C4-C5 fused pyrazol-3-amines: when the degree of unsaturation and electronic characteristics of the fused ring controls regioselectivity in Ullmann and acylation reactions

Pyrazol-3-amine is a scaffold present in a large number of compounds with a wide range of biological activities and, in many cases, the heterocycle is C4-C5 fused to a second ring. Among the different reactions used for the decoration of the pyrazole ring, Ullmann and acylation have been widely applied. However, there is some confusion in the literature regarding the regioselectivity of such reactions (substitution at N1 or N2 of the pyrazole ring) and no predictive rule has been so far established. As a part of our work on 3-amino-pyrazolo[3,4-b]pyridones 13, we have studied the regioselectivity of such reactions in different C4-C5 fused pyrazol-3-amines. As a rule of thumb, the Ullmann and acylation reactions take place, predominantly, at the NH and non-protonated nitrogen atom of the pyrazole ring respectively, of the most stable initial tautomer (1H- or 2H-pyrazole), which can be easily predicted by using DFT calculations

Principales medidas de profilaxis en endoscopia bariátrica. Guía Española de Recomendación de Expertos

Bariatric endoscopy (BE) encompasses a number of techniques -some consolidated, some under development- aiming to contribute to the management of obese patients and their associated metabolic diseases as a complement to dietary and lifestyle changes. To date different intragastric balloon models, suture systems, aspiration methods, substance injections and both gastric and duodenal malabsorptive devices have been developed, as well as endoscopic procedures for the revision of bariatric surgery. Their ongoing evolution conditions a gradual increase in the quantity and quality of scientific evidence about their effectiveness and safety. Despite this, scientific evidence remains inadequate to establish strong grades of recommendation allowing a unified perspective on prophylaxis in BE. This dearth of data conditions leads, in daily practice, to frequently extrapolate the measures that are used in bariatric surgery (BS) and/or in general therapeutic endoscopy. In this respect, this special article is intended to reach a consensus on the most common prophylactic measures we should apply in BE. The methodological design of this document was developed while attempting to comply with the following 5 phases: Phase 1: delimitation and scope of objectives, according to the GRADE Clinical Guidelines. Phase 2: setup of the Clinical Guide-developing Group: national experts, members of the Grupo Español de Endoscopia Bariátrica (GETTEMO, SEED), SEPD, and SECO, selecting 2 authors for each section. Phase 3: clinical question form (PICO): patients, intervention, comparison, outcomes. Phase 4: literature assessment and synthesis. Search for evidence and elaboration of recommendations. Based on the Oxford Centre for Evidence-Based Medicine classification, most evidence in this article will correspond to level 5 (expert opinions without explicit critical appraisal) and grade of recommendation C (favorable yet inconclusive recommendation) or D (inconclusive or inconsistent studies). Phase 5: External review by experts. We hope that these basic preventive measures will be of interest for daily practice, and may help prevent medical and/or legal conflicts for the benefit of patients, physicians, and BE in general

Abiotic Input of Fixed Nitrogen by Bolide Impacts to Gale Crater During the Hesperian : Insights From the Mars Science Laboratory

We acknowledge the NASA Mars Science Laboratory Program, Centre National d'Études Spatiales, the Universidad Nacional Autónoma de México (PAPIIT IN109416, IN111619, and PAPIME PE103216), and the Consejo Nacional de Ciencia y Tecnología de México (CONACyT 220626) for their support. We thank Fred Calef for constructing Figure 4 and appreciate the interest and support received from John P. Grotzinger and Joy A. Crisp throughout the Curiosity mission. The authors are grateful to the SAM and MSL teams for successful operation of the SAM instrument and the Curiosity rover. The data used in this paper are listed in the supporting information, figures, and references. SAM Data contained in this paper are publicly available through the NASA Planetary Data System at http://pds‐geosciences.wustl.edu/missions/msl/sam.htm. We would like to express gratitude to Pierre‐Yves Meslin from the Research Institute in Astrophysics and Planetology at Toulouse, France, and five anonymous reviewers whose comments/suggestions on earlier drafts helped improve and clarify this manuscript. The authors declare no conflicts of interests.Peer reviewedPublisher PD

Scientific output on transsexuality in the Spanish biomedical literature: Bibliometric and content analysis (1973-2011)

Objetivo: Explorar la evolución del conocimiento científico sobre transexualidad durante los últimos 40 años, a través de un análisis bibliométrico y de contenido de la producción de la literatura biomédica española sobre la transexualidad entre los años 1973 y 2011. Método: Descriptivo y transversal. Universo: artículos biomédicos españoles sobre transexualidad publicados entre 1973 y 2011. Fuente: ÍndiceMédico Español e ISOC-Ciencias Sociales y Humanidades. Análisis: bibliométrico y de contenido de las publicaciones biomédicas. Resultados: 65 artículos biomédicos analizados. Entre 1973 y 1984, en España, el conocimiento sobre transexualidad se produce y circula en revistas médicas. En 1996 se inicia una década de gran productividad, y en los años siguientes el número de revistas que publican sobre transexualidad se multiplica. Hasta 2006, año de mayor productividad biomédica, los discursos biomédicos reproducen representaciones de la transexualidad ancladas en el determinismo biológico. En el período 2008-2011, los y las profesionales incorporan teorías feministas y perspectivas sociales en sus discursos. Conclusiones: En el último cuarto del siglo xx, el discurso médico dominante ha considerado las manifestaciones de las personas transexuales desde una perspectiva biologicista que concibe la transexualidad como un error de correspondencia sexo/género. En los últimos años, la aparición de nuevas categorías de identidad y la reflexión desde posturas no esencialistas y normativas del género favorece la gestión clínica de la transexualidad.Objective: To explore the scientific output on transsexuality in the Spanish biomedical literature between 1973 and 2011, through bibliometric and content analyses. Methods: We carried out a descriptive, cross-sectional study of Spanish biomedical articles on transsexuality published between 1973 and 2011. The data sources consisted of Índice Médico Español and ISOC-Ciencias Sociales y Humanidades. Bibliometric and content analyses were performed. Results: A total of 65 papers were analyzed. Knowledge on transsexuality in Spain began to appear in medical journals between 1973 and 1984. A decade of intense productivity began in 1996 and the number of journals publishing articles on transsexuality multiplied in the following years. Until 2006, the year with the most biomedical productivity, biomedical discourses reproduced representations of transsexuality anchored in biological determinism. From 2008-2011, professionals writing on the topic incorporated feminist theories and social perspectives in their discourses. Conclusions: In the last quarter of the twentieth century, the dominant medical discourse considered manifestations of transsexual people from a biologist perspective that conceives transsexuality as a configuration mismatch between sex and gender. The emergence of new identity categories and medical reflection from non-essentialist and non-normative gender perspectives has improved the clinical management of transsexuality

TRY plant trait database – enhanced coverage and open access

Plant traits - the morphological, anatomical, physiological, biochemical and phenological characteristics of plants - determine how plants respond to environmental factors, affect other trophic levels, and influence ecosystem properties and their benefits and detriments to people. Plant trait data thus represent the basis for a vast area of research spanning from evolutionary biology, community and functional ecology, to biodiversity conservation, ecosystem and landscape management, restoration, biogeography and earth system modelling. Since its foundation in 2007, the TRY database of plant traits has grown continuously. It now provides unprecedented data coverage under an open access data policy and is the main plant trait database used by the research community worldwide. Increasingly, the TRY database also supports new frontiers of trait‐based plant research, including the identification of data gaps and the subsequent mobilization or measurement of new data. To support this development, in this article we evaluate the extent of the trait data compiled in TRY and analyse emerging patterns of data coverage and representativeness. Best species coverage is achieved for categorical traits - almost complete coverage for ‘plant growth form’. However, most traits relevant for ecology and vegetation modelling are characterized by continuous intraspecific variation and trait–environmental relationships. These traits have to be measured on individual plants in their respective environment. Despite unprecedented data coverage, we observe a humbling lack of completeness and representativeness of these continuous traits in many aspects. We, therefore, conclude that reducing data gaps and biases in the TRY database remains a key challenge and requires a coordinated approach to data mobilization and trait measurements. This can only be achieved in collaboration with other initiatives

Nurses' perceptions of aids and obstacles to the provision of optimal end of life care in ICU

Contains fulltext : 172380.pdf (publisher's version ) (Open Access

Preparation and characterization of persistent maltose-conjugated triphenylmethyl radicals

The condensation reaction of d-maltose to free radicals of the series of tris(2,4,6-trichlorophenyl)methyl (TTM) and tris(perchlorophenyl)methyl (PTM) has been described for the first time. The new persistent radicals 1 and 2 are very stable and have been characterized by EPR. Their cyclic voltammograms show a quasi-reversible process in the cathode, being reduced to the corresponding anions, with redox potentials a little lower than those of TTM and PTM, respectively. Their oxidant activity is in close relation with their reduction potentials. Therefore, while 2 is reduced by ascorbic acid, 1 remains unaltered.Financial support for this research from the MCI (Spain) through projects AGL2009-12374-C03-03/ALI and CTQ2009-13797 is gratefully acknowledged. J.A.M. gratefully acknowledges the Spanish Foreign Office Department for a predoctoral grant (AECI).Peer Reviewe

A food-web comparative modeling approach highlights ecosystem singularities of the Gulf of Alicante (Western Mediterranean Sea)

13 pages, 4 figures, 3 tables, supplementary data https://doi.org/10.1016/j.seares.2021.102073A food-web comparative modeling approach using Ecopath with Ecosim (EwE) was built to characterize the ecosystem of the Gulf of Alicante (GoA) and investigate its singularities. The GoA differs from neighboring ecosystems of the Western Mediterranean Sea because of its different oceanographic characteristics. We developed a model of the study area representing early 2010s, covering a total area of 7085 km2, and including the continental shelf and upper slope with depths from 50 to 800 m. In total, 45 functional groups considering all components of the food web (fish, marine mammals, seabirds, invertebrates, primary producers, and detritus) were selected to build the ecological model. The fishery was represented by the four main fleets operating in the area (i.e., bottom trawl, purse seine, longlines, and small-scale fisheries) and we included official landing data and estimated percentage of discarded species. Results were then compared with available outputs of available models representing adjacent ecosystems such as the Gulf of Cadiz (in the Atlantic side) and the North Western Mediterranean Sea (north of the study area). The study revealed that the major differences found between models were due to the lower primary production in the GoA. This led to lower catches and higher importance of the demersal compartment, where the most biomass was associated to the detritus. The main trophic flows in the GoA were originated at the basis of the food web, likely related to bottom-up flow control. Interactions between pelagic and demersal groups were weaker than in neighboring areas. Despite the high values of ecotrophic efficiencies and mortality rates, results showed a lower fishing pressure than in neighboring areas, suggesting a moderate exploitation level of marine resources in the GoA. This study fills a knowledge gap in the area and sets the baseline to develop future studies to test scenarios of change and management optionsData collection was co-funded by the EU through the European Maritime and Fisheries Fund(EMFF) within the National Program for the collection, management and use of data in the fisheries sector and support for scientific advice regarding the Common Fisheries Policy. M Coll and J.M. Bellido would like to acknowledge financial support by the Spanish Research project PELWEB (CTM2017-88939-R) funded by Spanish Ministry of Science, Innovation and Universities and the European Union's Horizon 2020 research and innovation programme under grant agreement No 869300 (FutureMARES)Peer reviewe

Perceived motivational climate, psychological needs and intrinsic motivation as Predictors of sport commitment in adolescent athletes.

El estudio analizó la predicción del clima motivacional percibido, la satisfacción de las necesidades psicológicas básicas y la motivación intrínseca sobre la adherencia a la práctica deportiva. Se utilizó una muestra de 580 deportistas con una edad media de 14.46 años. Se emplearon el Cuestionario del Clima Motivacional Percibido en el Deporte-2, la Escala de las Necesidades Psicológicas Básicas en el Ejercicio, el factor motivación intrínseca de la Escala de Motivación Deportiva y la Medida de la Intencionalidad para ser Físicamente Activo. Los resultados del modelo de ecuaciones estructurales mostraron que el clima motivacional que implica a la tarea predecía las tres necesidades psicológicas básicas y la intención de seguir siendo físicamente activo. Por otro lado, el clima motivacional que implica al ego predecía la necesidades de autonomía y de competencia, aunque con un peso de regresión en ambos casos mucho menor que como lo hacía el clima tarea. La satisfacción de las tres necesidades psicológicas básicas predijo positivamente la motivación intrínseca. Por su parte, la motivación intrínseca predijo la intención de ser físicamente activo en el futuro. Se discuten los resultados en relación a la importancia de fomentar un clima motivacional tarea en los practicantes para incrementar la adherencia a la práctica deportiva.The study analyzed the prediction of perceived motivational climate, basic psychological needs satisfaction and intrinsic motivation on adherence to sports. A sample of 580 athletes with a mean age of 14.46 years, participated in the study. The Perceived Motivational Climate in Sport Questionnaire-2, the Basic Psychological Needs in Exercise Scale, the intrinsic motivation factor of the Sport Motivation Scale and Intention of Being Physically Active were used. Structural equation modeling results showed that the taskinvolving motivational climate positively predicted the three basic psychological needs and the intention to practice physical activity into the future. Moreover, the ego-involving motivational climate predicted autonomy and competence needs, although with regression weight in both cases much less than it did the the task-involving motivational climate. The satisfaction of the three basic psychological needs positively predicted intrinsic motivation. Besides, intrinsic motivation predicted the intention to be physically active in the future. Results are discussed in relation to the importance of promoting a task-involving motivational climate to increase adherence to sport

Clima motivacional percibido, necesidades psicológicas y motivación intrínseca como predictores del compromiso deportivo en adolescentes

The study analyzed the prediction of perceived motivational climate, basic psychological needs satisfaction and intrinsic motivation on adherence to sports. A sample of 580 athletes with a mean age of 14.46 years, participated in the study. The Perceived Motivational Climate in Sport Questionnaire-2, the Basic Psychological Needs in Exercise Scale, the intrinsic motivation factor of the Sport Motivation Scale and Intention of Being Physically Active were used. Structural equation modeling results showed that the taskinvolving motivational climate positively predicted the three basic psychological needs and the intention to practice physical activity into the future. Moreover, the ego-involving motivational climate predicted autonomy and competence needs, although with regression weight in both cases much less than it did the the task-involving motivational climate. The satisfaction of the three basic psychological needs positively predicted intrinsic motivation. Besides, intrinsic motivation predicted the intention to be physically active in the future. Results are discussed in relation to the importance of promoting a task-involving motivational climate to increase adherence to sportEl estudio analizó la predicción del clima motivacional percibido, la satisfacción de las necesidades psicológicas básicas y la motivación intrínseca sobre la adherencia a la práctica deportiva. Se utilizó una muestra de 580 deportistas con una edad media de 14.46 años. Se emplearon el Cuestionario del Clima Motivacional Percibido en el Deporte-2, la Escala de las Necesidades Psicológicas Básicas en el Ejercicio, el factor motivación intrínseca de la Escala de Motivación Deportiva y la Medida de la Intencionalidad para ser Físicamente Activo. Los resultados del modelo de ecuaciones estructurales mostraron que el clima motivacional que implica a la tarea predecía las tres necesidades psicológicas básicas y la intención de seguir siendo físicamente activo. Por otro lado, el clima motivacional que implica al ego predecía la necesidades de autonomía y de competencia, aunque con un peso de regresión en ambos casos mucho menor que como lo hacía el clima tarea. La satisfacción de las tres necesidades psicológicas básicas predijo positivamente la motivación intrínseca. Por su parte, la motivación intrínseca predijo la intención de ser físicamente activo en el futuro. Se discuten los resultados en relación a la importancia de fomentar un clima motivacional tarea en los practicantes para incrementar la adherencia a la práctica deportiva