Compuestos ciclometalados de paladio y platino con iminofosforanos: preparación, caracterización y aplicaciones en catálisis

Los compuestos ciclometalados son compuestos organometálicos con estructura de anillo que presentan un enlace σ metal─carbono y un enlace covalente coordinado metal─heteroátomo. Son ampliamente estudiados debido a que pueden presentar propiedades muy interesantes tanto en el ámbito industrial como en el de la química médica, tales como la de actuar como catalizadores o como anticancerígenos. Los iminofosforanos son compuestos orgánicos que presentan un enlace doble P=N fuertemente polarizado y se pueden considerar como los análogos nitrogenados de los iluros de fósforo. En este trabajo se hicieron reaccionar ligandos iminofosforano tridentados [C,N,S], [C,N,O] y bidentados [C,N] con sales de paladio y platino con el objetivo de sintetizar nuevos compuestos ciclometalados con estos metales. Se estudió a su vez la reactividad de estos compuestos frente a diversos ligandos fosfina y difosfina, lo que dio lugar a nuevos compuestos ciclometalados. En función de la longitud de la cadena carbonada de los ligandos difosfina, estos actuaron como ligandos monodentados, bidentados quelato o bidentados puente. La caracterización de los compuestos se llevó a cabo mediante análisis elemental, espectroscopia de infrarrojo, difracción de rayos X y espectroscopia de RMN de 1H y 31P-{1H}. Posteriormente se investigaron las propiedades catalíticas de los paladaciclos obtenidos en la reacción de acoplamiento de Suzuki midiendo el porcentaje de conversión de los sustratos en distintos intervalos de tiempo. La catálisis de Suzuki es una reacción de enorme importancia en el ámbito de la química, tanto en investigación como a nivel industrial

Impact of removal and restriction of me-too medicines in a hospital drug formulary on in- and outpatient drug prescriptions: interrupted time series design with comparison group

Background: The study covered in- and out-of-hospital care in a region in north-western Spain. The intervention evaluated took the form of a change in the hospital drugs formulary. Before the intervention, the formulary contained four of the five low molecular weight heparins (LMWHs) marketed in Spain. The intervention consisted of withdrawing two LMWHs (bemiparin and dalteparin) from the formulary and restricting the use of another (tinzaparin), leaving only enoxaparin as an unrestricted prescription LMWH. Accordingly, the aim of this study was to evaluate the effect on in- and outpatient drug prescriptions of removing and restricting the use of several LMWHs in a hospital drugs formulary. Methods: We used a natural, before-after, quasi-experimental design with a control group and monthly data from January 2011 to December 2016. Based on data drawn from official Public Health Service sources, the following dependent variables were extracted: defined daily doses (DDD) per 1000 inhabitants per day (DDD/TID), DDD per 100 stays per day, and expenditure per DDD. Results: The two compounds that were removed from the formulary registered an immediate decrease at both an intra- and out-of-hospital level (66.6% and 55.6% for bemiparin and 73.0% and 92.2% for dalteparin, respectively); similarly, the compound that was restricted also registered an immediate decrease (36.1% and 9.0% at the in- and outpatient levels, respectively); in contrast, the remaining LMWH (enoxaparin) registered an immediate, significant increase at both levels (44.9% and 32.6%, respectively). The intervention led to an immediate reduction of 6.8% and a change in trend in out-of-hospital cost/DDD; it also avoided an expenditure of €477,317.1 in the 21 months following the intervention. Conclusions: The results indicate that changes made in a hospital drugs formulary towards more efficient medications may lead to better use of pharmacotherapeutic resources in its health catchment area.S

Analysis of audit domains in freshman students in Spain: three cross-sectional surveys (2005, 2012 and 2016)

Purpose: We aimed to evaluate changes in the frequency of drinking, alcohol dependence and alcohol-related harm in freshman college students from 2005, 2012 and 2016, and identify riskassociated factors. Method: A cross-sectional study involving 5009 freshman students was carried out in Spain in 2005, 2012 and 2016. The Dimensions of Alcohol Use Disorders Identification Test (frequency of drinking, symptoms of dependence and alcohol-related harm) was analysed. Adjusted relative risks (RRs) and their 95% confidence intervals were estimated using negative binomial regression. Results: Place of residence, positive expectancies and early onset of alcohol consumption continue to be crucial conditions for developing patterns of risky consumption, alcohol dependence and harm. Women and men were more vulnerable to alcohol harm and dependence when living away from home, having higher economic status and positive alcohol expectancies. Cohorts from 2012 and 2016 were at lower risk of risky alcohol consumption. Men belonging to the 2012 and 2016 cohorts were at lower risk of alcohol negative consequences compared with the 2005 cohort. However, women remained vulnerable over time to alcohol dependence and harm. Starting drinking after 16 protects them both from alcohol dependence and harm. Conclusions: Women are more vulnerable to alcohol dependence and harm in recent cohorts of freshmen. Limiting access to alcohol at a younger age and working on false positive expectancies could benefit freshmen by avoiding alcohol damage and alcohol dependenceFunding for this study was provided by the AES: Strategic Action in Health (PI20/00131). AES played no further role in this studyS

Study, preparation and characterization of thiosemicarbazone ligands and their compounds

The 20th International Electronic Conference on Synthetic Organic Chemistry session General Organic SynthesisThiosemicarbazones are formed by the condensation of an aldehyde or ketone with a thiosemicarbazide. They have high coordinative capacity given that they have several potential donor atoms through which they can bind to transition metals. This coordinative capacity can be increased if the R1 and R2 substituents include additional donor atoms. In addition, thiosemicarbazones as well as their semicarbazones analogues have considerable biological and pharmacological interest because of their antibacterial, antiviral and antitumor activity. This communication includes the preparation and characterization of a series of thiosemicarcarbazones and their applications in the synthesis of palladium organometallic compoundsWe wish to thank the financial support received from the Xunta de Galicia (Galicia, Spain) under the Grupos de Referencia Competitiva Programme Projects GRC2015/00

¿Influye la movilidad social en el estado de salud? Una revisión sistemática

Fundamentos: En el debate sobre los determinantes de la variación de la clase social en la salud, se ha sugerido que la movilidad social y los factores asociados a ella desempeñan un papel importante en esta variación. La movilidad social describe los cambios o la estabilidad entre las posiciones de clase social. El objetivo de este trabajo fue identificar estudios sobre la asociación entre movilidad social y salud. Métodos: Las bases de datos consultadas fueron MEDLINE/PubMed, Cochrane, SciELO, CRD. Las palabras clave utilizadas (en inglés), a través de la metodología MeSH, fueron: Salud (MajorTerm), Movilidad de clase, Movilidad vertical, Posición social, Factores socioeconómicos, Clase social, Condiciones sociales, Entorno social, Pobreza y Marginación social (MeSHTerm). El periodo de búsqueda fue de enero de 2010 a diciembre de 2019. La declaración de STROBE se ha utilizado para elaborar la lista de verificación. Finalmente, la evaluación de los estudios se ha realizado mediante una revisión sistemática cualitativa. Resultados: La búsqueda identificó 1.092 estudios potencialmente relevantes. Tras el análisis, se retuvieron 376 estudios y se revisaron sus textos completos en profundidad, resultando un conjunto final de 42 estudios. De ellos, se identificaron 2 estudios sobre Movilidad de clase y Salud; también se identificaron 5 estudios sobre Pobreza y Salud, mostrando evidencia del efecto sobre la Salud por la Movilidad Social; 9 estudios sobre Clase Social y Salud, mostrando el efecto de la Movilidad Social sobre la Salud y 8 estudios que mostraron efecto de la Posición Social sobre la Salud. Conclusiones: Las medidas de movilidad social transmiten información adicional a la de los índices de pobreza. Utilizar los índices de posición social y su impacto en las desigualdades en salud podría ser empíricamente útil. Se necesitan más estudios sobre esta cuestión.Financiación: H2020 Science with and for Society, Award Number: 64357

Functionalized thiosemicarbazone ligands and their complexes

The 20th International Electronic Conference on Synthetic Organic Chemistry session General Organic SynthesisThe purpose of this work is the design, synthesis and characterization of thiosemicarbazone ligands bearing a phenyl boronic acid functionality. The main interest is the synthesis of organopalladium compounds with the boronic acid included within the corresponding molecule. These could lead to further modification of the properties of the organometallic species applicable to the Suzuki-Miyaura reaction. The ligands were prepared by reaction of acetylphenylboronic acid with several thiosemicarbazides. The compounds were characterized by IR, 1H and 31P NMR spectroscopyWe wish to thank the financial support received from the Xunta de Galicia (Galicia, Spain) under the Grupos de Referencia Competitiva Programme Projects GRC2015/009

Synthesis of iminophosphoranes as ligands for organometallic compounds

Iminophosphoranes are organic compounds of general composition R3P=NR and can be considered as nitrogen analogues to phophorus ylides. They can be obtained by the Staudinger and Kirsanov reactions. This compounds have multiple applications: they can be used as intermediates in reactions such as the Aza-Wittig, as a protecting group for amines or as a ligands for coordinated or cyclometallated compounds. The P=N bond is highly polarized, so that the nitrogen bears a partial negative charge. This feature makes them act as σ-donors with only minor π-acceptor properties, so when forming coordination compounds they can be displaced by other ligandsWe wish to thank the financial support received from the Xunta de Galicia (Galicia, Spain) under the Grupos de Referencia Competitiva Programme Projects GRC2015/00

Ru-Catalyzed Isomerization of Achmatowicz Derivatives : A Sustainable Route to Biorenewables and Bioactive Lactones

A Ru-catalyzed isomerization of Achmatowicz derivatives that opens unexplored routes to diversify the biogenic furanic platform is reported. The mechanistic insights of this formally redox-neutral intramolecular process were studied computationally and by deuterium labeling. The transformation proved to be a robust synthetic tool to achieve the synthesis of bioderived-monomers and a series of 4-keto-δ-valerolactones that further enabled the development of a flexible strategy for the synthesis of acetogenins. A concise and protective group-free asymmetric total synthesis of two natural products, namely, (S,S)-muricatacin and the (S,S)-L-factor, is also described.publishedVersionPeer reviewe

Impact of a multifaceted intervention to improve antibiotic prescribing: a pragmatic cluster-randomised controlled trial

Objectives: This study sought to assess the effectiveness and return on investment (ROI) of a multifaceted intervention aimed at improving antibiotic prescribing for acute respiratory infections in primary care. Design: Large-sized, two-arm, open-label, pragmatic, cluster-randomised controlled trial. Setting: All primary care physicians working for the Spanish National Health Service (NHS) in Galicia (region in north-west Spain). Participants: The seven spatial clusters were distributed by unequal randomisation (3:4) of the intervention and control groups. A total of 1217 physicians (1.30 million patients) were recruited from intervention clusters and 1393 physicians (1.46 million patients) from control clusters. Interventions: One-hour educational outreach visits tailored to training needs identified in a previous study; an online course integrated in practice accreditation; and a clinical decision support system. Main outcome measures: Changes in the ESAC (European Surveillance of Antimicrobial Consumption) quality indicators for outpatient antibiotic use. We used generalised linear mixed and conducted a ROI analysis to ascertain the overall cost savings. Results: Median follow-up was 19 months. The adjusted effect on overall antibiotic prescribing attributable to the intervention was − 4.2% (95% CI: − 5.3% to − 3.2%), with this being more pronounced for penicillins − 6.5 (95% CI: − 7.9% to − 5.2%) and for the ratio of consumption of broad- to narrow-spectrum penicillins, cephalosporins, and macrolides − 9.0% (95% CI: − 14.0 to − 4.1%). The cost of the intervention was €87 per physician. Direct savings per physician attributable to the reduction in antibiotic prescriptions was €311 for the NHS and €573 for patient contributions, with an ROI of €2.57 and €5.59 respectively. Conclusions: Interventions designed on the basis of gaps in physicians’ knowledge of and attitudes to misprescription can improve antibiotic prescribing and yield important direct cost savings. Trial registration: Current Controlled Trials ISRCTN24158380. Registered 5 February 2009. © 2020, The Author(s).This work was supported in part by the Instituto de Salud Carlos III (ISCII) (PI081239, PI09/90609, PI19/01006) Spanish State Plan for Scientific and Technical Research and Innovation 2012–2016 and 2017–2020, co-financed by The European Regional Development Fund (ERDF) and the Mutua Madrileña insurance company.publishe

Covid-19: la malinterpretación de los datos de la pandemia daña la confianza del público

Postprint (published version