Enhancing Metalating Efficiency of the Sodium Amide NaTMP in Arene Borylation Applications

Though LiTMP (TMP=2,2',6,6'-tetramethylpiperidide) is a commonly used amide, surprisingly the heavier NaTMP has hardly been utilised. Here, by mixing NaTMP with tridentate donor PMDETA (N,N,N',N'',N''-pentamethyldiethylenetriamine), we provide structural, and mechanistic insights into the sodiation of non-activated arenes (e.g. anisole and benzene). While these reactions are low yielding, adding B(OiPr)3 has a profound effect, not only by intercepting the CAr -Na bond, but also by driving the metalation reaction towards quantitative formation of more stabilized sodium aryl boronates. Demonstrating its metalating power, regioselective C2-metalation/borylation of naphthalene has been accomplished contrasting with single-metal based protocols which are unselective and low yielding. Extension to other arenes allows for in situ generation of aryl boronates which can then directly engage in Suzuki-Miyaura couplings, furnishing a range of biaryls in a selective and efficient manner

Influencia de los estilos educativos paternos en el consumo de drogas en adolescentes

El presente estudio pretende examinar el papel predictivo de la percepcion de la educacion paterna por parte de los hijos, en el consumo de diferentes sustancias (alcohol, cannabis y tabaco) durante la adolescencia.Método: Se administro un cuestionario anonimo desarrollado para medir la cantidad de sustancias consumidas en una semana y el tipo de educacion percibida de sus padres, asi como diferentes variables personales. La muestra estaba compuesta por 1378 sujetos, con edades comprendidas entre los 13 y los 19 anos. El analisis se realizo a traves del Modelo de Regresion de Poisson.Resultados: El tipo de educacion recibida parece influir en funcion de la sustancia analizada. Se ha encontrado que un estilo educativo democratico autoritario es protector para el consumo de drogas y un estilo permisivo correlaciona con un mayor consumo. Por otro lado, la figura paterna influye en el consumo de alcohol y la de ambos padres en el consumo de cannabis y tabaco.Discusión: El tipo de educacion que reciben los adolescentes determina la utilizacion y el consumo que hacen de las drogas. Por tanto, es importante intervenir en el ambito familiar a traves de los programas de prevencion, ensenando a los padres las pautas mas adecuadas en la educacion de sus hijos

Meconio y exposición prenatal a neurotóxicos

6 pages, 1 figures, 2 tables.[ESP] Introducción. La ubicuidad con la que se encuentran la mayoría de las substancias neurotóxicas en el medio ambiente implica a los pediatras en la necesidad de desarrollar métodos para medir la magnitud de la exposición durante los periodos vulnerables del desarrollo. Una forma útil de abordar este problema consiste en analizar muestras biológicas que acumulen las substancias neurotóxicas o sus metabolitos durante el periodo fetal.Método. Revisión bibliográfica sistemática de los últimos 20 años obtenida principalmente de Medline; Science Citation Index y Embase sobre los estudios con meconio como matriz de exposición prenatal a substancias neurotóxicas. El perfil de búsqueda utilizado fue: meconium, prenatal exposure, biological markers, matrices, environmental pollutants, nervous system poisonings, neurotoxicity sindromes. Hemos seleccionado los trabajos más importantes y de sus referencias se han obtenido los más relevantes de los años previos a la búsqueda.Resultados. Tradicionalmente, los esfuerzos para determinar la exposición fetal se han centrado en el análisis de sangre de cordón u orina de la madre o el neonato. El meconio es fácilmente disponible, es inerte, acumula los neurotóxicos y/o sus metabolitos desde la semana 12 de gestación donde quedan “fosilizados” hasta el nacimiento. Puede constituir un instrumento muy importante para investigar la exposición fetal a los distintos contaminantes ambientales y en particular a neurotóxicos.Conclusiones. Las exposiciones fetales a los distintos neurotóxicos estudiados a través de sangre materna, de cordón, pelo, uña, placenta y orina parecen ser menos predictivas sobre los efectos neurológicos que las mediciones de los mismos realizadas en meconio. Son necesarios más estudios en este campo.Implementar y desarrollar la medida en meconio de una amplia gama de sustancias neurotóxicas ayudará en la práctica pediátrica a una intervención e identificación temprana mostrando las exposiciones que puedan provocar daño y facilitando el desarrollo de medidas preventivas y rehabilitadoras.[ENG] Brackground. The environmental ubiquity of most neurotoxicants implies the pediatricians in the development of methods for exposure measurement during the vulnerable periods of development. The analysis of biological samples able to accumulate the neurotoxicant substances or its metabolites during the fetal period is a useful approach to fulfil this objective.Material and methods. A systematic literature review of the last 20 years in Medline, Science Citation Index and Embase on the studies with meconium like womb of prenatal exposure to neurotoxicants has been undertaken. The search profile was: “meconium”, “prenatal exposure”, “biological markers”, “matrices”, “environmental pollutants”, “nervous system poisonings”, “neurotoxicity sindromes”. We selected the most relevant articles and retrieved more from their references.Results. Traditionally, the efforts to determine the fetal exposure have been centered in the analysis of cord blood, urinates of the mother or of the neonato. Meconium is easily available, inert, accumulates the neurotoxicants and/or its metabolitos from week 12 of gestation where they are "fossilized" until the birth. It can constitute a very important instrument for the investigation of the fetal exposure to the different environmental pollutants and in particular to neurotoxicants.Conclusions. Foetal exposure to different neurotoxicants monitored from maternal blood, cord blood, hair, fingernail, placenta and urinates seem to be less predictive for neurological effects than meconium. However, more studies are needed to confirm this hypothesis.Implementation and measurement in meconium of a wide range of neurotoxic substances will be of help in the pediatric practice for intervention and early identification as it will reveal harmful exposures and facilitate the implementation of preventive measures.Los autores quieren expresar su agradecimiento a los miembros de la red de Investigación Colaborativa INMA, y en especial a Amparo Quiles Latorre, Elena Romero Aliaga y Sandra Pérez Aliaga, por su apoyo y colaboración en la realización del trabajo de campo; al equipo de enfermería de la 7ª, 8ª y 9ª de la maternidad del Hospital Materno-Infantil Universitario La Fe y a los recién nacidos y sus felices padres que con su colaboración y entusiasmo hacen posible llevar a término estos estudios.Peer reviewe

Cocaína, violencia y género desde el punto de vista de los profesionales

Objetivo: El presente estudio pretende conocer los comportamientos violentos de hombres y mujeres consumidores de cocaína desde la perspectiva de los profesionales del área de drogodependencias y la violencia.Metodología: Se utilizó metodología cualitativa, concretamente se realizaron entrevistas semiestructuradas a una muestra representativa de profesionales de Unidades de Conductas Adictivas (UCA) y de Centros Mujer 24 Horas (CM24H) de la Comunitat Valenciana. El análisis de los datos, a excepción de las preguntas cerradas que se analizaron estadísticamente, se realizó siguiendo la Grounded Theory, lo que implica un método de comparaciones constantes que intenta generar teoría a partir de los datos empíricos y ofrece la posibilidad de comprensión del fenómeno desde el interior del mismo.Resultados: En opinión de los profesionales los hombres manifiestan más violencia de tipo físico que las mujeres, siendo más probable que éstas manifiesten su violencia verbalmente. Las conductas violentas suelen ir dirigidas hacia la pareja en el caso de los hombres y en el caso de las mujeres hacia sus hijos. Los hombres cocainómanos tienen más redes de apoyo en el proceso de tratamiento, normalmente reciben soporte de su pareja, no ocurriendo así en el caso de las mujeres cocainómanas que normalmente comienzan el tratamiento por voluntad propia y son apoyadas por algún miembro de su familia, que normalmente suele ser una mujer. Es habitual la existencia de violencia durante el proceso de tratamiento, pues las mujeres que se encuentran incluidas en estos programas de tratamiento suelen ser víctimas de violencia.Discusión: La relación entre consumo de cocaína y violencia es muy compleja, en este estudio se indica que las conductas violentas entre consumidores de cocaína pueden variar según género. Es importante continuar la tarea investigadora para profundizar en estas diferencias y mejorar así la calidad de los programas asistenciales dirigidos a esta población

Propiedades psicométricas de la adaptación española de la Clance Impostor Phenomenon Scale (S-CIPS)

The aim of this study was to examine the reliability, validity, and factorial structure of the Spanish version of the Clance Impostor Phenomenon Scale (CIPS). A sample of 271 Spanish students was recruited to complete a translated version of the original 20-item CIPS. In our sample, the instrument showed high internal consistency reliability (ωTotal=.90) and a moderate-to-strong correlation with measures of depression (r= .633), self-esteem (r= -.754) and fear of negative evaluation (r= .666), suggesting both nomological and discriminant validity. Althoughthe original valida-tion of the CIPS proposed a factorial structure with three factors, subsequent validations also revealed adjustment to two-and one-factor structures. Here, we used confirmatory factor analysis (CFA) to test the three different models. The results showed that in our adaptation, a 2-factor structure might be preferred. This adaptation of the CIPS to Spanish provides clinicians with a new method to gain insight into the psychological mechanisms behind the Impostor phenomenon and suitable treatmentsEl objetivo del presente estudio fue el de examinar la fiabilidad, validez y estructura factorial de la adaptación española de la Clance Impostor Phenomenon Scale (CIPS). Para ello, un total de 271 estudiantes españoles completaron una versión traducida de la escala original de 20 ítems. En nuestra muestra, el instrumento mostró una alta fiabilidad, medida como consistencia interna, (ωTotal=.90) y correlaciones moderadas-altas con medidas de depresión (r=.633), autoestima (r= -.754) y miedo a las evaluaciones negativas (r= .666), lo cual sugiere tanto una validez nomológica como discriminante. Aunque en la validación original se propuso una estructura de tres factores, otros estudios han encontrado ajuste a estructuras de uno y dos factores. Aquí, utilizamos un análisis factorial confirmatorio (AFC) para probar el ajuste de estos tres modelos. Nuestros resultados muestran que, en la adaptación a español, el modelo con dos factores es el preferido. Esta adaptación al español de la CIPS provee a los profesionales clínicos una de una nueva herramienta para poder investigar los mecanismos que subyacen al síndrome del impostor, así como futuros tratamientos

Temporal variability analysis reveals biases in electronic health records due to hospital process reengineering interventions over seven years

[EN] Objective To evaluate the effects of Process-Reengineering interventions on the Electronic Health Records (EHR) of a hospital over 7 years. Materials and methods Temporal Variability Assessment (TVA) based on probabilistic data quality assessment was applied to the historic monthly-batched admission data of Hospital La Fe Valencia, Spain from 2010 to 2016. Routine healthcare data with a complete EHR was expanded by processed variables such as the Charlson Comorbidity Index. Results Four Process-Reengineering interventions were detected by quantifiable effects on the EHR: (1) the hospital relocation in 2011 involved progressive reduction of admissions during the next four months, (2) the hospital services re-configuration incremented the number of inter-services transfers, (3) the care-services re-distribution led to transfers between facilities (4) the assignment to the hospital of a new area with 80,000 patients in 2015 inspired the discharge to home for follow up and the update of the pre-surgery planned admissions protocol that produced a significant decrease of the patient length of stay. Discussion TVA provides an indicator of the effect of process re-engineering interventions on healthcare practice. Evaluating the effect of facilities¿ relocation and increment of citizens (findings 1, 3¿4), the impact of strategies (findings 2¿3), and gradual changes in protocols (finding 4) may help on the hospital management by optimizing interventions based on their effect on EHRs or on data reuse. Conclusions The effects on hospitals EHR due to process re-engineering interventions can be evaluated using the TVA methodology. Being aware of conditioned variations in EHR is of the utmost importance for the reliable reuse of routine hospitalization data.F.J.P.B, C.S., J.M.G.G. and J.A.C. were funded Universitat Politecnica de Valencia, project "ANALISIS DE LA CALIDAD Y VARIABILIDAD DE DATOS MEDICOS". www.upv.es. J.M.G.G.is also partially supported by: Ministerio de Economia y Competitividad of Spain through MTS4up project (National Plan for Scientific and Technical Research and Innovation 2013-2016, No. DPI2016-80054-R); and European Commission projects H2020-SC1-2016-CNECT Project (No. 727560) and H2020-SC1-BHC-2018-2020 (No. 825750). The funders did not play any role in the study design, data collection and analysis, decision to publish, nor preparation of the manuscript.Perez-Benito, FJ.; Sáez Silvestre, C.; Conejero, JA.; Tortajada, S.; Valdivieso, B.; Garcia-Gomez, JM. (2019). Temporal variability analysis reveals biases in electronic health records due to hospital process reengineering interventions over seven years. PLoS ONE. 14(8):1-19. https://doi.org/10.1371/journal.pone.0220369S119148Aguilar-Savén, R. S. (2004). Business process modelling: Review and framework. International Journal of Production Economics, 90(2), 129-149. doi:10.1016/s0925-5273(03)00102-6Poulymenopoulou, M. 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Sodium Mediated Deprotonative Borylation of Arenes Using Sterically Demanding B(CH2SiMe3)3: Unlocking Polybasic Behaviour and Competing Lateral Borane Sodiation

Producción CientíficaThe deprotonative metalation of organic molecules has become a convenient route to prepare functionalised aromatic substrates. Amongst the different metallating reagents available, sodium bases have recently emerged as a more sustainable and powerful alternative to their lithium analogues. Here we report the study of the sterically demanding electrophilic trap B(CH2SiMe3)3 for the deprotonative borylation of arenes using NaTMP (TMP = 2,2,6,6-tetramethylpiperidide) in combination with tridentate Lewis donor PMDETA (PMDETA = N,N,N′,N′′,N′′-pentamethyldiethylenetriamine). Using anisole and benzene as model substrates, unexpected polybasic behaviour has been uncovered, which enables the formal borylation of two equivalents of the relevant arene. The combination of X-ray crystallographic and NMR monitoring studies with DFT calculations has revealed that while the first B–C bond forming process takes place via a sodiation/borylation sequence to furnish [(PMDETA)NaB(Ar)(CH2SiMe3)3] (I) species, the second borylation step is facilitated by the formation of a borata-alkene intermediate, without the need of an external base. For non-activated benzene, it has aslo been found that under stoichimetric conditions the lateral sodiation of B(CH2SiMe3)3 becomes a competitive reaction pathway furnishing a novel borata-alkene complex. Showing a clear alkali-metal effect, the use of the sodium base is key to access this reactivity, while the metalation/borylation of the amine donor PMDETA is observed instead when LiTMP is usedUniversidad de Valladolid. Margarita Salas Postdoctoral Fellowship (CONVREC-2021-221)University of Bern and the Swiss National Science Foundation (Grant numbers 188573, 210608 and R'Equip 206021_177033)The Irish Research Council (M.M. GOIPG/2021/88