Reductive Hydrogenation of Sulfido-Bridged Tantalum Alkyl Complexes: A Mechanistic Insight

Hydrogenolysis of a series of alkyl sulfido-bridged tantalum(IV) dinuclear complexes [Ta(?5-C5Me5)R(?-S)]2 [R = Me, nBu (1), Et, CH2SiMe3, C3H5, Ph, CH2Ph (2), p-MeC6H4CH2 (3)] has led quantitatively to the Ta(III) tetrametallic sulfide cluster [Ta(?5-C5Me5)(?3-S)]4 (4) along with the corresponding alkane. Mechanistic information for the formation of the unique low-valent tetrametallic compound 4 was gathered by hydrogenation of the phenyl-substituted precursor [Ta(?5-C5Me5)Ph(?- S)]2, which proceeds through a stepwise hydrogenation process, disclosing the formation of the intermediate tetranuclear hydride sulfide [Ta2(?5-C5Me5)2(H)Ph(?-S)(?3-S)]2 (5). Extending our studies toward tantalum alkyl precursors containing functional groups susceptible to hydrogenation, such as the allyl-and benzylsubstituted compounds [Ta(?5-C5Me5)(?3-C3H5)(?-S)]2 and [Ta(?5-C5Me5)(CH2Ph)(?-S)]2 (2), enables alternative reaction pathways en route to the formation of 4. In the former case, the dimetallic system undergoes selective hydrogenation of the unsaturated allyl moiety, forming the asymmetric complex [{Ta(?5-C5Me5)(?3-C3H5)}(?-S)2{Ta(?5-C5Me5)(C3H7)}] (6) with only one propyl fragment. Species 2, in addition to the hydrogenation of one benzyl fragment and concomitant toluene release, also undergoes partial hydrogenation and dearomatization of the phenyl ring on the vicinal benzyl unity to give a ?5-cyclohexadienyl complex [Ta2(?5-C5Me5)2(?-CH2C6H6)(?-S)2] (7). The mechanistic implications of the latter hydrogenation process are discussed by means of DFT calculationsComunidad de MadridUniversidad de AlcaláPrograma Estímulo a la Investigación de Jóvenes Investigadore

N=N Bond Cleavage by Tantalum Hydride Complexes: Mechanistic Insights and Reactivity.

A series of dinuclear tantalum(IV) hydrides [{TaCpRX2}2(mu-H)2] (CpR = eta5-C5Me5, eta5-C5H4SiMe3, eta5-C5HMe4; X = Cl, Br) show the ability to promote the N=N bond cleavage in their reactions with azobenzene and benzo[c]cinnoline in absence of reducing reagents. Both, characterization of intermediate species and DFT studies point to a mechanism in two stages, in which the Ta-Ta bond splitting is key for the reduction of the N=N bond and its complete scission.Consorcio Madroño - Universidad de Alcal

Usefulness of 18 F-FDG PET-CT for the management of invasive fungal infections: A retrospective cohort from a tertiary university hospital

Background: 18F-FDG PET-CT is a potentially useful technique to help manage invasive fungal infection (IFI), but information on this topic is scarce. Objectives: To describe our experience using 18F-FDG PET-CT for IFI management. Patients/Methods: Retrospective cohort of IFI episodes in a university hospital from 2018 to 2023 with a18F-FDG PET-CT performed during the episode. We analysed its impact on IFI management compared to conventional imaging. Results: Thirty-five patients diagnosed with 36 episodes of IFI (52.8% moulds, 44.4% yeasts and 2.8% Pneumocystis) underwent 55 18F-FDG PET-CT. 74.3% were immunocompromised, including 45.7% solid organ transplant recipients. Indications for 18F-FDG PET-CT were diagnostic (10.9%), staging (47.3%) and follow-up (41.8%). Altogether 18F-FDG PET-CT added value to IFI management in 50.9% episodes. In 26 patients who had both staging 18F-FDG PET-CT and conventional imaging, sites of IFI dissemination were detected in 53.8% and 19.2%, respectively. Staging 18F-FDG PET-CT unveiled occult sites in 34.6%, uncovering unknown dissemination in 19.2%. In the evaluation of endocarditis in patients with fungemia, it contributed in at least 38.5%. Follow-up 18F-FDG PET-CTs had an added value in 47.8% episodes. They were allowed to de-escalate antifungal therapy in 26.1%. There were discordant findings between 18F-FDG PET-CT and CT follow-up in 40% cases. Conclusions: Overall, 18F-FDG PET-CT added value to IFI management in more than 50% of the episodes. It increased the diagnosis of occult sites, unveiled disseminated disease missed out by conventional imaging, and contributed to diagnose or rule out endocarditis in fungemia. Follow-up 18F-FDG PET-CT helped adjust the treatment duration and deserves further stud

Dissolution and sorption processes on the surface of calcite in the presence of high Co2+ concentration

The interaction of the calcite surface with Co2+-rich aqueous solutions ([Co2+aq]initial = 1000 ppm, i.e., ca. 17 mM) was investigated by means of macroscopic experiments and surface spectroscopic techniques. In the case of the macroscopic experiments, calcite powder and monocrystals were immersed into solutions for different time periods (from 1 min to one month). The Ca concentrations in the filtrates was measured by means of atomic absorption spectrometry (AAS) while the interacted solids were studied using a combination of X-ray photoelectron spectroscopy (XPS) and 12C-rutherford backscattering spectrometry (12C-RBS). The macroscopic data showed a characteristic surface dissolution process, in parallel to the surface sorption processes. Adsorption and co-precipitation were seen for almost the entire immersion period for both calcite powder and monocrystals. The surface study by XPS (analyzed at a depth of approximately 12 nm) suggested that adsorption takes place in the first hour of the interaction, followed by incorporation of Co2+ into calcite surface layers, leading to the formation of a Co2+-bearing surface (co)precipitate, which occurs over a period of hours and days. The 12C-RBS measurements on calcite { 10 1 ¯ 4 } indicated that the thickness of this surface co-precipitate was 270 nm after one day and then stabilized at 320 nm after more than a week

Demostraciones prácticas para la promoción de las titulaciones de Grado en Química y Grado en Ingeniería Química

Memoria ID12-0251. Ayudas de la Universidad de Salamanca para la innovación docente, curso 2012-2013

The evolution of the ventilatory ratio is a prognostic factor in mechanically ventilated COVID-19 ARDS patients

Background: Mortality due to COVID-19 is high, especially in patients requiring mechanical ventilation. The purpose of the study is to investigate associations between mortality and variables measured during the first three days of mechanical ventilation in patients with COVID-19 intubated at ICU admission. Methods: Multicenter, observational, cohort study includes consecutive patients with COVID-19 admitted to 44 Spanish ICUs between February 25 and July 31, 2020, who required intubation at ICU admission and mechanical ventilation for more than three days. We collected demographic and clinical data prior to admission; information about clinical evolution at days 1 and 3 of mechanical ventilation; and outcomes. Results: Of the 2,095 patients with COVID-19 admitted to the ICU, 1,118 (53.3%) were intubated at day 1 and remained under mechanical ventilation at day three. From days 1 to 3, PaO2/FiO2 increased from 115.6 [80.0-171.2] to 180.0 [135.4-227.9] mmHg and the ventilatory ratio from 1.73 [1.33-2.25] to 1.96 [1.61-2.40]. In-hospital mortality was 38.7%. A higher increase between ICU admission and day 3 in the ventilatory ratio (OR 1.04 [CI 1.01-1.07], p = 0.030) and creatinine levels (OR 1.05 [CI 1.01-1.09], p = 0.005) and a lower increase in platelet counts (OR 0.96 [CI 0.93-1.00], p = 0.037) were independently associated with a higher risk of death. No association between mortality and the PaO2/FiO2 variation was observed (OR 0.99 [CI 0.95 to 1.02], p = 0.47). Conclusions: Higher ventilatory ratio and its increase at day 3 is associated with mortality in patients with COVID-19 receiving mechanical ventilation at ICU admission. No association was found in the PaO2/FiO2 variation

Clustering COVID-19 ARDS patients through the first days of ICU admission. An analysis of the CIBERESUCICOVID Cohort

Background Acute respiratory distress syndrome (ARDS) can be classified into sub-phenotypes according to different inflammatory/clinical status. Prognostic enrichment was achieved by grouping patients into hypoinflammatory or hyperinflammatory sub-phenotypes, even though the time of analysis may change the classification according to treatment response or disease evolution. We aimed to evaluate when patients can be clustered in more than 1 group, and how they may change the clustering of patients using data of baseline or day 3, and the prognosis of patients according to their evolution by changing or not the cluster.Methods Multicenter, observational prospective, and retrospective study of patients admitted due to ARDS related to COVID-19 infection in Spain. Patients were grouped according to a clustering mixed-type data algorithm (k-prototypes) using continuous and categorical readily available variables at baseline and day 3.Results Of 6205 patients, 3743 (60%) were included in the study. According to silhouette analysis, patients were grouped in two clusters. At baseline, 1402 (37%) patients were included in cluster 1 and 2341(63%) in cluster 2. On day 3, 1557(42%) patients were included in cluster 1 and 2086 (57%) in cluster 2. The patients included in cluster 2 were older and more frequently hypertensive and had a higher prevalence of shock, organ dysfunction, inflammatory biomarkers, and worst respiratory indexes at both time points. The 90-day mortality was higher in cluster 2 at both clustering processes (43.8% [n = 1025] versus 27.3% [n = 383] at baseline, and 49% [n = 1023] versus 20.6% [n = 321] on day 3). Four hundred and fifty-eight (33%) patients clustered in the first group were clustered in the second group on day 3. In contrast, 638 (27%) patients clustered in the second group were clustered in the first group on day 3.Conclusions During the first days, patients can be clustered into two groups and the process of clustering patients may change as they continue to evolve. This means that despite a vast majority of patients remaining in the same cluster, a minority reaching 33% of patients analyzed may be re-categorized into different clusters based on their progress. Such changes can significantly impact their prognosis

Treatment with tocilizumab or corticosteroids for COVID-19 patients with hyperinflammatory state: a multicentre cohort study (SAM-COVID-19)

Objectives: The objective of this study was to estimate the association between tocilizumab or corticosteroids and the risk of intubation or death in patients with coronavirus disease 19 (COVID-19) with a hyperinflammatory state according to clinical and laboratory parameters. Methods: A cohort study was performed in 60 Spanish hospitals including 778 patients with COVID-19 and clinical and laboratory data indicative of a hyperinflammatory state. Treatment was mainly with tocilizumab, an intermediate-high dose of corticosteroids (IHDC), a pulse dose of corticosteroids (PDC), combination therapy, or no treatment. Primary outcome was intubation or death; follow-up was 21 days. Propensity score-adjusted estimations using Cox regression (logistic regression if needed) were calculated. Propensity scores were used as confounders, matching variables and for the inverse probability of treatment weights (IPTWs). Results: In all, 88, 117, 78 and 151 patients treated with tocilizumab, IHDC, PDC, and combination therapy, respectively, were compared with 344 untreated patients. The primary endpoint occurred in 10 (11.4%), 27 (23.1%), 12 (15.4%), 40 (25.6%) and 69 (21.1%), respectively. The IPTW-based hazard ratios (odds ratio for combination therapy) for the primary endpoint were 0.32 (95%CI 0.22-0.47; p < 0.001) for tocilizumab, 0.82 (0.71-1.30; p 0.82) for IHDC, 0.61 (0.43-0.86; p 0.006) for PDC, and 1.17 (0.86-1.58; p 0.30) for combination therapy. Other applications of the propensity score provided similar results, but were not significant for PDC. Tocilizumab was also associated with lower hazard of death alone in IPTW analysis (0.07; 0.02-0.17; p < 0.001). Conclusions: Tocilizumab might be useful in COVID-19 patients with a hyperinflammatory state and should be prioritized for randomized trials in this situatio

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 &gt; 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