Picolyl−NHC Hydrotris(pyrazolyl)borate Ruthenium(II) Complexes: Synthesis, Characterization, and Reactivity with Small Molecules

Ruthenium(II) hydrotris(pyrazolyl)borate chloro complexes bearing picolyl-functionalized N-heterocyclic carbenes [TpRu- (κ2-C,N-picolyl-RI)Cl] (picolyl-MeI = 3-methyl-1-(2-picolyl)imidazol-2- ylidene) (1a), picolyl-iPrI = 3-isopropyl-1-(2-picolyl)imidazol-2-ylidene (1b), picolyl-Me45DClI = 3-methyl-1-(2-picolyl)-4,5-dichloroimidazol- 2-ylidene (1c), picolyl-PhI = 3-phenyl-1-(2-picolyl)imidazol-2-ylidene (1d), picolyl-MeBI = 3-methyl-1-(2-picolyl)benzoimidazol-2-ylidene (1e)) have been synthesized and characterized. Furthermore, cationic carbonyl derivatives 2a−e have been prepared, characterized, and used to study the donor properties of the picolylcarbene ligands (picolyl-RI) via infrared spectroscopy. Also, the reactivity of the 16-electron species [TpRu(κ2-C,N-picolyl-RI)]+, in situ generated using NaBArF 4 (ArF = 3,5-bis(trifluoromethyl)phenyl) as a halide scavenger, toward N2, CH3CN, H2, CH2CH2, S8, and O2 was studied indicating a strong influence of the NHC wingtip and backbone substituents in the product distribution. The crystal structures of [TpRu(κ2- C,N-picolyl-iPrI)Cl] (1b), [TpRu(κ2-C,N-picolyl-MeI)CO][BArF 4] (2a), [TpRu(κ2-C,N-picolyl-PhI)CO][BArF 4] (2d), [{TpRu(κ2- C,N-picolyl-MeI}2(μ-N2)][BArF 4]2 (3′a), [{TpRu(κ2-C,N-picolyl-PhI)}2(μ-N2)][BArF 4]2 (3′d), [TpRu(κ2-C,N-picolyl-iPrI)(η2- CH2CH2)][BArF 4] (5b), and [{TpRu(κ2-C,N-picolyl-MeI)}2(μ-S2)][BArF 4]2 (6) are reported

Ruthenium(II) Picolyl-NHC Complexes: Synthesis, Characterization, and Catalytic Activity in Amine N‑alkylation and Transfer Hydrogenation Reactions

Ruthenium(II) p-cymene complexes with picolylfunctionalized N-heterocyclic carbenes [(η6-p-cymene)Ru(L)(Cl)]- [PF6] (L = 3-methyl-1-(2-picolyl)imidazol-2-ylidene (1a), 3- isopropyl-1-(2-picolyl)imidazol-2-ylidene (1b), 3,4,5-trimethyl- 1-(2-picolyl)imidazol-2-ylidene (1c), 3-mesityl-1-(2-picolyl)- imidazol-2-ylidene (1d), 3-methyl-1-(2-picolyl)benzoimidazol- 2-ylidene (1e), 3-methyl-1-(2-picolyl)-4,5-dichloroimidazol-2- ylidene (1f), 3-phenyl-1-(2-picolyl)imidazol-2-ylidene (1g)) have been synthesized and characterized. Compounds 1a−g were recrystallized, and X-ray crystal structures are reported for 1a,f. Furthermore, compounds 1a−f show catalytic activity in transfer hydrogenation of ketones and N-alkylation of amines. Notably, complexes 1a,c,f were found to be very efficient and versatile catalysts toward transfer hydrogenation of a wide range of ketones and imines in addition to N-alkylation of several amines

Historia de los trasplantes

Transplants are a set of surgical techniques characterized by replacing damaged organs with new and healthy ones. There are historical references, from the earliest times of humanity where organ replacements, viscera or parts of the body are collected and even the combination of body parts of different animal species that recall the therapeutic substitution of the transplant. There are references in mythology, at the level of legends, in the description of miraculous facts, although there are more scientific data concerning various attempts of this type of substitutions. There are specific contributions on transplants, attempts made in animal experiments and, on the other hand, historical milestones that have made it possible for this type of technique to be considered routine in routine surgical practice. A historical journey is made in the work, analyzing these contributions.Los trasplantes constituyen un conjunto de técnicas quirúrgicas caracterizadas por sustituir órganos dañados por otros nuevos y sanos. Hay referencias históricas, desde los primeros tiempos de la humanidad en donde se recogen recambios de órganos, vísceras o partes del cuerpo e incluso la combinación de partes del cuerpo de diferentes especies animales que recuerdan la sustitución terapéutica del trasplante. Existen referencias en la mitología, a nivel de leyendas, en la descripción de hechos milagrosos, existiendo no obstante datos más científicos concernientes a diversos intentos de este tipo de sustituciones. Hay aportaciones puntuales sobre los trasplantes, intentos realizados en experimentación animal y por otra parte hitos históricos que han hecho posible que este tipo de técnicas puedan ser consideradas de rutina en la práctica quirúrgica habitual. Se realiza un recorrido histórico en el trabajo, analizando estas aportaciones

Historia de los trasplantes

Los trasplantes constituyen un conjunto de técnicas quirúrgicas caracterizadas por sustituir órganos dañados por otros nuevos y sanos. Hay referencias históricas, desde los primeros tiempos de la humanidad en donde se recogen recambios de órganos, vísceras o partes del cuerpo e incluso la combinación de partes del cuerpo de diferentes especies animales que recuerdan la sustitución terapéutica del trasplante. Existen referencias en la mitología, a nivel de leyendas, en la descripción de hechos milagrosos, existiendo no obstante datos más científicos concernientes a diversos intentos de este tipo de sustituciones. Hay aportaciones puntuales sobre los trasplantes, intentos realizados en experimentación animal y por otra parte hitos históricos que han hecho posible que este tipo de técnicas puedan ser consideradas de rutina en la práctica quirúrgica habitual. Se realiza un recorrido histórico en el trabajo, analizando estas aportaciones

Early Stepdown From Echinocandin to Fluconazole Treatment in Candidemia: A Post Hoc Analysis of Three Cohort Studies

Antifúngic; Candidèmia; DesescaladaAntifúngico; Candidemia; DesescaladaAntifungal; Candidemia; De-escalationBackground There are no clear criteria for antifungal de-escalation after initial empirical treatments. We hypothesized that early de-escalation (ED) (within 5 days) to fluconazole is safe in fluconazole-susceptible candidemia with controlled source of infection. Methods This is a multicenter post hoc study that included consecutive patients from 3 prospective candidemia cohorts (2007–2016). The impact of ED and factors associated with mortality were assessed. Results Of 1023 candidemia episodes, 235 met inclusion criteria. Of these, 54 (23%) were classified as the ED group and 181 (77%) were classified as the non-ED group. ED was more common in catheter-related candidemia (51.9% vs 31.5%; P = .006) and episodes caused by Candida parapsilosis, yet it was less frequent in patients in the intensive care unit (24.1% vs 39.2%; P = .043), infections caused by Nakaseomyces glabrata (0% vs 9.9%; P = .016), and candidemia from an unknown source (24.1% vs 47%; P = .003). In the ED and non-ED groups, 30-day mortality was 11.1% and 29.8% (P = .006), respectively. Chronic obstructive pulmonary disease (odds ratio [OR], 3.97; 95% confidence interval [CI], 1.48–10.61), Pitt score > 2 (OR, 4.39; 95% CI, 1.94–9.20), unknown source of candidemia (OR, 2.59; 95% CI, 1.14–5.86), candidemia caused by Candida albicans (OR, 3.92; 95% CI, 1.48–10.61), and prior surgery (OR, 0.29; 95% CI, 0.08–0.97) were independent predictors of mortality. Similar results were found when a propensity score for receiving ED was incorporated into the model. ED had no significant impact on mortality (OR, 0.50; 95% CI, 0.16–1.53). Conclusions Early de-escalation is a safe strategy in patients with candidemia caused by fluconazole-susceptible strains with controlled source of bloodstream infection and hemodynamic stability. These results are important to apply antifungal stewardship strategies.This research forms part of an activity that has received funding from EIT Health. EIT Health is supported by the European Institute of Innovation and Technology (EIT), a body of the European Union that receives support from the European Union´s Horizon 2020 Research and Innovation Program. This study has been cofunded by the European Regional Development Fund. E. M.-G. (PI18/01061), P. P.-A. (“Rio Hortega” contract CM18/00132), M. F.-R. (“Miguel Servet” contract CP18/00073), and C. G.-V. (FIS PI18/01061) have received research grants from the Ministerio de Sanidad y Consumo, Instituto de Salud Carlos III

Integrated study of factors affecting fetal weight in singleton pregnancies. Nomogram and development of basic and advanced fetal growth customized models

We have performed a multivariate analysis to explore the influence on birth and ultrasound fetal weight estimation of traditional factors as biochemical data and maternal characteristics in combination with non- traditionally explored predictors as paternal height, Pregnancy-associated plasma protein A (PAPP-A), single umbilical artery or Free-beta Human Chorionic Gonadotropin (fß- HCG). The study was performed for a Spanish population (region of Aragon) in singleton pregnancies at term (37-42 weeks). Also, we have created a nomogram and in order to predict the occurrence of SGA (small for gestational age) and LGA (large for gestational age) cases we provide a multivariate predictive model of fetal weight that have been compared with other models in the prediction of ultrasound and birth weights. After study we have created a software application for automated calculation of percentile fetal weight, adjusting the variables when they were significant

Deep-sea habitat characterization using acoustic data and underwater imagery in Gazul mud volcano (Gulf of Cádiz, NE Atlantic)

Gazul is the shallowest mud volcano (MV) within the Shallow Field of Fluid Expulsion (SFFE) of the northeastern Gulf of Cádiz (NE Atlantic; 300–1200 m depth). The SFFE represents an important geo- and biodiversity area that was designated as a Site of Community Importance under the European Habitats Directive in 2014. In this study, geological features, habitats and associated biodiversity, as well as anthropogenic impacts, were characterized at Gazul MV from underwater imagery and multibeam bathymetry. Multivariate methods using the Bray-Curtis similarity index identified six main habitats, each of which harbored a characteristic faunal assemblage that included: (1) sandy ripple bottoms typified by the actiniarian Actinauge richardi; (2) sandy, muddy, coarse sand and bioclastic bottoms dominated by the solitary coral Flabellum chunii; (3) coarse sand and bioclastic bottoms, together with soft sediments covered by scattered methane-derived authigenic carbonates (MDACs) (mixed bottoms), characterized by the echinoid Cidaris cidaris; (4) hard bottoms comprising MDACs dominated by a wide variety of sponges and gorgonians; (5) coral-rubble bottoms typified by the presence of colonial scleractinian communities dominated by Madrepora oculata; and (6) mixed bottoms characterized by the presence of a styelid ascidian. Slope and water depth were the main factors explaining assemblages’ distribution, which was also supported by the presence of MDACs such as slabs, crusts and chimneys on the seafloor, as well as by the geomorphologic diversity of Gazul MV. The results highlight Gazul MV as an eco-biologically important area harboring different vulnerable marine ecosystem (VME) elements with indicator taxa such as scleractinians, sponges, gorgonians and black corals. ROV images revealed abandoned or lost fishing gears and marine debris on the seafloor, indicating anthropogenic impacts in Gazul MV and adjacent areas. Indeed trawling fisheries activities have also been detected in Vessel Monitoring System datasets. A fishery restricted area is recommended in Gazul MV due to the occurrence of diverse VMEs and species included in different conservation directives and conventions.Postprin

Early Stepdown From Echinocandin to Fluconazole Treatment in Candidemia: A Post Hoc Analysis of Three Cohort Studies

[Background] There are no clear criteria for antifungal de-escalation after initial empirical treatments. We hypothesized that early de-escalation (ED) (within 5 days) to fluconazole is safe in fluconazole-susceptible candidemia with controlled source of infection.[Methods] This is a multicenter post hoc study that included consecutive patients from 3 prospective candidemia cohorts (2007–2016). The impact of ED and factors associated with mortality were assessed.[Results] Of 1023 candidemia episodes, 235 met inclusion criteria. Of these, 54 (23%) were classified as the ED group and 181 (77%) were classified as the non-ED group. ED was more common in catheter-related candidemia (51.9% vs 31.5%; P = .006) and episodes caused by Candida parapsilosis, yet it was less frequent in patients in the intensive care unit (24.1% vs 39.2%; P = .043), infections caused by Nakaseomyces glabrata (0% vs 9.9%; P = .016), and candidemia from an unknown source (24.1% vs 47%; P = .003). In the ED and non-ED groups, 30-day mortality was 11.1% and 29.8% (P = .006), respectively. Chronic obstructive pulmonary disease (odds ratio [OR], 3.97; 95% confidence interval [CI], 1.48–10.61), Pitt score > 2 (OR, 4.39; 95% CI, 1.94–9.20), unknown source of candidemia (OR, 2.59; 95% CI, 1.14–5.86), candidemia caused by Candida albicans (OR, 3.92; 95% CI, 1.48–10.61), and prior surgery (OR, 0.29; 95% CI, 0.08–0.97) were independent predictors of mortality. Similar results were found when a propensity score for receiving ED was incorporated into the model. ED had no significant impact on mortality (OR, 0.50; 95% CI, 0.16–1.53).[Conclusions] Early de-escalation is a safe strategy in patients with candidemia caused by fluconazole-susceptible strains with controlled source of bloodstream infection and hemodynamic stability. These results are important to apply antifungal stewardship strategies.This research forms part of an activity that has received funding from EIT Health. EIT Health is supported by the European Institute of Innovation and Technology (EIT), a body of the European Union that receives support from the European Union´s Horizon 2020 Research and Innovation Program. This study has been cofunded by the European Regional Development Fund. E. M.-G. (PI18/01061), P. P.-A. (“Rio Hortega” contract CM18/00132), M. F.-R. (“Miguel Servet” contract CP18/00073), and C. G.-V. (FIS PI18/01061) have received research grants from the Ministerio de Sanidad y Consumo, Instituto de Salud Carlos III.Peer reviewe

Multiple myeloma and SARS-CoV-2 infection : clinical characteristics and prognostic factors of inpatient mortality

There is limited information on the characteristics, prognostic factors, and outcomes of patients with multiple myeloma (MM) hospitalized with COVID-19. This retrospective case series investigated 167 patients reported from 73 hospitals within the Spanish Myeloma Collaborative Group network in March and April, 2020. Outcomes were compared with 167 randomly selected, contemporary, age-/sex-matched noncancer patients with COVID-19 admitted at six participating hospitals. Among MM and noncancer patients, median age was 71 years, and 57% of patients were male; 75 and 77% of patients, respectively, had at least one comorbidity. COVID-19 clinical severity was moderate-severe in 77 and 89% of patients and critical in 8 and 4%, respectively. Supplemental oxygen was required by 47 and 55% of MM and noncancer patients, respectively, and 21%/9% vs 8%/6% required noninvasive/invasive ventilation. Inpatient mortality was 34 and 23% in MM and noncancer patients, respectively. Among MM patients, inpatient mortality was 41% in males, 42% in patients aged >65 years, 49% in patients with active/progressive MM at hospitalization, and 59% in patients with comorbid renal disease at hospitalization, which were independent prognostic factors on adjusted multivariate analysis. This case series demonstrates the increased risk and identifies predictors of inpatient mortality among MM patients hospitalized with COVID-19