Palladium(II)-Catalyzed Rearrangement and Oligomerization Reactions of <i>cis</i>-Bicyclo[4.2.0]oct-7-ene

In the presence of several Pd­(II) catalysts, <i>cis</i>-bicyclo­[4.2.0]­oct-7-ene (<b>4a</b>) was found to undergo olefin isomerization (“ring walking”) and oligomerization, resulting in the formation of <i>cis</i>-bicyclo­[4.2.0]­oct-2-ene (<b>4d</b>) and the low-molecular-mass cycloaliphatic oligomers <b>5a</b>–<b>d</b>, respectively. The catalysts studied are [Pd­(NCEt)₄]­[BF₄]₂ (<b>1</b>), [(η³-allyl)­Pd­(solv)₂]­[SbF₆] (<b>2</b>; solv = CH₂Cl₂), [(1,10-phenanthroline)­Pd­(CH₃)­(NC­(CH₂)₆CH₃)]­[SbF₆] (<b>6</b>), and [(2,9-dimethyl-1,10-phenanthroline)­Pd­(CH₃)­(NC­(CH₂)₆CH₃)]­[SbF₆] (<b>7</b>). Isomerization included the formation of both <b>4d</b> and the olefinic end groups of <b>5a</b>–<b>d</b> and ranged from 94% using catalyst <b>7</b> to 29% employing catalyst <b>2</b>. Ab initio and DFT calculations at the LMP2/6-31G** and B3LYP/6-31G** levels show that the thermodynamic stabilities of the bicyclo[4.2.0]­octene isomers increase in the order 7-ene <b>4a</b> < 1(8)-ene <b>4b</b> < 1-ene <b>4c</b> ≈ 1(6)-ene <b>4e</b> ≈ 3-ene <b>4f</b> < 2-ene <b>4d</b>. A mechanism of isomerization via subsequent β-hydride eliminations and olefin reinsertions is proposed. These results are in contrast to the reactions of bicyclo[3.2.0]­hept-6-ene (<b>3a</b>) catalyzed by <b>1</b>, <b>2</b>, and <b>7</b> and the reaction of <b>4a</b> catalyzed by Cp₂ZrCl₂/MAO (Cp = η⁵-C₅H₅), all of which produced polymers in good yields (73–99%)

Punto de fuga. Punto de encuentro : aproximación interdisciplinar a las Vanguardias Artísticas de la segunda mitad del siglo XX

Resumen basado en el del proyecto. Premiado en la convocatoria: Premios para proyectos de innovación concluidos durante el curso 2007-2008, en los centros educativos no universitarios sostenidos con fondos públicos de la Comunidad Autónoma de Castilla-La Mancha (Orden 12-12-2008, de la Consejería de Educación y Ciencia de la Junta de Comunidades de Castilla-La Mancha. Resolución de 5-5-2009, de la Viceconsejería de Educación)El proyecto se desarrolla entre cinco centros: la Escuela de Arte de Guadalajarara, la Escuela de Hostelería y Turismo del IES Antonio Buero Vallejo de Guadalajara, el Conservatorio Provincial de Música de Guadalajara, el IES Profesor Domínguez Ortiz de Azuqueca de Henares y el Colegio Infantil y Primaria Castillo de Pioz. La idea central es la de abordar de forma interdisciplinar un tema común entre centros de distinta naturaleza armonizando el calendario de realización. Se buscan elementos integradores que permitan que el alumno se involucre activamente en un aprendizaje significativo con uno de los elementos clave en la educación, la motivación. Los objetivos son: fomentar la idea de que todas las áreas de conocimiento y creación humanas son producto de épocas y situaciones concretas englobadas en un todo; fomentar la participación activa en el proceso educativo; descubrir que el arte es algo vivo y que puede formar parte de la propia personalidad; fomentar el espíritu colectivo, la relevancia en el cumplimiento de los plazos y la valoración de la mirada del espectador sobre lo realizado; descubrir nuevos modos de comunicación y de relación; promover la reflexión anti-racista, anti-sexista, pacifista y solidaria. El tema elegido, la segunda mitad del siglo XX, especialmente las décadas de los 50, 60 y 70. Años de grandes transformaciones sociales y económicas en Europa. Su aproximación es multidisciplinar, desde la música, las artes plásticas, la literatura, la gastronomía, y el desarrollo del turismo como una industria potente que contribuirá además económicamente a sacar del ostracismo al pais.Castilla La ManchaConsejería de Educación, Ciencia y Cultura. Viceconsejería de Educación y Cultura. Servicio de Documentación; Bulevar del Río Alberche, s. n. - 1 Planta; 45071 Toledo; Tel. +34925286045; Fax +34925247410; [email protected]

Contemporary use of cefazolin for MSSA infective endocarditis: analysis of a national prospective cohort

Objectives: This study aimed to assess the real use of cefazolin for methicillin-susceptible Staphylococcus aureus (MSSA) infective endocarditis (IE) in the Spanish National Endocarditis Database (GAMES) and to compare it with antistaphylococcal penicillin (ASP). Methods: Prospective cohort study with retrospective analysis of a cohort of MSSA IE treated with cloxacillin and/or cefazolin. Outcomes assessed were relapse; intra-hospital, overall, and endocarditis-related mortality; and adverse events. Risk of renal toxicity with each treatment was evaluated separately. Results: We included 631 IE episodes caused by MSSA treated with cloxacillin and/or cefazolin. Antibiotic treatment was cloxacillin, cefazolin, or both in 537 (85%), 57 (9%), and 37 (6%) episodes, respectively. Patients treated with cefazolin had significantly higher rates of comorbidities (median Charlson Index 7, P <0.01) and previous renal failure (57.9%, P <0.01). Patients treated with cloxacillin presented higher rates of septic shock (25%, P = 0.033) and new-onset or worsening renal failure (47.3%, P = 0.024) with significantly higher rates of in-hospital mortality (38.5%, P = 0.017). One-year IE-related mortality and rate of relapses were similar between treatment groups. None of the treatments were identified as risk or protective factors. Conclusion: Our results suggest that cefazolin is a valuable option for the treatment of MSSA IE, without differences in 1-year mortality or relapses compared with cloxacillin, and might be considered equally effective

Respiratory support in patients with severe COVID-19 in the International Severe Acute Respiratory and Emerging Infection (ISARIC) COVID-19 study: a prospective, multinational, observational study

Background: Up to 30% of hospitalised patients with COVID-19 require advanced respiratory support, including high-flow nasal cannulas (HFNC), non-invasive mechanical ventilation (NIV), or invasive mechanical ventilation (IMV). We aimed to describe the clinical characteristics, outcomes and risk factors for failing non-invasive respiratory support in patients treated with severe COVID-19 during the first two years of the pandemic in high-income countries (HICs) and low middle-income countries (LMICs). Methods: This is a multinational, multicentre, prospective cohort study embedded in the ISARIC-WHO COVID-19 Clinical Characterisation Protocol. Patients with laboratory-confirmed SARS-CoV-2 infection who required hospital admission were recruited prospectively. Patients treated with HFNC, NIV, or IMV within the first 24 h of hospital admission were included in this study. Descriptive statistics, random forest, and logistic regression analyses were used to describe clinical characteristics and compare clinical outcomes among patients treated with the different types of advanced respiratory support. Results: A total of 66,565 patients were included in this study. Overall, 82.6% of patients were treated in HIC, and 40.6% were admitted to the hospital during the first pandemic wave. During the first 24 h after hospital admission, patients in HICs were more frequently treated with HFNC (48.0%), followed by NIV (38.6%) and IMV (13.4%). In contrast, patients admitted in lower- and middle-income countries (LMICs) were less frequently treated with HFNC (16.1%) and the majority received IMV (59.1%). The failure rate of non-invasive respiratory support (i.e. HFNC or NIV) was 15.5%, of which 71.2% were from HIC and 28.8% from LMIC. The variables most strongly associated with non-invasive ventilation failure, defined as progression to IMV, were high leukocyte counts at hospital admission (OR [95%CI]; 5.86 [4.83-7.10]), treatment in an LMIC (OR [95%CI]; 2.04 [1.97-2.11]), and tachypnoea at hospital admission (OR [95%CI]; 1.16 [1.14-1.18]). Patients who failed HFNC/NIV had a higher 28-day fatality ratio (OR [95%CI]; 1.27 [1.25-1.30]). Conclusions: In the present international cohort, the most frequently used advanced respiratory support was the HFNC. However, IMV was used more often in LMIC. Higher leucocyte count, tachypnoea, and treatment in LMIC were risk factors for HFNC/NIV failure. HFNC/NIV failure was related to worse clinical outcomes, such as 28-day mortality. Trial registration This is a prospective observational study; therefore, no health care interventions were applied to participants, and trial registration is not applicable

Respiratory support in patients with severe COVID-19 in the International Severe Acute Respiratory and Emerging Infection (ISARIC) COVID-19 study: a prospective, multinational, observational study

Background: Up to 30% of hospitalised patients with COVID-19 require advanced respiratory support, including high-flow nasal cannulas (HFNC), non-invasive mechanical ventilation (NIV), or invasive mechanical ventilation (IMV). We aimed to describe the clinical characteristics, outcomes and risk factors for failing non-invasive respiratory support in patients treated with severe COVID-19 during the first two years of the pandemic in high-income countries (HICs) and low middle-income countries (LMICs). Methods: This is a multinational, multicentre, prospective cohort study embedded in the ISARIC-WHO COVID-19 Clinical Characterisation Protocol. Patients with laboratory-confirmed SARS-CoV-2 infection who required hospital admission were recruited prospectively. Patients treated with HFNC, NIV, or IMV within the first 24 h of hospital admission were included in this study. Descriptive statistics, random forest, and logistic regression analyses were used to describe clinical characteristics and compare clinical outcomes among patients treated with the different types of advanced respiratory support. Results: A total of 66,565 patients were included in this study. Overall, 82.6% of patients were treated in HIC, and 40.6% were admitted to the hospital during the first pandemic wave. During the first 24 h after hospital admission, patients in HICs were more frequently treated with HFNC (48.0%), followed by NIV (38.6%) and IMV (13.4%). In contrast, patients admitted in lower- and middle-income countries (LMICs) were less frequently treated with HFNC (16.1%) and the majority received IMV (59.1%). The failure rate of non-invasive respiratory support (i.e. HFNC or NIV) was 15.5%, of which 71.2% were from HIC and 28.8% from LMIC. The variables most strongly associated with non-invasive ventilation failure, defined as progression to IMV, were high leukocyte counts at hospital admission (OR [95%CI]; 5.86 [4.83–7.10]), treatment in an LMIC (OR [95%CI]; 2.04 [1.97–2.11]), and tachypnoea at hospital admission (OR [95%CI]; 1.16 [1.14–1.18]). Patients who failed HFNC/NIV had a higher 28-day fatality ratio (OR [95%CI]; 1.27 [1.25–1.30]). Conclusions: In the present international cohort, the most frequently used advanced respiratory support was the HFNC. However, IMV was used more often in LMIC. Higher leucocyte count, tachypnoea, and treatment in LMIC were risk factors for HFNC/NIV failure. HFNC/NIV failure was related to worse clinical outcomes, such as 28-day mortality. Trial registration This is a prospective observational study; therefore, no health care interventions were applied to participants, and trial registration is not applicable