DEVELOPMENT OF PHOTOCATALYTIC MATERIALS FOR SOLAR LIGHT CONVERSION INTO FUELS

Solar light possesses a large amount of energy. The sun provides to our planet an intense flux of high energetic photons capable to promote extremely up-hill reactions, such as the photosynthetic fixation of CO2 in biological systems. This energy flow drives life on Earth. My PhD thesis is focused on solar driven conversion processes. While in the first year I principally investigated the photocatalytic reduction of CO2 with TiO2-based materials. In the second year I started to explore new promising visible light harvesting materials and in particular I worked on CdSe quantum dots synthesis and on their use as photocatalysts for hydrogen production under visible light, with special interest on the size dependent recombination of the photogenerated. Finally, during my stage by Professor Kamat\u2019s laboratory at Notre Dame University (Indiana, US), I started to work on the use of WO3/BiVO4 heterojunction photoanodes, for photoelectrocatalytic applications, and especially on charge carriers dynamics through transient absorption spectroscopy measurements. A short overview of the main themes treated during my PhD is outlined below. 1st year 1. Photocatalytic tests on TiO2 based materials in the photoassisted reactions of CO2 reduction and steam reforming of methanol, as a part of the research project FotoRiduCO2 PON01_02257. 2nd year 2. Synthesis and characterization of CdSe quantum dots with different size and their application in photocatalytic H2 production under visible light irradiation. 3. Preparation of WO3, BiVO4 and WO3/BiVO4 photoanodes for photoelectrochemical water splitting application and their study with transient absorption techniques. 3rd year 4. Preparation and characterization through femtosecond transient absorption spectroscopy of BiVO4 and WO3/BiVO4 films with variable BiVO4 thickness. The use of different pump energy allowed to suggest a new optical transition model that accounts for the electron transfer paths between the two oxides. Photoelectrochemical experiments validate the proposed model

Effective Visible Light Exploitation by Copper Molybdo-tungstate Photoanodes

The need for stable oxide-based semiconductors with a narrow band gap, able to maximize the exploitation of the visible light portion of the solar spectrum, is a challenging issue for photoelectrocatalytic (PEC) applications. In the present work, CuW1 12xMoxO4 (Eg = 2.0 eV for x = 0.5), which exhibits a significantly reduced optical band gap Eg compared with isostructural CuWO4 (Eg = 2.3 eV), was investigated as a photoactive material for the preparation of photoanodes. CuW0.5Mo0.5O4 electrodes with different thicknesses (80 12530 nm), prepared by a simple solution-based process in the form of multilayer films, effectively exhibit visible light photoactivity up to 650 nm (i.e., extended compared with CuWO4 photoanodes prepared by the same way). Furthermore, the systematic investigation on the effects on photoactivity of the CuW0.5Mo0.5O4 layer thickness evidenced that long-wavelength photons can better be exploited by thicker electrodes. PEC measurements in the presence of NaNO2, acting as a suitable hole scavenger ensuring enhanced photocurrent generation compared with that of water oxidation while minimizing dark currents, allowed us to elucidate the role that molybdenum incorporation plays on the charge separation efficiency in the bulk and on the charge injection efficiency at the photoanode surface. The adopted Mo for W substitution increases the visible light photoactivity of copper tungstate toward improved exploitation and storage of visible light into chemical energy via photoelectrocatalysis

Photoactivity and Stability of WO3/BiVO4 Photoanodes: Effects of the Contact Electrolyte and of Ni/Fe Oxyhydroxide Protection

Photoelectrodes with the WO3/BiVO4 heterojunction architecture are among the most efficient semiconductor oxide-based photoanodes for water oxidation. However, because of the different experimental conditions employed in their photoelectrochemical characterization (in particular the nature and concentration of the contact electrolyte and the pH of the solution), a direct and unambiguous comparison of their performance obtained in different labs is often quite difficult. In this work, we systematically tested identical WO3/BiVO4 photoanodes in contact with solutions of the most commonly used electrolytes, i.e. Na2SO4 and the potassium phosphate buffer (KPi), at various electrolyte concentration and pH. Furthermore, WO3/BiVO4 photoanodes protected with a Ni/Fe oxyhydroxide oxygen evolution catalyst were also tested under identical conditions. In contact with KPi solutions, both unprotected and protected electrodes produce higher photocurrent than in contact with Na2SO4 solutions, but they proved to be less stable, particularly under basic conditions. WO3/BiVO4 heterojunction systems modified by deposition of the Ni/Fe oxyhydroxide co-catayst proved to be more stable and to produce higher photocurrent, with a cathodic shift of the photocurrent onset

Efecto del manejo y del temperamento animal sobre indicadores de calidad de la carne bovina

The aim of this research was to study the effect of different handling conditions on physiological stress indicators and meat quality of beef cattle by studying animals with different temperaments. Forty animals classified by their temperament (calm and disturbed) were used. They were fed on pastures and finished with a mixed diet of corn grain and pasture. Biochemical indicators of animal stress were measured at slaughter (packed cell volume -PCV-, proteins, glucose, creatinine, alkaline phosphatase -APactivity, cortisol, insulin, glycogen). Also, ultimate pH and instrumental colour were chosen as meat quality markers. Animal temperament showed a significantly increase (p<0.05) on PCV levels and a significantly (p<0.05) decrease on muscle glycogen. Besides, levels of plasma glucose and total proteins showed significant (p<0.05) differences associated to management applied. Meat quality markers (pH and colour) did not show significant differences according to handling conditions or temperament. Mean cortisol levels at the exsanguination time were significantly higher (p<0.05) than the values obtained one week prior to slaughter, which suggests an important effect of stress associated to slaughter procedures. It would be interesting to focus attention on the assessment of acute stress at abattoir, in order to improve handling protocols, and therefore to assure meat quality in Argentinean beef production systems.El objetivo del presente trabajo fue estudiar el efecto de diferentes condiciones de manejo sobre indicadores fisiológicos de estrés y de calidad de carne en bovinos con temperamentos contrastantes. Se utilizaron cuarenta animales clasificados como calmos y excitables. Los mismos fueron alimentados inicialmente a base de pasturas y terminados con una dieta mixta de grano de maíz y pasturas. Se dosaron indicadores bioquímicos de estrés (hematocrito, proteínas plasmáticas, glucosa, creatinina, actividad fosfatasa alcalina, cortisol, insulina, contenido muscular de glucógeno). Como indicadores de calidad de carne se midieron el pH de 24 h y color instrumental. El temperamento animal demostró un incremento significativo (p<0,05) en los niveles de hematocrito y con una disminución significativa (p<0,05) del glucógeno muscular. Los niveles de glucemia y de proteínas totales mostraron modificaciones significativas (p<0,05) asociadas con el manejo. El incremento (p<0,05) en los niveles plasmáticos de cortisol durante la faena, independientemente del tratamiento o el temperamento animal, sugiere un importante efecto estresor por parte del proceso de faena. Sería interesante centrar la atención en el estudio del estrés agudo, a fin de mejorar protocolos de manejo animal, y consecuentemente, optimizar la calidad de la carne asociada en los sistemas de producción de Argentina.Fil: Pighin, D. G.. Instituto Nacional de Tecnología Agropecuaria. Centro Nacional de Investigaciones Agropecuarias. Centro de Investigación de Agroindustrias. Instituto de Tecnología de Alimentos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad de Moron; ArgentinaFil: Davies, P.. Instituto Nacional de Tecnología Agropecuaria; ArgentinaFil: Grigioni, Gabriela Maria. Instituto Nacional de Tecnología Agropecuaria. Centro Nacional de Investigaciones Agropecuarias. Centro de Investigación de Agroindustrias. Instituto de Tecnología de Alimentos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad de Moron; ArgentinaFil: Pazos, A. A.. Instituto Nacional de Tecnología Agropecuaria. Centro Nacional de Investigaciones Agropecuarias. Centro de Investigación de Agroindustrias. Instituto de Tecnología de Alimentos; Argentina. Universidad de Moron; ArgentinaFil: Ceconi, I.. Instituto Nacional de Tecnología Agropecuaria; ArgentinaFil: Mendez, Diego Eduardo. Instituto Nacional de Tecnología Agropecuaria; ArgentinaFil: Buffarini, M.. Instituto Nacional de Tecnología Agropecuaria; ArgentinaFil: Sancho, A.. Instituto Nacional de Tecnología Agropecuaria. Centro Nacional de Investigaciones Agropecuarias. Centro de Investigación de Agroindustrias. Instituto de Tecnología de Alimentos; Argentina. Universidad de Moron; ArgentinaFil: Gonzalez, Claudia Beatriz. Instituto Nacional de Tecnología Agropecuaria. Centro Nacional de Investigaciones Agropecuarias. Centro de Investigación de Agroindustrias. Instituto de Tecnología de Alimentos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de San Martín. Escuela de Ciencia y Tecnología; Argentin

Comparaison de deux méthodes de sélection classique avec l'haplodiploïdisation pour la résistance à la mouche de Hesse chez le blé tendre (Triticum aestivum)

L'efficacité des méthodes classiques et alternatives d'amélioration génétique repose sur l'évolution de la variabilité génétique des populations ségrégatives sous sélection. L'objectif de cette étude est de comparer l'évolution de la fréquence des gènes de résistance à la mouche de Hesse (Mayetiola destructor) sous deux méthodes classiques de sélection en comparaison avec la méthode de l'haplodiploïdisation. Les distributions et les proportions observées du caractère "résistance à la mouche de Hesse" ont été évaluées pour des lignées produites par la méthode de filiation unipare (FUP), la méthode " bulk " et l'haplodiploïdisation (DH) de quatre populations hybrides de blé tendre (Triticum aestivum). Ces populations sont issues des croisements entre des parents résistants à la mouche de Hesse marocaine et des parents sensibles mais adaptés aux conditions marocaines. Les résultats ont montré un effet marqué de la méthode d'amélioration génétique. En effet, malgré leur avancement à la génération F6, les lignées produites par les méthodes FUP et " bulk " présentent toujours un taux non négligeable d'hétérozygotie pour ce caractère alors que la méthode DH a abouti à une homozygotie parfaite. Les proportions de résistance observées chez les lignées FUP et haploïdes doublées sont approximativement les mêmes que celles théoriquement attendues. Cependant, la méthode " bulk " a permis une sélection naturelle au champ qui a favorisé le caractère résistant de manière significativeThe relative usefulness of conventional and alternative breeding methods relies on the evolution of genetic variability in segregating populations undergoing selection. The objective of this study was to compare the frequencies of genetic resistance to Hessian fly (Mayetiola destructor) in populations generated by two conventional breeding methods in comparison with lines advanced through doubled haploid method. Distribution and proportions of Hessian fly resistance were evaluated in four populations of bread wheat lines advanced through 'Single Seed Descent' (SSD), 'Bulk', and doubled-haploid (DH) methods. These populations were all derived from crosses involving resistant parents and susceptible lines adapted to Moroccan conditions. The results of this study have shown a clear effect of the breeding method. The Bulk and SSD (F6) derived lines have shown a substantial residual heterozygocity while DH method has produced completely homozygous material. The observed proportions of resistance did not deviate from expected in the populations of lines derived through SSD and DH methods while evidence of natural selection for resistance was significant in the lines derived through the Bulk method

Wavelength-Dependent Ultrafast Charge Carrier Separation in the WO3/BiVO4 Coupled System

Due to its 3c2.4 eV band gap, BiVO4 is a very promising photoanode material for harvesting the blue portion of the solar light for photoelectrochemical (PEC) water splitting applications. In WO3/BiVO4 heterojunction films, the electrons photoexcited in BiVO4 are injected into WO3, overcoming the lower charge carriers\u2019 diffusion properties limiting the PEC performance of BiVO4 photoanodes. Here, we investigate by ultrafast transient absorption spectroscopy the charge carrier interactions occurring at the interface between the two oxides in heterojunction systems to directly unveil their wavelength dependence. Under selective BiVO4 excitation, a favorable electron transfer from photoexcited BiVO4 to WO3 occurs immediately after excitation and leads to an increase of the trapped holes\u2019 lifetime in BiVO4. However, a recombination channel opens when both oxides are simultaneously excited, evidenced by a shorter lifetime of trapped holes in BiVO4. PEC measurements reveal the implication of these wavelength-dependent ultrafast interactions on the performances of the WO3/BiVO4 heterojunction

Effects of robotic upper limb treatment after stroke on cognitive patterns: A systematic review

BACKGROUND: Robotic therapy (RT) has been internationally recognized for the motor rehabilitation of the upper limb. Although it seems that RT can stimulate and promote neuroplasticity, the effectiveness of robotics in restoring cognitive deficits has been considered only in a few recent studies. OBJECTIVE: To verify whether, in the current state of the literature, cognitive measures are used as inclusion or exclusion criteria and/or outcomes measures in robotic upper limb rehabilitation in stroke patients. METHODS: The systematic review was conducted according to PRISMA guidelines. Studies eligible were identified through PubMed/MEDLINE and Web of Science from inception to March 2021. RESULTS: Eighty-one studies were considered in this systematic review. Seventy-three studies have at least a cognitive inclusion or exclusion criteria, while only seven studies assessed cognitive outcomes. CONCLUSION: Despite the high presence of cognitive instruments used for inclusion/exclusion criteria their heterogeneity did not allow the identification of a guideline for the evaluation of patients in different stroke stages. Therefore, although the heterogeneity and the low percentage of studies that included cognitive outcomes, seemed that the latter were positively influenced by RT in post-stroke rehabilitation. Future larger RCTs are needed to outline which cognitive scales are most suitable and their cut-off, as well as what cognitive outcome measures to use in the various stages of post-stroke rehabilitation

A pragmatic approach to the use of inotropes for the management of acute and advanced heart failure: An expert panel consensus

Inotropes aim at increasing cardiac output by enhancing cardiac contractility. They constitute the third pharmacological pillar in the treatment of patients with decompensated heart failure, the other two being diuretics and vasodilators. Three classes of parenterally administered inotropes are currently indicated for decompensated heart failure, (i) the beta adrenergic agonists, including dopamine and dobutamine and also the catecholamines epinephrine and norepinephrine, (ii) the phosphodiesterase III inhibitor milrinone and (iii) the calcium sensitizer levosimendan. These three families of drugs share some pharmacologic traits, but differ profoundly in many of their pleiotropic effects. Identifying the patients in need of inotropic support and selecting the proper inotrope in each case remain challenging. The present consensus, derived by a panel meeting of experts from 21 countries, aims at addressing this very issue in the setting of both acute and advanced heart failure. (C) 2019 The Authors. Published by Elsevier B.V.Peer reviewe

Atomically dispersed nickel-nitrogen-sulfur species anchored on porous carbon nanosheets for efficient water oxidation

Developing low-cost electrocatalysts to replace precious Ir-based materials is key for oxygen evolution reaction (OER). Here, we report atomically dispersed nickel coordinated with nitrogen and sulfur species in porous carbon nanosheets as an electrocatalyst exhibiting excellent activity and durability for OER with a low overpotential of 1.51 V at 10 mA cm(-2) and a small Tafel slope of 45 mV dec(-1) in alkaline media. Such electrocatalyst represents the best among all reported transition metal- and/or heteroatom-doped carbon electrocatalysts and is even superior to benchmark Ir/C. Theoretical and experimental results demonstrate that the well-dispersed molecular S vertical bar NiNx species act as active sites for catalyzing OER. The atomic structure of S vertical bar NiNx centers in the carbon matrix is clearly disclosed by aberration-corrected scanning transmission electron microscopy and synchrotron radiation X-ray absorption spectroscopy together with computational simulations. An integrated photoanode of nanocarbon on a Fe2O3 nanosheet array enables highly active solar-driven oxygen production

Gene-Based Tests of Association

Genome-wide association studies (GWAS) are now used routinely to identify SNPs associated with complex human phenotypes. In several cases, multiple variants within a gene contribute independently to disease risk. Here we introduce a novel Gene-Wide Significance (GWiS) test that uses greedy Bayesian model selection to identify the independent effects within a gene, which are combined to generate a stronger statistical signal. Permutation tests provide p-values that correct for the number of independent tests genome-wide and within each genetic locus. When applied to a dataset comprising 2.5 million SNPs in up to 8,000 individuals measured for various electrocardiography (ECG) parameters, this method identifies more validated associations than conventional GWAS approaches. The method also provides, for the first time, systematic assessments of the number of independent effects within a gene and the fraction of disease-associated genes housing multiple independent effects, observed at 35%–50% of loci in our study. This method can be generalized to other study designs, retains power for low-frequency alleles, and provides gene-based p-values that are directly compatible for pathway-based meta-analysis