the nanorod concentration decreases and splits into two peaks when the thiolate coverage chemically modifies the rod surface by a thin layer of nanometer size. This behavior is explained with a dielectric model based on ab initio calculations of thiolate-gold cluster surfaces., We gratefully acknowledge the support of the Basque Departamento de Educacion and the UPV/EHU (Grant No.IT-366-07) and Spanish Ministry of Economy and Competitiveness MINECO (FIS2013-48286-C2-1-P and FIS2013-41184-P) and the ETORTEK research program funded by the Basque Departamento de Industria and the Diputacion Foral de Guipuzcoa (nanoGUNE 2014). F.J. Recio thanks a Fondecyt 3130538 Postdoctoral Grant.

Well-dispersed magnetite nanoparticles of different sizes between 15 and 43 nm were synthesized by an electrochemical method in a controlled manner by simply changing the synthesis temperature. These nanoparticles were used as a reusable adsorbent to remove Cr(VI) from aqueous solution. The recovery efficiency was found to be highly dependent on environmental parameters, such as temperature and pH. In addition, it was demonstrated that the initial concentrations of both Cr(VI) and magnetite nanoparticles strongly influence the removal capability of these nanomaterials. Remarkably, the nanoparticle size has a key role on the Cr(VI) adsorption efficiency, which gradually increases as the diameter decreases due to the augmentation of the surface area. The low aggregation in the case of small particles that results from the low magnetization saturation values also contributes to the enhancement of the surface area available for Cr(VI) adsorption. In contrast, nanoparticles with larger sizes are more easily manipulated by a magnet, and the efficiency is largely maintained after five cycles. The adsorption process fits the Langmuir isotherm model well, and the reaction was found to follow a pseudo-second-order rate., The authors are grateful to the Spanish Ministry of Science and Innovation (MAT2012-37109-C02-02, MAT2013-47878-C2-1-R and CSD2008-00023).

The redox potential of macrocyclic complexes is a very predictive reactivity index for the electrocatalytic activity of these molecules and it can be easily measured under the same conditions of the kinetic experiments. It reflects directly the catalytic activity of a given complex. We have investigated the effect of the Co(II)/(I) formal potential of CoN4 macrocyclics complexes on the catalytic activity of a series of Co porphyrins and Co phthalocyanines for the electrooxidation of l -cysteine. The complexes were adsorbed on ordinary pyrolytic graphite. A correlation of log i (at constant potential) versus the Co(II)/(I) formal potential of the catalysts gives a volcano curve. Our results clearly show that the Co(II)/(I) formal potential of N 4 -macrocyclic complexes needs to be adjusted to values around −0.96 V vs. SCE to obtain the highest catalytic activity for the oxidation of l -cysteine at pH 13.

The M(II)/(I) formal potential of MN4 macrocyclic complexes dictates their electrocatalytic activity for many reactions and L-cysteine oxidation is not an exception. In this work we review the literature related to this reaction and propose a semi-empirical model that can describe the catalytic activity of these chelates in terms of their formal potential. A correlation of log i (at constant potential) versus the M(II)/(I) formal potential for M= Fe,Co) of the catalysts gives a volcano curve. Our results clearly show that the M (II)/(I) formal potential of N 4 -macrocyclic complexes needs to be adjusted to values around -1.0 V vs. SCE to obtain the highest catalytic activity for the oxidation of L-cysteine. When comparing chelates of different metals (M= Cr, Mn, Fe, Co) of tetrasulphonated phthalocyanines only a linear correlation is obtained.

Nanostructured nickel was electrodeposited on a stainless steel plate. The convective-diffusion mass transfer to this nanostructured electrode was compared to that of a planar, mirror polished solid nickel electrode using the limiting current technique, for the reduction of ferricyanide, hexacyanoferrate (III) ion in an undivided cell. The effect of introducing a turbulence promoter into the electrolyte channel was also evaluated for each electrode under steady state conditions. At a Reynolds number of 700, the product of mass transfer coefficient and active electrode area, kLA for the nanostructured nickel electrode increases over 11 times compared to the mirror polished planar nickel electrode. In the presence of a turbulence promoter, the nanostructured nickel electrode shows an approximately 23 times increase in kLA compared to the planar mirror polished nickel electrode. The dimensionless mass transfer correlations Sh=aRebScdLee are compared to others in the literature. © 2012 Elsevier Ltd., J. Recio, P. Herrasti and L. Vazquez are grateful to the Spanish Ministry of Science and Innovation (MAT2009-C02-02, FIS2009-12964-C05-04) for financial support. L. Vazquez also acknowledges the Comunidad Autónoma de Madrid project S2009/PPQ-1642, AVANSENS.

The critical conditions for hydrogen embrittlement (HE) risk of high strength galvanized steel (HSGS) wires and tendons exposed to alkaline concrete pore solutions have been evaluated by means of electrochemical and mechanical testing. There is a relationship between the hydrogen embrittlement risk in HSGS and the length of hydrogen evolution process in alkaline media. The galvanized steel suffers anodic dissolution simultaneously to the hydrogen evolution which does not stop until the passivation process is completed. HSGS wires exposed to a very high alkaline media have showed HE risk with loss in mechanical properties only if long periods with hydrogen evolution process take place with a simultaneous intensive galvanized coating reduction.

We have correlated the in vitro results of testing the susceptibility of Cryptococcus neoformans to fluconazole with the clinical outcome after fluconazole maintenance therapy in patients with AIDS-associated cryptococcal disease. A total of 28 isolates of C. neoformans from 25 patients (24 AIDS patients) were tested. The MICs were determined by the broth microdilution technique by following the modified guidelines described in National Committee for Clinical Standards (NCCLS) document M27-A, e.g., use of yeast nitrogen base medium and a final inoculum of 10 4 CFU/ml. The fluconazole MIC at which 50% of isolates are inhibited (MIC 50 ) and MIC 90 , obtained spectrophotometrically after 48 h of incubation, were 4 and 16 μg/ml, respectively. Of the 25 patients studied, 4 died of active cryptococcal disease and 2 died of other causes. Therapeutic failure was observed in five patients who were infected with isolates for which fluconazole MICs were ≥16 μg/ml. Four of these patients had previously had oropharyngeal candidiasis (OPC); three had previously had episodes of cryptococcal infection, and all five treatment failure patients had high cryptococcal antigen titers in either serum or cerebrospinal fluid (titers, >1:4,000). Although 14 of the 18 patients who responded to fluconazole therapy had previously had OPC infections, they each had only a single episode of cryptococcal infection. It appears that the clinical outcome after fluconazole maintenance therapy may be better when the infecting C. neoformans strain is inhibited by lower concentrations of fluconazole for eradication (MICs

We performed a prospective study to compare the Etest and the microdilution method (NCCLS guidelines) for determining the MICs of fluconazole, itraconazole, flucytosine and amphotericin B for 35 strains of Cryptococcus neoformans. For the microdilution method (MDM) RPMI 1640 medium with 2% glucose was used for fluconazole, itraconazole and flucytosine, and Antibiotic Medium 3 for amphotericin B. For the Etest, RPMI 1640 medium with 2% glucose and solidified with 1.5% agar was used for the four antifungal agents. Amphotericin B was also tested on Antibiotic Medium 3 solidified with 1.5% agar. Fluconazole and flucytosine MICs by the Etest showed good correlation with the broth MDM (81.1 and 89.2% agreement within two dilutions, respectively). With the tested population of itraconazole- and amphotericin B-susceptible isolates, the MIC agreement for itraconazole was 54%; amphotericin B showed the lowest agreement (8.1% on Antibiotic Medium 3 and 13.5% on RPMI).

Hematology and serum biochem­ ical data are presented for the Egyptian mon­ goose, Herpestes ichneumon, caught in Doñana National Park, southwestern Spain