High-throughput synthesis and characterization of vanadium mixed metal oxide pigments using synchroton radiation

UNA range of inorganic vanadium mixed metal oxides, with potential applications asinorganic pigments, have been synthesised and characterised in terms of their crystalstructure, and band gap energies using powder X-ray diffraction (PXD), synchrotron-basedX-ray absorption fine structure (XAFS) spectroscopy, solid state UV-Visible and Ramanspectroscopy, Scanning and Transmission electron microscopy (SEM and TEM).Vanadium mixed metal oxide BiMeVOX with Me = Mo, Cu and Fe, and calciumpyrovanadate with Me = Pb, Cd, Sr, doped systems, have been synthesised in sequentialand high throughput array by peroxo sol-gel methods and calcined at 700°C in an oxygenatmosphere. Powder X-ray diffraction studies show the synthesised BiMoVOX(Bi1-x/3Mo1-xVxO4) to have a tetragonal crystal structure in the space group I 41/a, BiCuVOXand BiFeVOX (Bi2V1-xMexO5.5-?) to have a tetragonal crystal structure in the space groupI 4/mmm, and pyrovanadate ((Ca2-x,Mex)V2O7) to have triclinic in the space group P-1.PXD profiles have displayed phase transitions from monoclinic to tetragonal crystal phasetogether with peak positions shift, reflecting the changes in d-spacing and consequentvolume cell growth by incorporation of the different ions into BiMeVOX; the calciumpyrovanadate kept their triclinic crystal structure.Raman and XAFS spectroscopy data analysis have shown isolated metal-oxygentetrahedra for both vanadium and molybdenum cations in the BiMoVOX materials.Vanadium coordination in both the BiFeVOX and the BiCuVOX materials is more complexwith three different cases: octahedral distorted, trigonal bipyramid and tetragonal ; thesestructure consists of alternating layers of [Bi2O2]2+ and [VO3.5?0.5]2-, where ? represents oxideion vacancies. Calcium pyrovanadate materials display vanadium-oxygen polyhedra for atetrameric chain comprising two edge-shared VO5 pyramids, and each also sharing a cornerwith a VO4 tetrahedron.UV-Visible spectroscopy of these materials reveals broad reflectance bands and asteep absorption edge, which is directly related to the band gap energy of the compound. Byvarying the doping levels on the vanadium and calcium site with different cations the colourof the compounds can be seen to visibly alter. This can be attributed to a modification in theband gap energies as direct result of the fine-tuning of the electronegativity differencebetween cations and anions, their overall contribution to the molecular orbitals of thematerials, and the total concentration of oxygen vacancies.SEM and TEM analysis showed a more round particle shape for samples made by theperoxo sol-gel reaction compared to samples made by calcinations reaction in the BiMoVOXseries

High-throughput synthesis and characterization of BiMoVOX materials

The high throughput synthesis and characterization of a particular family of ceramic materials, bismuth molybdenum vanadium oxides (BiMoVOX), suitable as inorganic yellow pigments and low temperature oxidation catalysts, is described. Samples, synthesized by calcination and peroxo sol-gel methods, are characterized by X-ray powder diffraction, UV-visible and XAFS spectroscopy. A combined high-throughput XRD/XAFS study of a 54 samples array, with simultaneous refinement of data of both techniques, has been performed. Molybdenum doping of bismuth vanadate results in a phase transition from monoclinic BiV04 to tetragonal Bi(V,Mo)04, both of scheelite type. Both central metals, V5+ and Mo6+, remain in a tetrahedral coordination. UV/visible spectroscopy identifies a linear blue shift as a function of Mo6+ amount

High Throughput In Situ XAFS Screening of Catalysts

We outline and demonstrate the feasibility of high-throughput (HT) in situ XAFS for synchrotron radiation studies. An XAS data acquisition and control system for the analysis of dynamic materials libraries under control of temperature and gaseous environments has been developed. The system is compatible with the 96-well industry standard and coupled to multi-stream quadrupole mass spectrometry (QMS) analysis of reactor effluents. An automated analytical workflow generates data quickly compared to traditional individual spectrum acquisition and analyses them in quasi-real time using an HT data analysis tool based on IFFEFIT. The system was used for the automated characterization of a library of 91 catalyst precursors containing ternary combinations of Cu, Pt, and Au on ?-Al2O3, and for the in situ characterization of Au catalysts supported on Al2O3 and TiO2

O USO TRANSFORMADOR DA REALIDADE VIRTUAL NO ENSINO DE GEOGRAFIA DURANTE O ESTÁGIO SUPERVISIONADO NO ENSINO FUNDAMENTAL I

This article addresses the transformative potential of Virtual Reality (VR) in teaching Geography during supervised internships in Elementary Education I. VR offers an immersive experience that allows students to explore geographic environments virtually and engagingly, providing a more tangible understanding of geographical concepts. Furthermore, VR promotes active learning by enabling students to interact with virtual scenarios, make decisions, and experience consequences, fostering essential cognitive skills such as critical thinking and problem-solving.The diversity of resources offered by VR, such as virtual trips to geographic locations, simulations of natural phenomena, and 3D data analysis, enriches the teaching and learning process, making it more engaging and contextualized. Additionally, VR can be an inclusive tool, catering to different learning styles and special needs, promoting a more accessible and equitable education. However, it's important to consider the challenges associated with implementing VR, such as the costs involved in acquiring equipment and the need for proper training for educators. Overcoming these obstacles requires a significant commitment, but the careful application of VR can enhance Geography classes, preparing future educators for an innovative and effective approach to teaching.Este artículo aborda el potencial transformador de la Realidad Virtual (RV) en la enseñanza de la Geografía durante las prácticas supervisadas en la Educación Primaria I. La RV ofrece una experiencia inmersiva que permite a los estudiantes explorar entornos geográficos de manera virtual y cautivadora, brindando una comprensión más tangible de los conceptos geográficos. Además, la RV fomenta el aprendizaje activo al permitir que los estudiantes interactúen con los escenarios virtuales, tomen decisiones y experimenten las consecuencias, desarrollando habilidades cognitivas esenciales como el pensamiento crítico y la resolución de problemas. La diversidad de recursos ofrecidos por la RV, como viajes virtuales a ubicaciones geográficas, simulaciones de fenómenos naturales y análisis de datos en 3D, enriquece el proceso de enseñanza y aprendizaje, haciéndolo más atractivo y contextualizado. Además, la RV puede ser una herramienta inclusiva que atiende a diferentes estilos de aprendizaje y necesidades especiales, promoviendo una educación más accesible y equitativa. Sin embargo, es importante considerar los desafíos asociados con la implementación de la RV, como los costos involucrados en la adquisición de equipos y la necesidad de una capacitación adecuada para los educadores. Superar estos obstáculos requiere un compromiso significativo, pero la aplicación cuidadosa de la RV puede enriquecer las clases de Geografía, preparando a los futuros educadores para un enfoque innovador y efectivo en la enseñanza.Este artigo aborda o potencial transformador da Realidade Virtual (RV) no ensino de Geografia durante o estágio supervisionado no Ensino Fundamental I. A RV oferece uma experiência imersiva que possibilita aos alunos explorar ambientes geográficos de maneira virtual e envolvente, proporcionando uma compreensão mais tangível dos conceitos geográficos. Além disso, a RV promove o aprendizado ativo, permitindo que os alunos interajam com os cenários virtuais, tomem decisões e experimentem as consequências, desenvolvendo habilidades cognitivas essenciais, como pensamento crítico e resolução de problemas. A diversidade de recursos oferecidos pela RV, como viagens virtuais a locais geográficos, simulações de fenômenos naturais e análise de dados em 3D, enriquece o processo de ensino e aprendizagem, tornando-o mais envolvente e contextualizado. Além disso, a RV pode ser uma ferramenta inclusiva, atendendo a diferentes estilos de aprendizagem e necessidades especiais, o que promove uma educação mais acessível e equitativa. No entanto, é importante considerar os desafios associados à implementação da RV, como os custos envolvidos na aquisição de equipamentos e a necessidade de capacitação adequada para os educadores. Superar esses obstáculos requer um compromisso significativo, mas a aplicação cuidadosa da RV pode enriquecer as aulas de Geografia, preparando os futuros educadores para uma abordagem inovadora e eficaz no ensino.Este artigo aborda o potencial transformador da Realidade Virtual (RV) no ensino de Geografia durante o estágio supervisionado no Ensino Fundamental I. A RV oferece uma experiência imersiva que possibilita aos alunos explorar ambientes geográficos de maneira virtual e envolvente, proporcionando uma compreensão mais tangível dos conceitos geográficos. Além disso, a RV promove o aprendizado ativo, permitindo que os alunos interajam com os cenários virtuais, tomem decisões e experimentem as consequências, desenvolvendo habilidades cognitivas essenciais, como pensamento crítico e resolução de problemas. A diversidade de recursos oferecidos pela RV, como viagens virtuais a locais geográficos, simulações de fenômenos naturais e análise de dados em 3D, enriquece o processo de ensino e aprendizagem, tornando-o mais envolvente e contextualizado. Além disso, a RV pode ser uma ferramenta inclusiva, atendendo a diferentes estilos de aprendizagem e necessidades especiais, o que promove uma educação mais acessível e equitativa. No entanto, é importante considerar os desafios associados à implementação da RV, como os custos envolvidos na aquisição de equipamentos e a necessidade de capacitação adequada para os educadores. Superar esses obstáculos requer um compromisso significativo, mas a aplicação cuidadosa da RV pode enriquecer as aulas de Geografia, preparando os futuros educadores para uma abordagem inovadora e eficaz no ensino

High-throughput synthesis and characterization of vanadium mixed metal oxide pigments using synchrotron radiation

UNA range of inorganic vanadium mixed metal oxides, with potential applications as inorganic pigments, have been synthesised and characterised in terms of their crystal structure, and band gap energies using powder X-ray diffraction (PXD), synchrotron-based X-ray absorption fine structure (XAFS) spectroscopy, solid state UV-Visible and Raman spectroscopy, Scanning and Transmission electron microscopy (SEM and TEM). Vanadium mixed metal oxide BiMeVOX with Me = Mo, Cu and Fe, and calcium pyrovanadate with Me = Pb, Cd, Sr, doped systems, have been synthesised in sequential and high throughput array by peroxo sol-gel methods and calcined at 700°C in an oxygen atmosphere. Powder X-ray diffraction studies show the synthesised BiMoVOX (Bi1-x/3Mo1-xVxO4) to have a tetragonal crystal structure in the space group I 41/a, BiCuVOX and BiFeVOX (Bi2V1-xMexO5.5-γ) to have a tetragonal crystal structure in the space group I 4/mmm, and pyrovanadate ((Ca2-x,Mex)V2O7) to have triclinic in the space group P-1. PXD profiles have displayed phase transitions from monoclinic to tetragonal crystal phase together with peak positions shift, reflecting the changes in d-spacing and consequent volume cell growth by incorporation of the different ions into BiMeVOX; the calcium pyrovanadate kept their triclinic crystal structure. Raman and XAFS spectroscopy data analysis have shown isolated metal-oxygen tetrahedra for both vanadium and molybdenum cations in the BiMoVOX materials. Vanadium coordination in both the BiFeVOX and the BiCuVOX materials is more complex with three different cases: octahedral distorted, trigonal bipyramid and tetragonal ; these structure consists of alternating layers of [Bi2O2]2+ and [VO3.5□0.5]2-, where □ represents oxide ion vacancies. Calcium pyrovanadate materials display vanadium-oxygen polyhedra for a tetrameric chain comprising two edge-shared VO5 pyramids, and each also sharing a corner with a VO4 tetrahedron. UV-Visible spectroscopy of these materials reveals broad reflectance bands and a steep absorption edge, which is directly related to the band gap energy of the compound. By varying the doping levels on the vanadium and calcium site with different cations the colour of the compounds can be seen to visibly alter. This can be attributed to a modification in the band gap energies as direct result of the fine-tuning of the electronegativity difference between cations and anions, their overall contribution to the molecular orbitals of the materials, and the total concentration of oxygen vacancies. SEM and TEM analysis showed a more round particle shape for samples made by the peroxo sol-gel reaction compared to samples made by calcinations reaction in the BiMoVOX series.EThOS - Electronic Theses Online ServiceGBUnited Kingdo

High-throughput structure/function screening of materials and catalysts with multiple spectroscopic techniques

High throughput screening methodologies are expanded to synchrotron based x-ray absorption techniques. An environmental chamber, based on ultra-high vacuum equipment, has been developed allowing in situ studies on arrays of samples while X-ray absorption fine structure spectroscopy, Raman spectroscopy, mass spectrometry and/or Xray diffraction can be applied simultaneously to characterize the system under process conditions in a time-resolved manner. The chamber accommodates a diverse range of samples from surface science to materials chemistry to heterogeneous catalysis. Data acquisition and data logging software is developed to handle large quantities of divers but related information. New data logging, processing and analysis procedures and programs are developed which will allow fast structure-function relationships characterization

A gender gap in primary and secondary heart dysfunctions in systemic sclerosis: A EUSTAR prospective study

Objectives. In agreement with other autoimmune diseases, systemic sclerosis (SSc) is associated with a strong sex bias. However, unlike lupus, the effects of sex on disease phenotype and prognosis are poorly known. Therefore, we aimed to determine sex effects on outcomes. Method. We performed a prospective observational study using the latest 2013 data extract from the EULAR scleroderma trials and research (EUSTAR) cohort. We looked at (i) sex influence on disease characteristics at baseline and (ii) then focused on patients with at least 2 years of follow-up to estimate the effects of sex on disease progression and survival. Results. 9182 patients with SSc were available (1321 men) for the baseline analyses. In multivariate analysis, male sex was independently associated with a higher risk of diffuse cutaneous subtype (OR: 1.68, (1.45 to 1.94); p<0.001), a higher frequency of digital ulcers (OR: 1.28 (1.11 to 1.47); p<0.001) and pulmonary hypertension (OR: 3.01 (1.47 to 6.20); p<0.003). In the longitudinal analysis (n=4499), after a mean follow-up of 4.9 (±2.7) years, male sex was predictive of new onset of pulmonary hypertension (HR: 2.66 (1.32 to 5.36); p=0.006) and heart failure (HR: 2.22 (1.06 to 4.63); p=0.035). 908 deaths were recorded, male sex predicted deaths of all origins (HR: 1.48 (1.19 to 1.84); p<0.001), but did not significantly account for SSc-related deaths. Conclusions. Although more common in women, SSc appears as strikingly more severe in men. Our results obtained through the largest worldwide database demonstrate a higher risk of severe cardiovascular involvement in men. These results raise the point of including sex in the management and the decisionmaking process

Update on the profile of the EUSTAR cohort: an analysis of the EULAR Scleroderma Trials and Research group database

Objectives Systemic sclerosis (SSc) is a rare disease requiring multicentre collaboration to reveal comprehensive details of disease-related causes for morbidity and mortality.Methods The European League Against Rheumatism (EULAR) Scleroderma Trials and Research (EUSTAR) group initiated a database to prospectively gather key data of patients with SSc using a minimal essential dataset that was reorganised in 2008 introducing new items. Baseline visit data of patients who were registered between 2004 and 2011 were analysed using descriptive statistics.Results In June 2011, 7655 patients (2838 with diffuse cutaneous (dc) and 4481 with limited cutaneous (lc) SSc who fulfilled the American College of Rheumatology diagnostic criteria had been registered in 174 centres, mainly European. The most prominent hallmarks of disease were Raynaud's phenomenon (96.3%), antinuclear antibodies (93.4%) and a typical capillaroscopic pattern (90.9%). Scleroderma was more common on fingers and hands than on any other part of the skin. Proton pump inhibitors (65.2%), calcium channel blockers (52.7%), and corticosteroids (45.3%) were most often prescribed. Among the immunosuppressant agents, cyclophosphamide was used more often in dcSSc than in lcSSc.Conclusions The EUSTAR database provides an abundance of information on the true clinical face of SSc that will be helpful in improving the classification of SSc and its subsets and for developing more specific therapeutic recommendations

Phenotypes Determined by Cluster Analysis and Their Survival in the Prospective European Scleroderma Trials and Research Cohort of Patients With Systemic Sclerosis

Objective Systemic sclerosis (SSc) is a heterogeneous connective tissue disease that is typically subdivided into limited cutaneous SSc (lcSSc) and diffuse cutaneous SSc (dcSSc) depending on the extent of skin involvement. This subclassification may not capture the entire variability of clinical phenotypes. The European Scleroderma Trials and Research (EUSTAR) database includes data on a prospective cohort of SSc patients from 122 European referral centers. This study was undertaken to perform a cluster analysis of EUSTAR data to distinguish and characterize homogeneous phenotypes without any a priori assumptions, and to examine survival among the clusters obtained. Methods A total of 11,318 patients were registered in the EUSTAR database, and 6,927 were included in the study. Twenty-four clinical and serologic variables were used for clustering. Results Clustering analyses provided a first delineation of 2 clusters showing moderate stability. In an exploratory attempt, we further characterized 6 homogeneous groups that differed with regard to their clinical features, autoantibody profile, and mortality. Some groups resembled usual dcSSc or lcSSc prototypes, but others exhibited unique features, such as a majority of lcSSc patients with a high rate of visceral damage and antitopoisomerase antibodies. Prognosis varied among groups and the presence of organ damage markedly impacted survival regardless of cutaneous involvement. Conclusion Our findings suggest that restricting subsets of SSc patients to only those based on cutaneous involvement may not capture the complete heterogeneity of the disease. Organ damage and antibody profile should be taken into consideration when individuating homogeneous groups of patients with a distinct prognosis

Outcomes of patients with systemic sclerosis treated with rituximab in contemporary practice: a prospective cohort study.

Objective To assess the safety and efficacy of rituximab in systemic sclerosis (SSc) in clinical practice. Methods We performed a prospective study including patients with SSc from the European Scleroderma Trials and Research (EUSTAR) network treated with rituximab and matched with untreated patients with SSc. The main outcomes measures were adverse events, skin fibrosis improvement, lung fibrosis worsening and steroids use among propensity score-matched patients treated or not with rituximab. Results 254 patients were treated with rituximab, in 58% for lung and in 32% for skin involvement. After a median follow-up of 2 years, about 70% of the patients had no side effect. Comparison of treated patients with 9575 propensity-score matched patients showed that patients treated with rituximab were more likely to have skin fibrosis improvement (22.7 vs 14.03 events per 100 person-years; OR: 2.79 [1.47-5.32]; p=0.002). Treated patients did not have significantly different rates of decrease in forced vital capacity (FVC)&gt;10% (OR: 1.03 [0.55-1.94]; p=0.93) nor in carbon monoxide diffusing capacity (DLCO) decrease. Patients having received rituximab were more prone to stop or decrease steroids (OR: 2.34 [1.56-3.53], p&lt;0.0001). Patients treated concomitantly with mycophenolate mofetil had a trend for better outcomes as compared with patients receiving rituximab alone (delta FVC: 5.22 [0.83-9.62]; p=0.019 as compared with controls vs 3 [0.66-5.35]; p=0.012). Conclusion Rituximab use was associated with a good safety profile in this large SSc-cohort. Significant change was observed on skin fibrosis, but not on lung. However, the limitation is the observational design. The potential stabilisation of lung fibrosis by rituximab has to be addressed by a randomised trial