Oxygen reduction in acid media: influence of the heat treatment on the FeNPc(1–20 isomer mixture impregnated on carbon blacks and active charcoals

Oxygen reduction with the aid of a number of FeNPc(1–2) impregnated carbon supports in sulphuric acid solutions has been investigated.\ud \ud Loading of the carbon samples amounted to about 10 wt.%. After a 10 day stay in the aerated solutions the samples were investigated with rotating disk electrode and X-ray photoelectron spectroscopy techniques. The most active and stable samples correspond to mono- or submonolayers of FeNPc deposited on high dibutylphthalate adsorption carbon blacks. Comparison with data obtained previously on Norit BrX impregnations emphasizes the rôle of the electron density on the inner nitrogen atoms rather than that on the iron centres

Oxygen reduction in acid media on supported iron naphthalocyanine: Effect of isomer configuration and pyrolysis

O2 reduction in H2SO4 medium has been investigated on FeNPc impregnations on Norit BrX by the rotating disk electrode technique. Important differences in activity and stability were found between the 1,2- and 2,3-FeNPc isomers (pyrolysed or not). XPS analyses show, for the most inactive sample, strong demetallation and nitrogen losses. This phenomenon can be attributed to the differences in flexibility between the FeNPc isomers, which influences their stabilization on the substrate

Oxygen reduction in an acid medium : electrocatalysis by CoNPc(1,2) impregnated on a carbon black support; effect of loading and heat treatment

O2 reduction in an acid medium has been investigated on a transition metal macrocycle, CoNPc(1,2), impregnated on a carbon black support with a high dibutylphthalate adsorption value, using a rotating disk electrode and voltammetry techniques described previously, combined with X-ray photoelectron spectroscopy measurements. Optimal activity was found for a bilayer coverage (n = 2) at 17%-18% w/w loading. Heat treatment seems to be beneficial for n 3: it increases the overall number N of exchanged electrons and improves the electrode wetting. For the most active samples, mixed Co(II)/Co(III) valencies were displayed

Oxygen reduction in acid media: effect of iron substitution by cobalt on heat-treated naphthalocyanine impregnations supported on preselected carbon blacks

FeNPc(1.2) impregnations were investigated at various loadings using a rotating-disk electrode, voltammetry and X-ray photoelectron spectroscopy (XPS) techniques. Optimal activity takes place at monolayer coverage, and major demetallation occurs after prolonged exposure to acid solution. The substitution of Fe by Co enables the electrochemical performances to reach those presented by 10% Pt on Vulcan and stops the demetallation process. The application of fast atomic bombardment secondary ion mass spectrometry (FABS) together with XPS sheds light on the detrimental role of some electrophilic groups attached to the carbon black-catalyst interface

Comparing the performance of conventional and robotic catheters in transcatheter aortic valve implantation

In this paper we investigate the performance of a recently developed robotic catheterization platform in comparison to conventional surgical equipment. Transcather aortic valve implantation (TAVI) was chosen as the test case and 12 interventionists (6 experts and 6 novices) participated in experiments with a silicon aorta model. Video sequences of the fluoroscopic monitor, used for guiding the instruments, were captured and processed with specialized software. To evaluate and compare the two systems the 2-D position of the catheter/guidewire tip is tracked and the shape of the phantom model is extracted in the video frames. In our analysis, we focus on three metrics; the procedure time, the average speed and the average distance to the vessel wall. The obtained results show that procedure time is capable of discriminating the participants of the different experience groups, achieving p=0.008 in the first stage of the experiment. In addition, experts consistently exhibit a higher average speed than novices. Ultimately, the increased average distance to the vessel wall demonstrated by the robotic system is an indication of improved precision and safer catheter/guidewire navigation

Tafonomía del titanosaurio Aeolosaurus colhuehuapensis, Cretácico Superior, Patagonia central, Argentina: un ejemplo de preservación en facies fluviales de desbordamiento

Aeolosaurus colhuehuapensis es un titanosaurio procedente del lago Colhué Huapi, en el Sur de Chubut, Argentina. Los materiales estudiados incluyen veintiuna vértebras caudales y siete hemapófisis, y se hallaron articulados en facies correspondientes a depósitos de desbordamientos vinculados a sistemas fluviales multicanalizados y de alta sinuosidad presentes en los aquí denominados ?estratos del lago Colhué Huapi? de edad Campaniano-Maastrichtiano. Estos sistemas poseían importantes fluctuaciones estacionales en la paleodescarga y estaban enmarcados en un clima semi-árido. La historia tafonómica fue inferida a partir del análisis de diversas características presentes en los restos y de observaciones sedimentológicas macro y microscópicas. La presencia tenue de estriamiento longitudinal, la escasa exfoliación, el grado de articulación y el arqueamiento dorsal de la serie caudal, sugieren un corto tiempo de exposición subaérea y rápido sepultamiento. La falta de marcas de abrasión en los elementos conservados indica escaso o nulo transporte, por lo que los mismos podrían ser considerados autóctonos. El curvamiento dorsal de la cola muestra un arqueamiento opistótono, también presente en algunos terópodos y saurópodos, pero aun no documentado en el Grupo Chubut. Las condiciones climáticas actuales, con variaciones de extrema humedad y sequía, afectaron marcadamente los elementos fósiles preservados. El presente trabajo constituye el primer caso de estudio tafonómico en detalle de un dinosaurio preservado en facies de planicie de inundación proximal para el Grupo Chubut. Finalmente, el hallazgo de saurópodos en estas facies es relevante, dado que este tipo de subambiente posee una alta tasa de aporte sedimentario y reducido a nulo retrabajo de los restos óseos, favoreciendo la preservación de elementos esqueletales articulados. Esto es de suma importancia para el análisis taxonómico y filogenético del clado de los titanosaurios, donde la mayoría de los taxones están representados por restos desarticulados y aislados. Palabras clave: Tafonomía, Postura opistótona, Titanosauria, Patagonia.Fil: Casal, Gabriel A.. Universidad Nacional de la Patagonia "san Juan Bosco"; ArgentinaFil: Ibiricu, Lucio Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Nacional Patagónico; ArgentinaFil: Allard, Jose Oscar. Universidad Nacional de la Patagonia "san Juan Bosco"; ArgentinaFil: Martínez, Rubén D.. Universidad Nacional de la Patagonia "san Juan Bosco"; ArgentinaFil: Luna, Marcelo. Universidad Nacional de la Patagonia "san Juan Bosco"; ArgentinaFil: Gonzalez Riga, Bernardo Javier. Universidad Nacional de Cuyo; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Científico Tecnológico Mendoza. Instituto Argentino de Nivología, Glaciología y Ciencias Ambientales; Argentin

A Survey on the Current Status and Future Challenges Towards Objective Skills Assessment in Endovascular Surgery

Minimally-invasive endovascular interventions have evolved rapidly over the past decade, facilitated by breakthroughs in medical imaging and sensing, instrumentation and most recently robotics. Catheter based operations are potentially safer and applicable to a wider patient population due to the reduced comorbidity. As a result endovascular surgery has become the preferred treatment option for conditions previously treated with open surgery and as such the number of patients undergoing endovascular interventions is increasing every year. This fact coupled with a proclivity for reduced working hours, results in a requirement for efficient training and assessment of new surgeons, that deviates from the “see one, do one, teach one” model introduced by William Halsted, so that trainees obtain operational expertise in a shorter period. Developing more objective assessment tools based on quantitative metrics is now a recognised need in interventional training and this manuscript reports the current literature for endovascular skills assessment and the associated emerging technologies. A systematic search was performed on PubMed (MEDLINE), Google Scholar, IEEXplore and known journals using the keywords, “endovascular surgery”, “surgical skills”, “endovascular skills”, “surgical training endovascular” and “catheter skills”. Focusing explicitly on endovascular surgical skills, we group related works into three categories based on the metrics used; structured scales and checklists, simulation-based and motion-based metrics. This review highlights the key findings in each category and also provides suggestions for new research opportunities towards fully objective and automated surgical assessment solutions

Trends and socioeconomic inequalities in cancer survival in England and Wales up to 2001.

We examined national trends and socioeconomic inequalities in cancer survival in England and Wales during the 1990s, using population-based data on 2.2 million patients who were diagnosed with one of the 20 most common cancers between 1986 and 1999 and followed up to 2001. Patients were assigned to one of five deprivation categories (from 'affluent' to 'deprived') using characteristics of their electoral ward of residence at diagnosis. We estimated relative survival up to 5 years after diagnosis, adjusting separately in each deprivation category for background mortality by age, sex and calendar period. We estimated trends in survival and in the difference in survival between deprivation categories ('deprivation gap') over the periods 1986-90, 1991-95 and 1996-99. We used period analysis to examine likely survival rates in the near future. Survival improved for most cancers in both sexes during the 1990s, and appears likely to continue improving for most cancers in the near future. The deprivation gap in survival between rich and poor was wider for patients diagnosed in the late 1990s than in the late 1980s. Increases in cancer survival in England and Wales during the 1990s are shown to be significantly associated with a widening deprivation gap in survival

Clinical validation of an algorithm for rapid and accurate automated segmentation of intracoronary optical coherence tomography images

Objectives: The analysis of intracoronary optical coherence tomography (OCT) images is based on manual identification of the lumen contours and relevant structures. However, manual image segmentation is a cumbersome and time-consuming process, subject to significant intra- and inter-observer variability. This study aims to present and validate a fully-automated method for segmentation of intracoronary OCT images. Methods: We studied 20 coronary arteries (mean length = 39.7 ± 10.0 mm) from 20 patients who underwent a clinically-indicated cardiac catheterization. The OCT images (n = 1812) were segmented manually, as well as with a fully-automated approach. A semi-automated variation of the fully-automated algorithm was also applied. Using certain lumen size and lumen shape characteristics, the fully- and semi-automated segmentation algorithms were validated over manual segmentation, which was considered as the gold standard. Results: Linear regression and Bland–Altman analysis demonstrated that both the fully-automated and semiautomated segmentation had a very high agreement with the manual segmentation, with the semi-automated approach being slightly more accurate than the fully-automated method. The fully-automated and semiautomated OCT segmentation reduced the analysis time by more than 97% and 86%, respectively, compared to manual segmentation. Conclusions: In the current work we validated a fully-automated OCT segmentation algorithm, as well as a semiautomated variation of it in an extensive “real-life” dataset of OCT images. The study showed that our algorithm can perform rapid and reliable segmentation of OCT images

Designing Urban Spaces to Enhance Active and Sustainable Mobility: An Analysis of Physical and Symbolic Affordances in School Squares in the Metropolitan Area of Milan, Italy

As thresholds to cities, public spaces adjacent to schools play an important role in children’s everyday mobilities, potentially shaping their future mobility habits and affective experiences. The purpose of this paper is to investigate the urban design conditions of such spaces, defined as “school squares”, and, with the aid of affordance theory, to analyze spatial features and characteristics that might encourage or hinder active and sustainable mobility practices. In the first part of the paper, we define sustainable mobility, conduct a literature review on affective responses to the urban environment, and discuss active school travel (AST) in relation to the design of school squares. By focusing on 416 primary and lower secondary schools in the metropolitan area of Milan, we present an assessment method that is composed of on-desk and on-site surveys. In particular, Phase 1 defines the type of school squares, Phase 2 investigates physical affordances (spatial features and characteristics that directly influence active mobility practices, such as bicycle racks, protective barriers, benches, and parked cars), and Phase 3 discusses symbolic affordances (elements and characteristics that might induce different affective responses to a school square with regard to active mobility, such as bicycle racks, parked cars, greenery, and dustbins). The results indicate that in most cases school squares are characterized by typological confusion that has nothing to do with the school environment: narrow sidewalks, disorder, and low levels of safety. In order to promote active and sustainable mobility choices and enhance children’s mobile experiences, it is necessary to address the aforementioned features. The ultimate goal of this paper is to provide insights for developing an urban regeneration framework that considers school squares a safe context and a starting point from which to perform sustainable mobility practices