Study of the influence of phosphoric acid in steel anaerobic corrosion via the hydrogen evolution reaction.

Although it is well known that the phosphate species are quiet electrochemically inert when considering their calculated redox potential, few studies since the end of 80’s reported electrochemical phenomenon observed in the reduction domain which were linked to the presence of phosphate species. Some authors proposed that phosphate ions and weak acids in general catalysed the electrochemical reduction of water [1-3] following the kind of reactions written above: Electrochemical reactions H2PO4- + e- Had + HPO42- (1) Had + H2PO4- + e- H2 + HPO42- (2) Acido-basic equilibrium H2PO4- + OH-- H2O + HPO42- (3) Combining the reactions, the reduction of water was obtained 2 H2O + 2e- H2 + 2OH- (4) Marinovic and Despic [1] assumed that the hydrogen evolution was more likely to occur from species other than water, since the bond between the hydrogen atom and the rest of the molecule is weaker in weak acid compared with the hydrogen-oxygen bond in a water molecule. This was shown on silver electrodes [2] and also on platinum ones [1]. In a previous work [3], we showed that phosphate ions exhibited the same electrochemical behaviour on stainless steel. A theoretical model was proposed according to the experimental data the model showed that a significant quantity of molecular hydrogen was produced by the mechanism presented above. In the present paper, the influence of phosphoric acid on hydrogen evolution reaction has been studied by voltammetry on platinum and stainless steel rotating disc electrodes. A linear correlation between acid concentration and the absolute value of the current at certain reduction potential has been verified. The effect of the pH value of the solution in the obtained current has demonstrated to be strongly related to the dissociation state of the acid. In a second part, as the hydrogen evolution reaction is the principal cathodic reaction of metal corrosion in anaerobic aqueous environments, the role that weak acids can play in this process was studied. Corrosion experiments on carbon steel were carried out in phosphoric acid solution under anaerobic conditions. The influence of hydrogen in the solution was also studied. In the absence of oxygen, a substantial increase of corrosion rate was found when carbon steel samples were submerged in low phosphoric acid concentration solution compared to that obtained in distilled water

Hydrogen production by electrolysis of a phosphate solution on a stainless steel cathode

The catalytic properties of phosphate species, already shown on the reduction reaction in anaerobic corrosion of steels, are exploited here for hydrogen production. Phosphate species work as a homogeneous catalyst that enhances the cathodic current at mild pH values. A voltammetric study of the hydrogen evolution reaction is performed using phosphate solutions at different concentrations on 316L stainless steel and platinum rotating disk electrodes. Then, hydrogen is produced in an electrolytic cell using a phosphate solution as the catholyte. Results show that 316L stainless steel electrodes have a stable behaviour as cathodes in the electrolysis of phosphate solutions. Phosphate (1 M,pH 4.0/5.0) as the catholyte can equal the performance of a KOH 25%w solution with the advantage of working at mild pH values. The use of phosphate and other weak acids as catalysts of the hydrogen evolution reaction could be a promising technology in the development of electrolysis units that work at mild pH values with low-cost electrodes and construction materials

Combining phosphate species and stainless steel cathode to enhance hydrogen evolution in microbial electrolysis cell (MEC)

Microbial electrolysis cells (MEC) must work around neutral pH because of microbial catalysis at the anode. To develop a hydrogen evolution cathode that can work at neutral pH remains a major challenge in MEC technology. Voltammetry performed at pH 8.0 on rotating disk electrodes showed that the presence of phosphate species straightforwardly multiplied the current density of hydrogen evolution, through the so-called cathodic deprotonation reaction. The mechanism was stable on stainless steel cathodes whereas it rapidly vanished on platinum. The phosphate/stainless steel system implemented in a 25 L MEC with a marine microbial anode led to hydrogen evolution rates of up to 4.9 L/h/m2 under 0.8 V voltage, which were of the same order than the best performance values reported so far. Keywords: Hydrogen; Microbial electrolysis cell (MEC); Stainless steel; Phosphat

Des aspects positifs issus des recherches en biocorrosion : de la production d'hydrogène aux biopiles à combustible

La corrosion induite par des microorganismes ou biocorrosion est un problème qui génère de lourdes pertes économiques mondiales (plusieurs milliards d'euros par an). Malgré de nombreux progrès dans la compréhension des mécanismes, la complexité du phénomène a empêché de trouver des solutions définitives au problème et inspire encore beaucoup de travaux de recherche. La participation dans le phénomène de biocorrosion de mécanismes catalytiques induits par les acides faibles a été étudiée dans ce travail. Un autre objectif de la thèse a été d'exploiter les phénomènes catalytiques mis en évidence dans les recherches en biocorrosion pour réaliser d'autres applications : production d'énergie dans des biopiles à combustible ou production d'hydrogène par voie électrochimique dans des conditions douces. Les travaux ont montré que la présence des acides faibles et des acides aminés dans des biofilms pourrait jouer un rôle important dans la biocorrosion des aciers en accélérant le phénomène par la catalyse de la réduction de l'eau. La réversibilité de ce mécanisme, pressentie et prouvée, pourrait expliquer l’augmentation de la corrosion lorsque l'hydrogène produit est évacué (consommation, agitation, …). Par ailleurs, les phosphates permettent la production d'hydrogène par électrolyse dans des conditions douces de pH (pH 4,0 - 8,0) avec une performance égale ou meilleure que celle de l'électrolyse alcaline. Enfin, les matériaux industriels, tels que l'acier et le titane, pourraient être utilisés pour la fabrication d’électrodes enzymatiques en vue d’une utilisation dans des biocapteurs ou des microsystèmes. L’utilisation du système glucose oxydase/glucose dans une pile à combustible aqueuse dont la cathode est en acier inoxydable, permet d’améliorer les performances de la pile grâce à la production du peroxyde d'hydrogène qui est très facile à réduire. En outre, l’utilisation de matériaux avec des microstructures comme les aciers grenaillés mériterait d’être approfondie pour exploiter la remarquable réactivité qu’ils présentent par rapport aux électrodes lisses. ABSTRACT : Microbially influenced corrosion or biocorrosion is a problem that generates heavy global economic losses (several billion euros per year). In spite of the progress made on the understanding of the underlying mechanisms, the complexity of the phenomenon has prevented finding definitive solutions to the problem and continues to inspire many research works. The participation in biocorrosion of catalytic mechanisms induced by weak acids was studied in this work. Another objective of the thesis has been to take advantage from catalytic phenomena found in biocorrosion research to apply them in other areas: energy production with biofuel cells or electrochemical hydrogen production in mild conditions. This work has shown that the presence of weak acids and amino acids inside biofilms could play a major role in steel biocorrosion accelerating the phenomenon through the catalysis of the water reduction reaction. The reversibility of this mechanism, discerned and proved here, could explain the corrosion increase when hydrogen is removed (bacterial consumption, agitation ...). In addition, phosphates allow the production of hydrogen by electrolysis in mild pH conditions (pH 4.0 - 8.0) with an equal or better performance than those found in alkaline electrolysis. Finally, industrial materials like stainless steel and titanium could be used in the fabrication of enzymatic electrodes for biosensors or microsystems. The use of the glucose oxidase/glucose system in an aqueous fuel cell with a stainless steel cathode, allows the improvement of the cell performance thanks to the production of hydrogen peroxide that is easily reduced. Moreover, the use of materials with microstructured surfaces like sandblasted steels deserve to be studied in detail to exploit the remarkable reactivity they present compared to smooth electrodes

Anti-atherogenic properties associated with the antioxidant activity from the hydrophilic extracts of Halimeda incrassata (Chlorophyta, Bryopsidales)

Seaweeds are a source of natural antioxidants having potential application in oxidative stress and associated diseases. In this work, anti-atherogenic properties associated with the antioxidant activity from the hydrophilic extracts of Halimeda incrassata were studied. The phenolic content assessed inthe aqueous extract and fraction phenolic acids (FPA) was 0.13 ± 0.05 and 0.47 ± 0.09 mg of gallic acid equivalents (GAE)/g dry seaweed, respectively. In DPPH?, radical scavenging assay fractions exhibited a dependent concentration. The seaweeds extract inhibited the desoxirribose oxidation in the presenceor absence of EDTA (IC50 = 1.91± 0.09 mg/mL) (IC50 = 2.95 ± 0.01 mg/mL). In vivo antioxidant properties of FPA-H.incrassata were investigated in rats with a CCl4-induced liver injury. Pre-treatment with H.incrassata led to approximately 50% reductions in liver TBARS levels. The treatment with H. incrassataFPA also increased the activity of the CAT enzyme, which in turn resulted in an enhanced antioxidantdefense. The expression of Catalase by PCR-RT technique demonstrated a higher gene expression when compared with that which was observed in the CCl 4-treated group. Antiatherogenic properties were studied in the inhibition of lipoprotein oxidation mediated by Cu2+ or HRP/H2O2, free radicalscavenging, and metal ion chelation, and it was dose dependent with a higher concentration needed for the aqueous extract than for the FPA fraction. Antioxidant activity was also improved in macrophages as evaluated in the cell supernatant (by TBARS formation); and by luminol enhanced chemiluminescence after cell activation with zymosan; and a degree of cell lipoperoxidation wasdecreased by the Halimeda incrassata extract. The results of this work add to the antioxidant potential of the seaweed for its application in oxidative stress associated conditions.Fil: Vidal-Novoa, Alexis. Universidad de la Habana. Facultad de Biología; CubaFil: Costa-Mugica, Ariadna. Universidad de la Habana. Facultad de Biología; CubaFil: Zulueta Díaz, Yenisleidy de Las Mercedes. Universidad de la Habana. Facultad de Biología; Cuba. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigaciones en Química Biológica de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Centro de Investigaciones en Química Biológica de Córdoba; ArgentinaFil: Diaz-Gutierrez, Daylín. Universidad de la Habana. Facultad de Biología; CubaFil: de Oliveira e Silva, Ana, Mara. Universidade de Sao Paulo; BrasilFil: Vazquez, Ana María. Center For Molecular Inmunology; CubaFil: Claudina, Zaldívar-Munoz. Universidad de la Habana. Facultad de Biología; CubaFil: Dalva, Assuncao Portari de Mancini. Institute Butantan Sao Paulo; BrasilFil: Mancini-Filho, Jorge. Universidade de Sao Paulo; Brasi

A recursive paradigm for aligning observed behavior of large structured process models

The alignment of observed and modeled behavior is a crucial problem in process mining, since it opens the door for conformance checking and enhancement of process models. The state of the art techniques for the computation of alignments rely on a full exploration of the combination of the model state space and the observed behavior (an event log), which hampers their applicability for large instances. This paper presents a fresh view to the alignment problem: the computation of alignments is casted as the resolution of Integer Linear Programming models, where the user can decide the granularity of the alignment steps. Moreover, a novel recursive strategy is used to split the problem into small pieces, exponentially reducing the complexity of the ILP models to be solved. The contributions of this paper represent a promising alternative to fight the inherent complexity of computing alignments for large instances.Peer ReviewedPostprint (author's final draft

Estimulación eléctrica en la reparación ósea de defectos creados en cráneos de conejos

Electrical stimulation has been used in different conditions for tissue regeneration. The aim of this study was to analyze the tissue response of defects created in rabbit skulls to electrical stimulation. Two groups were formed, each with 9 New Zealand rabbits; two 5 mm defects were made, one in each parietal, with one being randomly filled with autogenous bone extracted as particles and the other maintained only with blood clotting. The rabbits were euthanized at 8 weeks and 15 weeks to then study the samples collected histologically. In the 8-week analysis bone formation was observed in the defects in the test and control filled with bone graft, whereas the defects with clotting presented a very early stage of bone formation with abundant connective tissue. At 15 weeks an advanced stage of bone regeneration was identified in the defects with bone graft, whereas no significant differences were found in the electrically stimulated defects. In conclusion, electrical stimulus does not alter the sequence of bone formation; new studies could help establish patterns and influences of the stimulus on bone regeneration.Electrical stimulation has been used in different conditions for tissue regeneration. The aim of this study was to analyze the tissue response of defects created in rabbit skulls to electrical stimulation. Two groups were formed, each with 9 New Zealand r33311461150sem informaçãosem informaçãoLa estimulación eléctrica ha sido empleada en diferentes condiciones para la regeneración de tejidos. El objetivo de esta investigación es analizar la respuesta tisular de defectos creados en cráneo de conejos a la estimulación eléctrica. Se formaron 2 g

Influence Of Stimulus Frequency On Blockade Induced By Pancuronium And Rocuronium: Study On Rats Phrenic Nerve-diaphragm Preparation.

To evaluate the influence of two stimulation frequencies on the installation of neuromuscular blockade produced by pancuronium and rocuronium on the rat diaphragm. Diaphragms were submitted to an indirect frequency stimulation of 0.1 and 1 Hz (Groups I and II, respectively). Subgroups were formed (n=5) according to the neuromuscular blocker employed (pancuronium-2 microg/ml and rocuronium-4 microg/ml). The twitch height depression was evaluated at 5, 15 and 30 minutes after adding the neuromuscular blocker. The decrease in twitch height was greater (p<0.01) with a frequency of 1 Hz at all time periods studied both in preparations that are blocked with pancuronium and in those that are blocked with rocuronium. The frequency of stimulation interferes significantly with the installation of neuromuscular blockade produced by pancuronium and rocuronium, since the reduction in amplitude of the rat diaphragm response was greater for 1 Hz frequencies, at all periods studied.22446-5

Dispositif d’électrolyse de l’eau et son utilisation pour produire de l’hydrogène

Dispositif d’électrolyse destiné à produire de l’hydrogène par réduction de l’eau comprenant un compartiment cathodique, un compartiment anodique, un élément reliant lesdits compartiments et permettant la migration des ions entre eux, le dispositif étant caractérisé en ce que le compartiment cathodique contient au moins un acide faible apte à catalyser la réduction et une solution électrolytique dont le pH est dans la gamme comprise entre 3 et 9

Cluster-randomized, crossover trial of head positioning in acute stroke

The role of supine positioning after acute stroke in improving cerebral blood flow and the countervailing risk of aspiration pneumonia have led to variation in head positioning in clinical practice. We wanted to determine whether outcomes in patients with acute ischemic stroke could be improved by positioning the patient to be lying flat (i.e., fully supine with the back horizontal and the face upwards) during treatment to increase cerebral perfusion. METHODS In a pragmatic, cluster-randomized, crossover trial conducted in nine countries, we assigned 11,093 patients with acute stroke (85% of the strokes were ischemic) to receive care in either a lying-flat position or a sitting-up position with the head elevated to at least 30 degrees, according to the randomization assignment of the hospital to which they were admitted; the designated position was initiated soon after hospital admission and was maintained for 24 hours. The primary outcome was degree of disability at 90 days, as assessed with the use of the modified Rankin scale (scores range from 0 to 6, with higher scores indicating greater disability and a score of 6 indicating death). RESULTS The median interval between the onset of stroke symptoms and the initiation of the assigned position was 14 hours (interquartile range, 5 to 35). Patients in the lying-flat group were less likely than patients in the sitting-up group to maintain the position for 24 hours (87% vs. 95%, P\u3c0.001). In a proportional-odds model, there was no significant shift in the distribution of 90-day disability outcomes on the global modified Rankin scale between patients in the lying-flat group and patients in the sitting-up group (unadjusted odds ratio for a difference in the distribution of scores on the modified Rankin scale in the lying-flat group, 1.01; 95% confidence interval, 0.92 to 1.10; P = 0.84). Mortality within 90 days was 7.3% among the patients in the lying-flat group and 7.4% among the patients in the sitting-up group (P = 0.83). There were no significant betweengroup differences in the rates of serious adverse events, including pneumonia. CONCLUSIONS Disability outcomes after acute stroke did not differ significantly between patients assigned to a lying-flat position for 24 hours and patients assigned to a sitting-up position with the head elevated to at least 30 degrees for 24 hours