Mapping the multi-step mechanism of a photoredox catalyzed atom-transfer radical polymerization reaction by direct observation of the reactive intermediates

The rapid development of new applications of photoredox catalysis has so far outpaced the mechanistic studies important for rational design of new classes of catalysts. Here, we report the use of ultrafast transient absorption spectroscopic methods to reveal both mechanistic and kinetic details of multiple sequential steps involved in an organocatalyzed atom transfer radical polymerization reaction. The polymerization system studied involves a N,N-diaryl dihydrophenazine photocatalyst, a radical initiator (methyl 2-bromopropionate) and a monomer (isoprene). Time-resolved spectroscopic measurements spanning sub-picosecond to microseconds (i.e., almost 8 orders of magnitude of time) track the formation and loss of key reactive intermediates. These measurements identify both the excited state of the photocatalyst responsible for electron transfer and the radical intermediates participating in propagation reactions, as well as quantifying their lifetimes. The outcomes connect the properties of N,N-diaryl dihydrophenazine organic photocatalysts with the rates of sequential steps in the catalytic cycle

Early childhood development and education: theoretical convergences and divergences

This article introduces a theoretical study about convergent and divergent aspects between the concepts of education and early childhood development. This, set up from a social and educational approach, based on a in-depth theoretical review. The beliefs of children’s parents and caregivers are highlighted as a significant aspect on children’s development; all, considering the practices used for educating them, promoting a holistic child development, or the contrary. These insights make it possible to understand the rationality and applicability of child development and education theories. Hence, we advocate in this manuscript for an interdisciplinary and holistic perspective to approach child development taking into consideration factors and conditions, as well as fusing conceptual frameworks from various disciplines such as psychology, sociology, and philosophy

Fin whales as bioindicators of multi-decadal change in carbon and oxygen stable isotope shifts in the North Atlantic

Global changes, and particularly the massive release of CO2 to the atmosphere and subsequent global warming, have altered the baselines of carbon and oxygen stable isotopic ratios. Temporal shifts in these baselines can be advantageously monitored through cetacean skin samples because these animals are highly mobile and therefore integrate in their tissues the heterogeneity of local environmental signals. In this study, we examine variation of delta C-13 and delta O-18 values in the skin of fin whales sampled over three decades in two different North Atlantic feeding grounds: west Iceland and northwest Spain. These locations are situated about 2700 km apart and thus represent a wide latitudinal range within the North Atlantic Ocean. The delta C-13 decrease in both areas is attributed to the burning of fossil fuels and increased deforestation worldwide, the so-called Suess effect. The dissimilarity in the magnitude of the shift between the two areas is coincidental with previous information on local shifts and lies within the ranges of variation observed. delta O-18 values experienced a minimal, yet significant change in fin whales from W Iceland (a decline of - 0.44 parts per thousand between 1986 and 2013) but not in those from NW Spain. This is in concordance with a higher rise in temperatures in the former area than in the latter. The study validates the use of cetacean skin to monitor temporal and geographical shifts in stable isotopic values and alerts that, when applying this tool to ecological research, comparisons between sample sets should take into account temporal and latitudinal scales

Low temperature degradation behaviour of 10Ce-TZP/Al2O3 bioceramics obtained by microwave sintering technology

Zirconia is one of the most used ceramics, especially for biomedical applications, due to its exceptional mechanical properties. However, it is commonly known that its properties can be diminished owing to a low temperature degradation (LTD). This phenomenon consists on a spontaneous phase transformation, from tetragonal to monoclinic, under certain conditions, which is accelerated when the samples are exposed under high levels of humidity at a temperature range between 20-300 ºC. In addition to the fact that the monoclinic phase presents worse mechanical properties than the tetragonal one, there is a volume change of 4% between phases that gives rise to defects in the material as microcracks. Due to this reason, zirconia prostheses failed catastrophically inside the human body between 1999 and 2001 (1). Previous researches reveal that Al2O3 addition suppress the propagation of phase transformation (2). Thus, the aim of the present work is to study the hydrothermal ageing of zirconia doped with ceria and toughened with alumina (10Ce-TZP/Al2O3) composite, which has been sintered by microwave employing two different frequencies: 2.45 and 5.8 GHz. Microwave heating technology is based on the absorption of electromagnetic radiation by the material, which allows the sample to be heated. So far, most microwave heating equipments use 2.45 GHz; accordingly, the novelty of this study is to employ a frequency of 5.8 GHz and to investigate its effect on LTD. LTD is carried out in an autoclaved in steam at 120 ºC and 1.2 bar, because these conditions accelerate the hydrothermal aging process (3). In order to characterize the degraded samples, micro-Raman spectroscopy, AFM, nanoindentation technique and electronic microscopy have been performed. References 1. Norton, M. R., Yarlagadda, R., Anderson, G. H. J. Bone Joint Surg. Br., 2002, 84–B, 631–635. 2. Fabbri, P., Piconi, C., Burresi, E., Magnani, G., Mazzanti, F., Mingazzini, C. Dent. Mater., 2014. 3. Presenda, Á., Salvador, M. D., Moreno, R., Borrell, A. J. Am. Ceram. Soc., 2015, 98, 3680–3689

Trends in socioeconomic inequalities in cancer mortality in Barcelona: 1992–2003

<p>Abstract</p> <p>Background</p> <p>The objective of this study was to assess trends in cancer mortality by educational level in Barcelona from 1992 to 2003.</p> <p>Methods</p> <p>The study population comprised Barcelona inhabitants aged 20 years or older. Data on cancer deaths were supplied by the system of information on mortality. Educational level was obtained from the municipal census. Age-standardized rates by educational level were calculated. We also fitted Poisson regression models to estimate the relative index of inequality (RII) and the Slope Index of Inequalities (SII). All were calculated for each sex and period (1992–1994, 1995–1997, 1998–2000, and 2001–2003).</p> <p>Results</p> <p>Cancer mortality was higher in men and women with lower educational level throughout the study period. Less-schooled men had higher mortality by stomach, mouth and pharynx, oesophagus, larynx and lung cancer. In women, there were educational inequalities for cervix uteri, liver and colon cancer. Inequalities of overall and specific types of cancer mortality remained stable in Barcelona; although a slight reduction was observed for some cancers.</p> <p>Conclusion</p> <p>This study has identified those cancer types presenting the greatest inequalities between men and women in recent years and shown that in Barcelona there is a stable trend in inequalities in the burden of cancer.</p

First insights into the phylogenetic diversity of Mycobacterium tuberculosis in Nepal

BACKGROUND: Tuberculosis (TB) is a major public health problem in Nepal. Strain variation in Mycobacterium tuberculosis may influence the outcome of TB infection and disease. To date, the phylogenetic diversity of M. tuberculosis in Nepal is unknown. METHODS AND FINDINGS: We analyzed 261 M. tuberculosis isolates recovered from pulmonary TB patients recruited between August 2009 and August 2010 in Nepal. M. tuberculosis lineages were determined by single nucleotide polymorphisms (SNP) typing and spoligotyping. Drug resistance was determined by sequencing the hot spot regions of the relevant target genes. Overall, 164 (62.8%) TB patients were new, and 97 (37.2%) were previously treated. Any drug resistance was detected in 50 (19.2%) isolates, and 16 (6.1%) were multidrug-resistant. The most frequent M. tuberculosis lineage was Lineage 3 (CAS/Delhi) with 106 isolates (40.6%), followed by Lineage 2 (East-Asian lineage, includes Beijing genotype) with 84 isolates (32.2%), Lineage 4 (Euro-American lineage) with 41 (15.7%) isolates, and Lineage 1 (Indo-Oceanic lineage) with 30 isolates (11.5%). Based on spoligotyping, we found 45 different spoligotyping patterns that were previously described. The Beijing (83 isolates, 31.8%) and CAS spoligotype (52, 19.9%) were the dominant spoligotypes. A total of 36 (13.8%) isolates could not be assigned to any known spoligotyping pattern. Lineage 2 was associated with female sex (adjusted odds ratio [aOR] 2.58, 95% confidence interval [95% CI] 1.42-4.67, p = 0.002), and any drug resistance (aOR 2.79; 95% CI 1.43-5.45; p = 0.002). We found no evidence for an association of Lineage 2 with age or BCG vaccination status. CONCLUSIONS: We found a large genetic diversity of M. tuberculosis in Nepal with representation of all four major lineages. Lineages 3 and 2 were dominating. Lineage 2 was associated with clinical characteristics. This study fills an important gap on the map of the M. tuberculosis genetic diversity in the Asian reg

Socioeconomic inequalities in the quality of life of older Europeans in different welfare regimes

Background: Whether socioeconomic inequalities in health and well-being persist into old age and are narrower in more generous welfare states is debated. We investigated the magnitude of socioeconomic inequality in the quality of life of Europeans in early old age and the influence of the welfare regime type on these relationships.&lt;p&gt;&lt;/p&gt; Methods: Data from individuals aged 50–75 years (n = 16 074) residing in 13 European countries were derived from Waves 2 and 3 of the Survey of Health, Ageing and Retirement in Europe. Slope indices of inequality (SIIs) were calculated for the association between socioeconomic position and CASP-12, a measure of positive quality of life. Multilevel linear regression was used to assess the overall relationship between socioeconomic position and quality of life, using interaction terms to investigate the influence of the type of welfare regime (Southern, Scandinavian, Post-communist or Bismarckian).&lt;p&gt;&lt;/p&gt; Results: Socioeconomic inequalities in quality of life were narrowest in the Scandinavian and Bismarckian regimes, and were largest by measures of current wealth. Compared with the Scandinavian welfare regime, where narrow inequalities in quality of life by education level were found in both men (SII = 0.02, 95% CI: −1.09 to 1.13) and women (SII = 1.11, 95% CI: 0.05–2.17), the difference in quality of life between the least and most educated was particularly wide in Southern and Post-communist regimes.&lt;p&gt;&lt;/p&gt; Conclusion: Individuals in more generous welfare regimes experienced higher levels of quality of life, as well as narrower socioeconomic inequalities in quality of life.&lt;p&gt;&lt;/p&gt

Utilitat de la metodologia de simulació per adquirir competències en habilitats de comunicació

Podeu consultar la Vuitena trobada de professorat de Ciències de la Salut completa a: http://hdl.handle.net/2445/66524Metodología: Se describen los talleres y seminarios de simulación empleados desde el año académico 2010-11 en la Facultad de Medicina de la Universidad de Barcelona, que se ofrecen a los alumnos a partir de 2 año de grado, con el fin de ofrecer a los alumnos de forma transversal la adquisición y refuerzo continuo de competencias en habilidades de comunicación. Siguiendo las definiciones del Libro Blanco de las Facultades de Medicina y de la Guía de la Facultad de Medicina de la UB, se ofrece formación en los siguientes aspectos de la competencia de comunicación: • Escuchar con atención, obtener y sintetizar información pertinente acerca de los problemas que aquejan al enfermo, y comprender el contenido de esta información. • Comunicación de malas noticias • Obtener un consentimiento Informado • Comunicación entre profesionales Se describen el nivel de aprendizaje, el personal docente requerido, la duración de los seminarios o talleres, los objetivos docentes, el material necesario en cada actividad y el año de la formación de grado en que se aplica. Se describe la utilización de la estrategia de feed-back para la autoevaluación de la actividad práctica, empleando grabaciones de los talleres y simulaciones de los grupos de alumnos. Se describe así mismo, las encuestas empleadas para la evaluación por el docente y los compañeros de clase de las actividades de simulación y la metodología empleada de evaluación de los seminarios y su calificación dentro de la nota final de cada asignatura. Finalmente se describen las asignaturas optativas existentes en la Facultad de Medicina de la UB para reforzar las habilidades de comunicación y los planes futuros de desarrollo de actividades formativas complementarias y de refuerzo y las propuestas evaluativas de la competencia