70 research outputs found

    Group 10 Metal Benzene-1,2-dithiolate Derivatives in the Synthesis of Coordination Polymers Containing Potassium Countercations

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    This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/abs/10.1021/acs.inorgchem.7b01775The use of theoretical calculations has allowed us to predict the coordination behavior of dithiolene [M(SC6H4S)2]2- (M = Ni, Pd, Pt) entities, giving rise to the first organometallic polymers {[K2(ÎŒ-H2O)2][Ni(SC6H4S)2]}n and {[K2(ÎŒ-H2O)2(thf)]2[K2(ÎŒ-H2O)2(thf)2][Pd3(SC6H4S)6]}n by one-pot reactions of the corresponding d10 metal salts, 1,2-benzenedithiolene, and KOH. The polymers are based on σ,π interactions between potassium atoms and [M(SC6H4S)2]2- (M = Ni, Pd) entities. In contrast, only σ interactions are observed when the analogous platinum derivative is used instead, yielding the coordination polymer {[K2(ÎŒ-thf)2][Pt(SC6H4S)2]}nThis work was supported in part by the MICINN (grants MAT2016-77608-C3-1-P and MAT2016-75883-C2-1-P), Generalitat Valenciana (PrometeoII/2014/076), and ISIC. J.I.M. acknowledges financial support by the “Ramon y Cajal ́ ” Program of MINECO (RYC-2015-17730

    Clinical characteristics and outcome of Spanish patients with ANCA-associated vasculitides: Impact of the vasculitis type, ANCA specificity, and treatment on mortality and morbidity

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    Spain; ANCA; VasculitidesEspanya; ANCA; VasculitisEspaña; ANCA; VasculitisThe aim of this study was to describe the clinical characteristics of ANCA-associated vasculitides (AAV) at presentation, in a wide cohort of Spanish patients, and to analyze the impact of the vasculitis type, ANCA specificity, prognostic factors, and treatments administered at diagnosis, in the outcome.A total of 450 patients diagnosed between January 1990 and January 2014 in 20 Hospitals from Spain were included. Altogether, 40.9% had granulomatosis with polyangiitis (GPA), 37.1% microscopic polyangiitis (MPA), and 22% eosinophilic granulomatosis with polyangiitis (EGPA). The mean age at diagnosis was 55.6 ± 17.3 years, patients with MPA being significantly older (P < 0.001). Fever, arthralgia, weight loss, respiratory, and ear-nose-throat (ENT) symptoms, were the most common at disease onset. ANCAs tested positive in 86.4% of cases: 36.2% C-ANCA-PR3 and 50.2% P-ANCA-MPO. P-ANCA-MPO was significantly associated with an increased risk for renal disease (OR 2.6, P < 0.001) and alveolar hemorrhage (OR 2, P = 0.010), while C-ANCA-PR3 was significantly associated with an increased risk for ENT (OR 3.4, P < 0.001) and ocular involvement (OR 2.3, P = 0.002). All patients received corticosteroids (CS) and 74.9% cyclophosphamide (CYC). The median follow-up was 82 months (IQR 100.4). Over this period 39.9% of patients suffered bacterial infections and 14.6% opportunistic infections, both being most prevalent in patients with high-cumulated doses of CYC and CS (P < 0.001). Relapses were recorded in 36.4% of cases with a mean rate of 2.5 ± 2.3, and were more frequent in patients with C-ANCA-PR3 (P = 0.012). The initial disease severity was significantly associated with mortality but not with the occurrence of relapses. One hundred twenty-nine (28.7%) patients (74 MPA, 41 GPA, 14 EGPA) died. The mean survival was 58 months (IQR 105) and was significantly lower for patients with MPA (P < 0.001). Factors independently related to death were renal involvement (P = 0.010), cardiac failure (P = 0.029) and age over 65 years old (P < 0.001) at disease onset, and bacterial infections (P < 0.001). An improved outcome with significant decrease in mortality and treatment-related morbidity was observed in patients diagnosed after 2000, and was related to the implementation of less toxic regimens adapted to the disease activity and stage, and a drastic reduction in the cumulated CYC and CS dose

    Rational design of copper(II)-uracil nanoprocessed coordination polymers to improve their cytotoxic activity in biological media

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    This work is focused on the rational structural design of two isostructural Cu(II) nano-coordination polymers (NCPs) with uracil-1-acetic acid (UAcOH) (CP1n) and 5-fluorouracil-1-acetic acid (CP2n). Suitable single crystals for ꭕ-ray diffraction studies of CP1 and CP2 were prepared under hydrothermal conditions, enabling their structural determination as 1D-CP ladder-like polymeric structures. The control of the synthetic parameters allows their processability into water colloids based on nanoplates (CP1n and CP2n). These NCPs are stable in water at physiological pHs for long periods. However, interestingly, CP1n is chemically altered in culture media. These transformations provoke the partial release of its building blocks and the formation of new species, such as [Cu(UAcO)2(H2O)4]·2H2O (Cu(II)-complex), and species corresponding to the partial reduction of the Cu(II) centers. The cytotoxic studies of CP1n versus human pancreatic adenocarcinoma and human uveal melanoma cells show that CP1n produces a decrease in the cell viability, while their UAcOH and Cu(II)-complex are not cytotoxic under similar conditions. The copper reduction species detected in the hydrolysis of CP1n are closely related to the formation of the reactive oxygen species (ROS) detected in the cytotoxic studies. These results prompted us to prepare CP2n that was designed to improve the cytotoxicity by the substitution of UAcO by 5-FUAcO, taking into account the anticancer activity of the 5-fluorouracil moiety. The new CP2n has a similar behavior to CP1n both in water and in biological media. However, its subtle structural differences are vital in improving its cytotoxic activity. Indeed, the release during the hydrolysis of species containing the 5-fluorouracil moiety provokes a remarkable increase in cellular toxicity and a significant increase in ROS species formationThe authors thank the financial support from the Spanish Ministerio de EconomĂ­a y Competitividad (PID2019- 108028GB-C22, PID2019-108028GB-C21, MAT2016-77608- C3-1-P, MAT2016-75883-C2-1-P, MAT2016-75883-C2-2-P, MAT2016-75586-C4-4-P, and CTQ2017-87201-PAEI/ FEDER, UE) and the Generalidad Valenciana (Prometeo/ 2019/076

    La Red Internacional de Inventarios Forestales (BIOTREE-NET) en Mesoamérica: avances, retos y perspectivas futuras

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    Conservation efforts in Neotropical regions are often hindered by lack of data, since for many species there is a vacuum of information, and many species have not even been described yet. The International Network of Forest Inventory Plots (BIOTREE-NET) gathers and facilitates access to tree data from forest inventory plots in Mesoamerica, while encouraging data exchange between researchers, managers and conservationists. The information is organised and standardised into a single database that includes spatially explicit data. This article describes the scope and objectives of the network, its progress, and the challenges and future perspectives. The database includes above 50000 tree records of over 5000 species from more than 2000 plots distributed from southern Mexico through to Panama. Information is heterogeneous, both in nature and shape, as well as in the geographical coverage of inventory plots. The database has a relational structure, with 12 inter-connected tables that include information about plots, species names, dbh, and functional attributes of trees. A new system that corrects typographical errors and achieves taxonomic and nomenclatural standardization was developed using The Plant List (http://theplantlist.org/) as reference. Species distribution models have been computed for around 1700 species using different methods, and they will be publicly accessible through the web site in the future (http://portal.biotreenet.com). Although BIOTREE-NET has contributed to the development of improved species distribution models, its main potential lies, in our opinion, in studies at the community level. Finally, we emphasise the need to expand the network and encourage researchers willing to share data and to join the network and contribute to the generation of further knowledge about forest biodiversity in Neotropical regions

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

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    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

    Marejadas rurales y luchas por la vida, vol. iv: permanencias, resistencias y luchas por la vida

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    Volumen 4. Permanencias, resistencias y luchas por la vida, coordinado por: Elisabeth A. Mager Hois, Miguel Ángel Paz Frayre y Carla Zamora LomelĂ­, integra 15 capĂ­tulos y estĂĄ dividido en tres secciones, la primera denominada Permanencia, contiene 5 capĂ­tulos que intentan establecer como eje comĂșn la lucha continua en las comunidades campesinas para continuar con la vida rural. La segunda, Identidad y resistencia, estĂĄ compuesta por 4 capĂ­tulos que reflexionan sobre varios procesos de resistencia de la vida rural ante los cambios globales e internos en su propio proceso de vida, otros trabajos intentan encontrar aquellos elementos que generan y mantienen alguna forma de identidad, y la tercera secciĂłn, Lucha por la vida, contiene 6 trabajos que demuestran todas aquellas posibilidades que existen en el medio rural para sostenerse y mantenerse, generando diferentes formas y estrategias que los une en la continua lucha por vivir con pocas pretensiones y con difĂ­ciles perspectivas pero siempre encontrando alternativas.ASOCIACIÓN MEXICANA DE ESTUDIOS RURALES, INSTITUTO DE CIENCIAS AGROPECUARIAS Y RURALES (ICAR), UNIVERSIDAD DE GUADALAJARA, FACULTAD DE ESTUDIOS SUPERIORES ACATLÁN-UNAM, ECOSUR, CUCOSTA SUR GRANA, EL COLEGIO DE MICHOACÁN A.C., UNIVERSIDAD MICHOACANA DE SAN NICOLAS HIDALG

    Reducing the environmental impact of surgery on a global scale: systematic review and co-prioritization with healthcare workers in 132 countries

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    Abstract Background Healthcare cannot achieve net-zero carbon without addressing operating theatres. The aim of this study was to prioritize feasible interventions to reduce the environmental impact of operating theatres. Methods This study adopted a four-phase Delphi consensus co-prioritization methodology. In phase 1, a systematic review of published interventions and global consultation of perioperative healthcare professionals were used to longlist interventions. In phase 2, iterative thematic analysis consolidated comparable interventions into a shortlist. In phase 3, the shortlist was co-prioritized based on patient and clinician views on acceptability, feasibility, and safety. In phase 4, ranked lists of interventions were presented by their relevance to high-income countries and low–middle-income countries. Results In phase 1, 43 interventions were identified, which had low uptake in practice according to 3042 professionals globally. In phase 2, a shortlist of 15 intervention domains was generated. In phase 3, interventions were deemed acceptable for more than 90 per cent of patients except for reducing general anaesthesia (84 per cent) and re-sterilization of ‘single-use’ consumables (86 per cent). In phase 4, the top three shortlisted interventions for high-income countries were: introducing recycling; reducing use of anaesthetic gases; and appropriate clinical waste processing. In phase 4, the top three shortlisted interventions for low–middle-income countries were: introducing reusable surgical devices; reducing use of consumables; and reducing the use of general anaesthesia. Conclusion This is a step toward environmentally sustainable operating environments with actionable interventions applicable to both high– and low–middle–income countries

    Disturbances and Coupling Compensation for Trajectory Tracking of a Multi-link Aerial Robot

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    International audienceThe actual paper presents the concept of a multi-link unmanned aerial system (ML-UAS) intended to transport multi-cargo payload. The mathematical model is obtained through the Euler-Lagrange energy-based while the controller relies on a classical linear scheme. The system is composed of three rotorcrafts attached by two bar like links. As the system is highly coupled, due to its inherent dynamics and cargo influences, a dynamic extension of the equations of motion to apply a Linear Kalman filter is proposed to meet the trajectory tracking specification. The suggested state observer is validated via close to reality numerical simulations

    Mini-AUV Hydrodynamic Parameters Identification via CFD Simulations and Their Application on Control Performance Evaluation

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    This manuscript presents a fully detailed methodology in order to identify the hydrodynamic parameters of a mini autonomous underwater vehicle (mini-AUV) and evaluate its performance using different controllers. The methodology consists of close-to-reality simulation using a Computed Fluid Dynamics (CFD) module of the ANSYS&trade; Workbench software, the processing of the data, obtained by simulation, with a set of Savistky&ndash;Golay filters; and, the application of the Least Square Method in order to estimate the hydrodynamic parameters of the mini-AUV. Finally, these parameters are considered to design the three different controllers that are based on the robot manipulators theory. Numerical simulations are carried out to evaluate the performance of the controllers
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