Insights into water coordination associated with the Cu(II)/Cu(I) electron transfer at a biomimetic Cu centre.

International audienceThe coordination properties of the biomimetic complex [Cu(TMPA)(H2O)](CF3SO3)2 (TMPA = tris(2-pyridylmethyl)amine) have been investigated by electrochemistry combined with UV-Vis and EPR spectroscopy in different non-coordinating media including imidazolium-based room-temperature ionic liquids, for different water contents. The solid-state X-ray diffraction analysis of the complex shows that the cupric centre lies in a N4O coordination environment with a nearly perfect trigonal bipyramidal geometry (TBP), the water ligand being axially coordinated to Cu(II). In solution, the coordination geometry of the complex remains TBP in all media. Neither the triflate ion nor the anions of the ionic liquids were found to coordinate the copper centre. Cyclic voltammetry in all media shows that the decoordination of the water molecule occurs upon monoelectronic reduction of the Cu(II) complex. Back-coordination of the water ligand at the cuprous state can be detected by increasing the water content and/or decreasing the timescale of the experiment. Numerical simulations of the voltammograms allow the determination of kinetics and thermodynamics for the water association-dissociation mechanism. The resulting data suggest that (i) the binding/unbinding of water at the Cu(I) redox state is relatively slow and equilibrated in all media, and (ii) the binding of water at Cu(I) is somewhat faster in the ionic liquids than in the non-coordinating solvents, while the decoordination process is weakly sensitive to the nature of the solvents. These results suggest that ionic liquids favour water exchange without interfering with the coordination sphere of the metal centre. This makes them promising media for studying host-guest reactions with biomimetic complexes

Clonal chromosomal mosaicism and loss of chromosome Y in elderly men increase vulnerability for SARS-CoV-2

The pandemic caused by severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2, COVID-19) had an estimated overall case fatality ratio of 1.38% (pre-vaccination), being 53% higher in males and increasing exponentially with age. Among 9578 individuals diagnosed with COVID-19 in the SCOURGE study, we found 133 cases (1.42%) with detectable clonal mosaicism for chromosome alterations (mCA) and 226 males (5.08%) with acquired loss of chromosome Y (LOY). Individuals with clonal mosaic events (mCA and/or LOY) showed a 54% increase in the risk of COVID-19 lethality. LOY is associated with transcriptomic biomarkers of immune dysfunction, pro-coagulation activity and cardiovascular risk. Interferon-induced genes involved in the initial immune response to SARS-CoV-2 are also down-regulated in LOY. Thus, mCA and LOY underlie at least part of the sex-biased severity and mortality of COVID-19 in aging patients. Given its potential therapeutic and prognostic relevance, evaluation of clonal mosaicism should be implemented as biomarker of COVID-19 severity in elderly people. Among 9578 individuals diagnosed with COVID-19 in the SCOURGE study, individuals with clonal mosaic events (clonal mosaicism for chromosome alterations and/or loss of chromosome Y) showed an increased risk of COVID-19 lethality

Diseño estratégico de vanguardia

La integración del diseño con la vanguardia se observa natural, esto es, el diseño es una disciplina abductiva y la vanguardia persigue fines prospectivos, es decir, en ambos casos se trata de objetivos de posibilidad futura. De tal suerte, este libro, emanado de una parte de las ponencias rigurosamente arbitradas del Coloquio Internacional de Diseño 2016, está dividido en tres secciones o capítulos, a saber, el capítulo uno relacionado con la teoría y metodología para proyectos de diseño de vanguardia, el segundo sobre la tecnología, la innovación y la sostenibilidad de vanguardia de dichos proyectos, y finalmente el último capítulo, vinculado con la gestión estratégica de proyectos de vanguardia.La historia se forja de hechos e interpretaciones, de pasados construidos y de presentes en procesos constantes, estudiados en forma estricta por las ciencias. Por su parte, el futuro ostenta la posibilidad de ser indefinidamente planeado con base en las variopintas aproximaciones teóricas y empíricas que dan fundamento a este tipo de ciencia; éstas son denominadas prospectivas y sus bases vanguardias. Resulta importante señalar, que estas posibilidades sólo permiten tener una idea hipotética de lo que será la realidad y el mundo de vida de los seres vivos y su contexto, no obstante, se trata de la única manera racional que tiene el ser humano de prever ese futuro posible. Las distintas ciencias y disciplinas nos permiten construir históricamente estas posibilidades partiendo de datos, hechos, significados y un sinfín de informaciones que le dan cuerpo y sentido a tales posibilidades. En este sentido, la vanguardia, como base del conocimiento prospectivo, observa la necesidad de ser escrita, leída y discutida en los términos más estrictos con el fin de volver las predicciones más precisas. El diseño por su parte, es definido de manera sucinta como la disciplina proyectual estratégica y sistémica de la posibilidad, dirigida a procesos de significación utilitaria y simbólica para la comprensión –o interpretación– y modificación –o proyectación– de niveles de realidad (referentes y sujetos) desde diversos aparatos teóricos y empíricos –perspectivas disciplinarias–

Mortality from gastrointestinal congenital anomalies at 264 hospitals in 74 low-income, middle-income, and high-income countries: a multicentre, international, prospective cohort study

Summary Background Congenital anomalies are the fifth leading cause of mortality in children younger than 5 years globally. Many gastrointestinal congenital anomalies are fatal without timely access to neonatal surgical care, but few studies have been done on these conditions in low-income and middle-income countries (LMICs). We compared outcomes of the seven most common gastrointestinal congenital anomalies in low-income, middle-income, and high-income countries globally, and identified factors associated with mortality. Methods We did a multicentre, international prospective cohort study of patients younger than 16 years, presenting to hospital for the first time with oesophageal atresia, congenital diaphragmatic hernia, intestinal atresia, gastroschisis, exomphalos, anorectal malformation, and Hirschsprung’s disease. Recruitment was of consecutive patients for a minimum of 1 month between October, 2018, and April, 2019. We collected data on patient demographics, clinical status, interventions, and outcomes using the REDCap platform. Patients were followed up for 30 days after primary intervention, or 30 days after admission if they did not receive an intervention. The primary outcome was all-cause, in-hospital mortality for all conditions combined and each condition individually, stratified by country income status. We did a complete case analysis. Findings We included 3849 patients with 3975 study conditions (560 with oesophageal atresia, 448 with congenital diaphragmatic hernia, 681 with intestinal atresia, 453 with gastroschisis, 325 with exomphalos, 991 with anorectal malformation, and 517 with Hirschsprung’s disease) from 264 hospitals (89 in high-income countries, 166 in middleincome countries, and nine in low-income countries) in 74 countries. Of the 3849 patients, 2231 (58·0%) were male. Median gestational age at birth was 38 weeks (IQR 36–39) and median bodyweight at presentation was 2·8 kg (2·3–3·3). Mortality among all patients was 37 (39·8%) of 93 in low-income countries, 583 (20·4%) of 2860 in middle-income countries, and 50 (5·6%) of 896 in high-income countries (p<0·0001 between all country income groups). Gastroschisis had the greatest difference in mortality between country income strata (nine [90·0%] of ten in lowincome countries, 97 [31·9%] of 304 in middle-income countries, and two [1·4%] of 139 in high-income countries; p≤0·0001 between all country income groups). Factors significantly associated with higher mortality for all patients combined included country income status (low-income vs high-income countries, risk ratio 2·78 [95% CI 1·88–4·11], p<0·0001; middle-income vs high-income countries, 2·11 [1·59–2·79], p<0·0001), sepsis at presentation (1·20 [1·04–1·40], p=0·016), higher American Society of Anesthesiologists (ASA) score at primary intervention (ASA 4–5 vs ASA 1–2, 1·82 [1·40–2·35], p<0·0001; ASA 3 vs ASA 1–2, 1·58, [1·30–1·92], p<0·0001]), surgical safety checklist not used (1·39 [1·02–1·90], p=0·035), and ventilation or parenteral nutrition unavailable when needed (ventilation 1·96, [1·41–2·71], p=0·0001; parenteral nutrition 1·35, [1·05–1·74], p=0·018). Administration of parenteral nutrition (0·61, [0·47–0·79], p=0·0002) and use of a peripherally inserted central catheter (0·65 [0·50–0·86], p=0·0024) or percutaneous central line (0·69 [0·48–1·00], p=0·049) were associated with lower mortality. Interpretation Unacceptable differences in mortality exist for gastrointestinal congenital anomalies between lowincome, middle-income, and high-income countries. Improving access to quality neonatal surgical care in LMICs will be vital to achieve Sustainable Development Goal 3.2 of ending preventable deaths in neonates and children younger than 5 years by 2030

Les sels fondus d’hydroxydes pour le traitement de déchets

International audienc

Waste treatment in molten salt hydroxide

International audienc

O-O bond cleavage by electrochemical reduction of a side-on peroxo dicopper model of hemocyanin.

International audienceThe redox properties of the μ-η2:η2 peroxo complex [Cu2(H6M4h)(O2)]2+ were elucidated. This study constitutes the first full electrochemical and spectroelectrochemical characterization of a side-on peroxo Cu2:O2 bioinorganic model complex. The peroxo complex is irreversibly reduced in a two- electron process localized on the peroxo ligand triggering the cleavage of the O-O bondLes propriétés redox du complexe peroxo μ-η2:η2 [Cu2(H6M4h)(O2)]2+, modèle de l’hémocyanine, ont été élucidées par des études électrochimiques et spectroélectrochimiques. La réduction du complexe peroxo est irréversible et s’effectue selon un processus à deux électrons localisé sur le ligand peroxyde, déclenchant la rupture de la liaison O-O

The Caldera. No. 12

El decreto 1290 de abril del 2009, que modifica al decreto 0230 que venía rigiendo para la evaluación y promoción de los estudiantes, otorga a las instituciones educativas la autonomía para determinar la forma cómo los estudiantes serán evaluados y promovidos al finalizar el año escolar. Este es un espacio para la reflexión sobre el deber ser de un proceso en el cual interesa formar personas responsables y con sólidos conocimientos en todas las áreas del saber, que les permitan el desarrollo de sus competencias en los ámbitos del SER, el CONOCER, y el SABER HACER. El instituto Caldas, consciente del reto que para promover el aprendizaje plantea este decreto, ha estado trabajando sobre el mismo con el fin de mejorar lo que se ha venido haciendo. Partimos del SENTIDO de lo que, en un proceso educativo, debe representar la evaluación: un momento de reflexión tanto para estudiantes como para maestros, que permite acceder no sólo a la comprensión de un conocimiento específico, sino al desarrollo de las competencias. Desde esta mirada, estamos trabajando para la generación de estrategias que permitan al estudiante, en primera instancia, avanzar en su proceso de crecimiento personal y en lo académico, lograr la apropiación de los conceptos básicos de cada asignatura, teniendo como resultado la aprobación de su año escolar. En el 2011, año en el cual ya estaremos funcionando dentro del calendario A, aplicaremos el nuevo sistema de evaluación y promoción, el cual será dado a conocer antes de finalizar el 2010.Sobre la promoción de los estudiantes... 1 De la debilidad a la fortaleza. Democracia... 2 GOBIERNO ESCOLAR 2010-06 ¡¡ JORNADA EN LA QUE GANAMOS TODOS !!. Bicentenario... 3 Cuento ganador Ulibro 2009 El gato arrepentid. Escribir si paga... 4 La dificultad de "ser" hoy. Preguntar, Sinónimo de diferentes realidades. El fracaso que salvó la Navidad... 5 Galería de Artistas Caldistas. Pintores de Manga. Un baile de generaciones... 6 La discapacidad está en la mente. Una mariposa de abril Prom 2010. El encanto de las fabulas Festivalito Ruitoqueño. El día de la Tierra. Día del Árbol o Día de los Búcaros WELCOME TO THE WORLD OF PHOTOGRAPHY Living in Colombia INAUGURACIÓN DE LOS JUEGOS INTERCLASES 2010 Campeonato nacional de Patinaje de Carreras Cartagena de Indias2010Decree 1290 of April 2009, which modifies Decree 0230 that had been governing the evaluation and promotion of students, grants educational institutions the autonomy to determine how students will be evaluated and promoted at the end of the school year. This is a space for reflection on the duty to be of a process in which it is interesting to train responsible people with solid knowledge in all areas of knowledge, which allow them to develop their skills in the areas of BEING, KNOWING, and the KNOW-HOW. The Caldas Institute, aware of the challenge that this decree poses to promote learning, has been working on it in order to improve what has been done. We start from the SENSE of what, in an educational process, evaluation must represent: a moment of reflection for both students and teachers, which allows access not only to the understanding of specific knowledge, but also to the development of competences. From this point of view, we are working to generate strategies that allow the student, in the first instance, to advance in their process of personal and academic growth, achieve the appropriation of the basic concepts of each subject, resulting in the approval of their school year. In 2011, the year in which we will already be working within calendar A, we will apply the new evaluation and promotion system, which will be announced before the end of 2010.Modalidad Virtua