REHABILITACIÓN CASA E. Trazas del habitar

Intervenir el pasado para proyectar el presente requiere descubrir una historia que comenzó el año 1917 con un conjunto de viviendas obreras, al sur de la ciudad de Santiago de Chile, en el Barrio Matta. Rehabilitar significó aproximarse a los modos previos de habitar y a los vestigios constructivos para abordar un nuevo ciclo en el continuum habitable. Bajo esta perspectiva, la renovación de la casa E estableció un diálogo con las preexistencias materiales y funcionales, a través de operaciones arquitectónicas que reordenaron espacios, develando materiales ocultos descubiertos en el proceso

The carbonyl-lock mechanism underlying non-aromatic fluorescence in biological matter

Challenging the basis of our chemical intuition, recent experimental evidence reveals the presence of a new type of intrinsic fluorescence in biomolecules that exists even in the absence of aromatic or electronically conjugated chemical compounds. The origin of this phenomenon has remained elusive so far. In the present study, we identify a mechanism underlying this new type of fluorescence in different biological aggregates. By employing non-adiabatic ab initio molecular dynamics simulations combined with a data-driven approach, we characterize the typical ultrafast non-radiative relaxation pathways active in non-fluorescent peptides. We show that the key vibrational mode for the non-radiative decay towards the ground state is the carbonyl elongation. Non-aromatic fluorescence appears to emerge from blocking this mode with strong local interactions such as hydrogen bonds. While we cannot rule out the existence of alternative non-aromatic fluorescence mechanisms in other systems, we demonstrate that this carbonyl-lock mechanism for trapping the excited state leads to the fluorescence yield increase observed experimentally, and set the stage for design principles to realize novel non-invasive biocompatible probes with applications in bioimaging, sensing, and biophotonics.Recent experimental evidence shows a new type of intrinsic fluorescence in biomolecules void of aromatic chemical compounds whose origin is unclear. Here, the authors use non-adiabatic AIMD simulations to show a potential carbonyl-lock mechanism originating this phenomenon

Burnout among surgeons before and during the SARS-CoV-2 pandemic: an international survey

Background: SARS-CoV-2 pandemic has had many significant impacts within the surgical realm, and surgeons have been obligated to reconsider almost every aspect of daily clinical practice. Methods: This is a cross-sectional study reported in compliance with the CHERRIES guidelines and conducted through an online platform from June 14th to July 15th, 2020. The primary outcome was the burden of burnout during the pandemic indicated by the validated Shirom-Melamed Burnout Measure. Results: Nine hundred fifty-four surgeons completed the survey. The median length of practice was 10 years; 78.2% included were male with a median age of 37 years old, 39.5% were consultants, 68.9% were general surgeons, and 55.7% were affiliated with an academic institution. Overall, there was a significant increase in the mean burnout score during the pandemic; longer years of practice and older age were significantly associated with less burnout. There were significant reductions in the median number of outpatient visits, operated cases, on-call hours, emergency visits, and research work, so, 48.2% of respondents felt that the training resources were insufficient. The majority (81.3%) of respondents reported that their hospitals were included in the management of COVID-19, 66.5% felt their roles had been minimized; 41% were asked to assist in non-surgical medical practices, and 37.6% of respondents were included in COVID-19 management. Conclusions: There was a significant burnout among trainees. Almost all aspects of clinical and research activities were affected with a significant reduction in the volume of research, outpatient clinic visits, surgical procedures, on-call hours, and emergency cases hindering the training. Trial registration: The study was registered on clicaltrials.gov "NCT04433286" on 16/06/2020

Global disparities in surgeons’ workloads, academic engagement and rest periods: the on-calL shIft fOr geNEral SurgeonS (LIONESS) study

: The workload of general surgeons is multifaceted, encompassing not only surgical procedures but also a myriad of other responsibilities. From April to May 2023, we conducted a CHERRIES-compliant internet-based survey analyzing clinical practice, academic engagement, and post-on-call rest. The questionnaire featured six sections with 35 questions. Statistical analysis used Chi-square tests, ANOVA, and logistic regression (SPSS® v. 28). The survey received a total of 1.046 responses (65.4%). Over 78.0% of responders came from Europe, 65.1% came from a general surgery unit; 92.8% of European and 87.5% of North American respondents were involved in research, compared to 71.7% in Africa. Europe led in publishing research studies (6.6 ± 8.6 yearly). Teaching involvement was high in North America (100%) and Africa (91.7%). Surgeons reported an average of 6.7 ± 4.9 on-call shifts per month, with European and North American surgeons experiencing 6.5 ± 4.9 and 7.8 ± 4.1 on-calls monthly, respectively. African surgeons had the highest on-call frequency (8.7 ± 6.1). Post-on-call, only 35.1% of respondents received a day off. Europeans were most likely (40%) to have a day off, while African surgeons were least likely (6.7%). On the adjusted multivariable analysis HDI (Human Development Index) (aOR 1.993) hospital capacity > 400 beds (aOR 2.423), working in a specialty surgery unit (aOR 2.087), and making the on-call in-house (aOR 5.446), significantly predicted the likelihood of having a day off after an on-call shift. Our study revealed critical insights into the disparities in workload, access to research, and professional opportunities for surgeons across different continents, underscored by the HDI

Worldwide trends in underweight and obesity from 1990 to 2022: a pooled analysis of 3663 population-representative studies with 222 million children, adolescents, and adults

Background Underweight and obesity are associated with adverse health outcomes throughout the life course. We estimated the individual and combined prevalence of underweight or thinness and obesity, and their changes, from 1990 to 2022 for adults and school-aged children and adolescents in 200 countries and territories. Methods We used data from 3663 population-based studies with 222 million participants that measured height and weight in representative samples of the general population. We used a Bayesian hierarchical model to estimate trends in the prevalence of different BMI categories, separately for adults (age ≥20 years) and school-aged children and adolescents (age 5–19 years), from 1990 to 2022 for 200 countries and territories. For adults, we report the individual and combined prevalence of underweight (BMI <18·5 kg/m2) and obesity (BMI ≥30 kg/m2). For schoolaged children and adolescents, we report thinness (BMI <2 SD below the median of the WHO growth reference) and obesity (BMI >2 SD above the median). Findings From 1990 to 2022, the combined prevalence of underweight and obesity in adults decreased in 11 countries (6%) for women and 17 (9%) for men with a posterior probability of at least 0·80 that the observed changes were true decreases. The combined prevalence increased in 162 countries (81%) for women and 140 countries (70%) for men with a posterior probability of at least 0·80. In 2022, the combined prevalence of underweight and obesity was highest in island nations in the Caribbean and Polynesia and Micronesia, and countries in the Middle East and north Africa. Obesity prevalence was higher than underweight with posterior probability of at least 0·80 in 177 countries (89%) for women and 145 (73%) for men in 2022, whereas the converse was true in 16 countries (8%) for women, and 39 (20%) for men. From 1990 to 2022, the combined prevalence of thinness and obesity decreased among girls in five countries (3%) and among boys in 15 countries (8%) with a posterior probability of at least 0·80, and increased among girls in 140 countries (70%) and boys in 137 countries (69%) with a posterior probability of at least 0·80. The countries with highest combined prevalence of thinness and obesity in school-aged children and adolescents in 2022 were in Polynesia and Micronesia and the Caribbean for both sexes, and Chile and Qatar for boys. Combined prevalence was also high in some countries in south Asia, such as India and Pakistan, where thinness remained prevalent despite having declined. In 2022, obesity in school-aged children and adolescents was more prevalent than thinness with a posterior probability of at least 0·80 among girls in 133 countries (67%) and boys in 125 countries (63%), whereas the converse was true in 35 countries (18%) and 42 countries (21%), respectively. In almost all countries for both adults and school-aged children and adolescents, the increases in double burden were driven by increases in obesity, and decreases in double burden by declining underweight or thinness. Interpretation The combined burden of underweight and obesity has increased in most countries, driven by an increase in obesity, while underweight and thinness remain prevalent in south Asia and parts of Africa. A healthy nutrition transition that enhances access to nutritious foods is needed to address the remaining burden of underweight while curbing and reversing the increase in obesit

Les bases moléculaires de la thermophorèse

Thermophoresis or thermodiffusion is a thermally-driven process whereby the composition of a mixture becomes inhomogeneous under a temperature gradient, a phenomenon known as the Soret effect. The nature of thermophoresis is still not completely understood and it remains highly debated, though it is a phenomenon fairly present in the nature. One important framework field is that thermophoresis together with thermal convection could unveil the precursor accumulation in prebiotic conditions, a crucial process for the emergence of life in the absence of any compartmentalization.The main goal of this project is to understand the molecular bases for thermophoresis in dilute aqueous solutions. Thermophoresis is in essence a non-equilibrium phenomenon, and some molecular theories have focused on the interpretation of the observed concentration gradients in terms of transport coefficients. However, recent experiments have suggested that thermophoresis steady-states could be understood using equilibrium thermodynamic considerations.Molecular dynamics simulations are an ideally suited tool to decipher these questions on small model systems. We especially scoped small and amphiphilic molecules in water, which encompasses the basic molecular features of solutes with hydrophilic and hydrophobic moieties. Firstly, we proposed a robust and reliable molecular dynamic approach to undertake thermophoresis in dilute realistic solutions using all-atom molecular dynamics simulations. Secondly, we enquired into multiple physical properties that could be correlated with the Soret coefficient (i.e., the extent of the concentration-gradient in response to a temperature-gradient). Finally, we checked the viability of this thermally-driven process could be understood in terms of equilibrium thermodynamics of kinetics, as suggested before in the literatureEl objetivo principal de este proyecto es entender las bases moleculares de la termoforesis en soluciones acuosas diluidas. La termoforesis es en esencia un fenómeno de no equilibrio y algunas teorías moleculares se han centrado en la interpretación de los gradientes de concentración observados en términos de coeficientes de transporte. Sin embargo, experimentos recientes han sugerido que la termoforesis en condiciones de estado estacionario podría entenderse tomando consideraciones termodinámicas en el equilibrio.Las simulaciones de dinámica molecular son una herramienta muy útil para estudiar estos fenómenos utilizando pequeños sistemas. En esta tesis nos hemos centrado específicamente en pequeñas moléculas anfifílicas en el agua, estas moléculas abarcan características moleculares básicas con partes hidrofílicas e hidrofóbicas. En primer lugar, propusimos una metodología de dinámica molecular robusta y fiable para llevar a cabo la termoforesis en soluciones diluidas realistas, mediante simulaciones de dinámica molecular de “all atom”. En segundo lugar, investigamos las múltiples propiedades físicas que podrían correlacionarse con el coeficiente de Soret (es decir, la magnitud del gradiente de concentración en respuesta a un gradiente de temperatura). Por último, comprobamos la viabilidad de que este proceso térmico pudiera entenderse en términos de termodinámica y cinética en equilibrio, como la literatura ha sugerido anteriormente.La thermophorèse ou thermodiffusion est un processus thermique par lequel la composition d’un mélange devient inhomogène sous l'effet d'un gradient de température, ce phénomène est connu sous le nom d'effet Soret. La nature de la thermophorèse n'est pas encore complètement comprise et reste très débattue, par contre est un phénomène assez présent dans la nature. Un cadre de recherche important où la thermophorèse avec la convection thermique pourrait expliquer l'accumulation de précurseurs dans des conditions prébiotiques, un processus crucial pour l'émergence de la vie en l'absence de toute compartimentation.L'objectif principal de ce projet est de comprendre les bases moléculaires de la thermophorèse dans les solutions aqueuses diluées. La thermophorèse est par essence un phénomène de non-équilibre, et certaines théories moléculaires se sont concentrées sur l'interprétation des gradients de concentration observés en termes de coefficients de transport. Néanmoins, expériences récentes ont suggéré que la thermophorèse en conditions d’état stationnaire peut-être comprise en prenant des considérations thermodynamiques dans équilibre.Les simulations dans le cadre de dynamique moléculaire sont un outil idéal pour déchiffrer ces questions sur de petits systèmes modèles. Nous nous sommes particulièrement intéressés aux petites molécules amphiphiles dans l'eau, qui englobent les caractéristiques moléculaires de base des solutés avec des parties hydrophiles et hydrophobes. Tout d'abord, nous avons proposé une approche de dynamique moléculaire robuste et fiable pour simuler la thermophorèse dans des solutions diluées réalistes en utilisant des simulations de dynamique moléculaire tout-atome. Ensuite, nous avons recherché des multiples propriétés physiques qui pourraient être corrélées avec le coefficient de Soret (c'est-à-dire l'ampleur du gradient de concentration en réponse à un gradient de température). Finalement, nous avons vérifié la viabilité de ce processus thermique qui pourrait être compris en termes de thermodynamique ou de cinétique à l'équilibre, comme c’est suggéré précédemment dans la littérature

Les bases moléculaires de la thermophorèse

La thermophorèse ou thermodiffusion est un processus thermique par lequel la composition d’un mélange devient inhomogène sous l'effet d'un gradient de température, ce phénomène est connu sous le nom d'effet Soret. La nature de la thermophorèse n'est pas encore complètement comprise et reste très débattue, par contre est un phénomène assez présent dans la nature. Un cadre de recherche important où la thermophorèse avec la convection thermique pourrait expliquer l'accumulation de précurseurs dans des conditions prébiotiques, un processus crucial pour l'émergence de la vie en l'absence de toute compartimentation.L'objectif principal de ce projet est de comprendre les bases moléculaires de la thermophorèse dans les solutions aqueuses diluées. La thermophorèse est par essence un phénomène de non-équilibre, et certaines théories moléculaires se sont concentrées sur l'interprétation des gradients de concentration observés en termes de coefficients de transport. Néanmoins, expériences récentes ont suggéré que la thermophorèse en conditions d’état stationnaire peut-être comprise en prenant des considérations thermodynamiques dans équilibre.Les simulations dans le cadre de dynamique moléculaire sont un outil idéal pour déchiffrer ces questions sur de petits systèmes modèles. Nous nous sommes particulièrement intéressés aux petites molécules amphiphiles dans l'eau, qui englobent les caractéristiques moléculaires de base des solutés avec des parties hydrophiles et hydrophobes. Tout d'abord, nous avons proposé une approche de dynamique moléculaire robuste et fiable pour simuler la thermophorèse dans des solutions diluées réalistes en utilisant des simulations de dynamique moléculaire tout-atome. Ensuite, nous avons recherché des multiples propriétés physiques qui pourraient être corrélées avec le coefficient de Soret (c'est-à-dire l'ampleur du gradient de concentration en réponse à un gradient de température). Finalement, nous avons vérifié la viabilité de ce processus thermique qui pourrait être compris en termes de thermodynamique ou de cinétique à l'équilibre, comme c’est suggéré précédemment dans la littérature.Thermophoresis or thermodiffusion is a thermally-driven process whereby the composition of a mixture becomes inhomogeneous under a temperature gradient, a phenomenon known as the Soret effect. The nature of thermophoresis is still not completely understood and it remains highly debated, though it is a phenomenon fairly present in the nature. One important framework field is that thermophoresis together with thermal convection could unveil the precursor accumulation in prebiotic conditions, a crucial process for the emergence of life in the absence of any compartmentalization.The main goal of this project is to understand the molecular bases for thermophoresis in dilute aqueous solutions. Thermophoresis is in essence a non-equilibrium phenomenon, and some molecular theories have focused on the interpretation of the observed concentration gradients in terms of transport coefficients. However, recent experiments have suggested that thermophoresis steady-states could be understood using equilibrium thermodynamic considerations.Molecular dynamics simulations are an ideally suited tool to decipher these questions on small model systems. We especially scoped small and amphiphilic molecules in water, which encompasses the basic molecular features of solutes with hydrophilic and hydrophobic moieties. Firstly, we proposed a robust and reliable molecular dynamic approach to undertake thermophoresis in dilute realistic solutions using all-atom molecular dynamics simulations. Secondly, we enquired into multiple physical properties that could be correlated with the Soret coefficient (i.e., the extent of the concentration-gradient in response to a temperature-gradient). Finally, we checked the viability of this thermally-driven process could be understood in terms of equilibrium thermodynamics of kinetics, as suggested before in the literatureEl objetivo principal de este proyecto es entender las bases moleculares de la termoforesis en soluciones acuosas diluidas. La termoforesis es en esencia un fenómeno de no equilibrio y algunas teorías moleculares se han centrado en la interpretación de los gradientes de concentración observados en términos de coeficientes de transporte. Sin embargo, experimentos recientes han sugerido que la termoforesis en condiciones de estado estacionario podría entenderse tomando consideraciones termodinámicas en el equilibrio.Las simulaciones de dinámica molecular son una herramienta muy útil para estudiar estos fenómenos utilizando pequeños sistemas. En esta tesis nos hemos centrado específicamente en pequeñas moléculas anfifílicas en el agua, estas moléculas abarcan características moleculares básicas con partes hidrofílicas e hidrofóbicas. En primer lugar, propusimos una metodología de dinámica molecular robusta y fiable para llevar a cabo la termoforesis en soluciones diluidas realistas, mediante simulaciones de dinámica molecular de “all atom”. En segundo lugar, investigamos las múltiples propiedades físicas que podrían correlacionarse con el coeficiente de Soret (es decir, la magnitud del gradiente de concentración en respuesta a un gradiente de temperatura). Por último, comprobamos la viabilidad de que este proceso térmico pudiera entenderse en términos de termodinámica y cinética en equilibrio, como la literatura ha sugerido anteriormente

Youth as consumers in the digital age

With this article we intend to justify the need for an education that encourages adolescents to reflect upon the changes in the construction of knowledge created by the access to new technologies, which are the main cause of excessive consumption in our society today. Firstly, we discuss the ways in which ICTs are influencing the construction of knowledge, and we then focus on the role that families, schools and public administration play in consumer education, which should highlight and respect children’s rights as consumers..

Modeling Complex Metabolic Reactions, Ecological Systems, and Financial and Legal Networks with MIANN Models Based on Markov-Wiener Node Descriptors

The use of numerical parameters in Complex Network analysis is expanding to new fields of application. At a molecular level, we can use them to describe the molecular structure of chemical entities, protein interactions, or metabolic networks. However, the applications are not restricted to the world of molecules and can be extended to the study of macroscopic nonliving systems, organisms, or even legal or social networks. On the other hand, the development of the field of Artificial Intelligence has led to the formulation of computational algorithms whose design is based on the structure and functioning of networks of biological neurons. These algorithms, called Artificial Neural Networks (ANNs), can be useful for the study of complex networks, since the numerical parameters that encode information of the network (for example centralities/node descriptors) can be used as inputs for the ANNs. The Wiener index (<i>W</i>) is a graph invariant widely used in chemoinformatics to quantify the molecular structure of drugs and to study complex networks. In this work, we explore for the first time the possibility of using Markov chains to calculate analogues of node distance numbers/<i>W</i> to describe complex networks from the point of view of their nodes. These parameters are called Markov-Wiener node descriptors of order <i>k</i>^th (<i>W_k</i>). Please, note that these descriptors are not related to Markov-Wiener stochastic processes. Here, we calculated the <i>W</i>_<i>k</i>(<i>i</i>) values for a very high number of nodes (>100,000) in more than 100 different complex networks using the software MI-NODES. These networks were grouped according to the field of application. Molecular networks include the Metabolic Reaction Networks (MRNs) of 40 different organisms. In addition, we analyzed other biological and legal and social networks. These include the Interaction Web Database Biological Networks (IWDBNs), with 75 food webs or ecological systems and the Spanish Financial Law Network (SFLN). The calculated <i>W</i>_<i>k</i>(<i>i</i>) values were used as inputs for different ANNs in order to discriminate correct node connectivity patterns from incorrect random patterns. The MIANN models obtained present good values of Sensitivity/Specificity (%): MRNs (78/78), IWDBNs (90/88), and SFLN (86/84). These preliminary results are very promising from the point of view of a first exploratory study and suggest that the use of these models could be extended to the high-throughput re-evaluation of connectivity in known complex networks (collation)

Diastereoselective Construction of the 6‑Oxa-2-azabicyclo[3.2.1]octane Scaffold from Chiral α‑Hydroxyaldehyde Derivatives by the Aza-Prins Reaction

(<i>R</i>)-2,3-Di-<i>O</i>-benzylglyceraldehyde and <i>N</i>-tosyl homoallylamine undergo aza-Prins cyclization to afford (1<i>R</i>,5<i>S</i>,7<i>S</i>)-7-[(benzyloxy)­methyl]-2-tosyl-6-oxa-2-azabicyclo­[3.2.1]­octane in a highly diastereoselective manner through an unexpected intramolecular nucleophilic attack. Our work has opened a new route toward the asymmetric synthesis of 7-(alkyl or aryl)-6-oxa-2-azabicyclo[3.2.1]­octane derivatives from chiral α-hydroxyaldehyde derivatives in one step