Síntesis de polímeros organoborados retardantes a la llama

Durante las últimas décadas, la sustitución de materiales convencionales por polímerossintéticos ha aumentado de forma importante debido a la multitud de aplicaciones, pero lamayoría de ellos son extremadamente inflamables y en presencia de una fuente de calor y de xígeno se queman fácil y rápidamente.La estrategia comúnmente más utilizada para minimizar la inflamabilidad de unmaterial, es la incorporación de sustancias retardamtes a la llama. Aunque en los últimos años ha habido un incremento en el número de heteroelementos utilizados en compuestosretardantes a la llama, el mercado está todavía dominado por compuestos que contienenhalógenos, especialmente cloro y bromo. Estos compuestos, son muy efectivos ya sea comoaditivos o como reactivos pero presentan un inconveniente importante: incrementan lascantidades de humos y productos de descomposición tóxicos que se desprenden durante lacombustión del polímero. Es por ello, que cada vez más se están dedicando grandes esfuerzos en investigación a la búsqueda de nuevos retardantes a la llama libres de halógenos, querespeten el medio ambiente y no resulten agresivos.El ácido bórico y sus sales han sido empleados como aditivos retardantes a la llamadesde 1800. La mayoría de retardantes a la llama que contienen boro se descomponentérmicamente generando ácido bórico liberando agua en una reacción endotérmica, por tanto, pueden actuar como retardantes físicos al absorber calor en el proceso de descomposición,diluir los volátiles en la fase gaseosa o formar una capa de vapor de agua sobre la fase sólida.Además, el ácido bórico puede actuar formando un recubrimiento intumescente queincrementa la efectividad de la capa protectora. Estos compuestos de boro son los másutilizados, ya que resultan baratos y de amplia aplicación, pero presentan, al igual que todoslos aditivos, multiples desventajas frente a los reactivos retardantes a la llama. Loscompuestos organoborados que actúan como reactivos retardantes a la llama, no han sidoestudiados hasta, relativamente, hace poco tiempo, sin embargo, los resultados obtenidossobre la retardancia a la llama, en los diferentes polímeros modificados químicamente concompuestos de boro, han sido satisfactorios.Como objetivo general de este trabajo, se planteó la obtención de nuevos sistemaspoliméricos termoestables resistentes al fuego, libres de halógenos, sin detrimento de laspropiedades del material y que respeten el medio ambiente. Para ello se sintetizaron ycaracterizaron tres nuevos tipos de sistemas poliméricos basados en:- Resinas novolaca con boro, obtenidas por modificación química de una resinanovolaca comercial con dos compuestos organoborados: bis(benzo-1,3,2-dioxaborolanilo) y óxido de bis(4,4,5,5-tetrametil-1,3,2-dioxaborolanilo).Posteriormente, con la finalidad de mejorar sus propiedades mecánicas, estas resinasse entrecruzaron con hexametilentetraamina (HMTA) y diglicidil éter de bisfenol A(DGEBA).- Resinas epoxi-novolaca modificadas con compuestos organoborados yposteriormente entrecruzadas térmicamente con catalizador.- Polímeros estirénicos preparados a partir de monómeros que contienen boro.Finalmente, se evaluaron las propiedades térmicas, termodinamomecánicas y deretardancia a la llama de los sistemas anteriormente comentados. Pudiéndose concluir que el entrecruzamiento de las resinas novolaca con HMTA o DGEBA y de las epoxi-novolaca en presencia de un catalizador, permite obtener materiales con una buena integridad mecánica, permitiendo así establecer relaciones cualitativas de niveles de entrecruzamiento. La degradación térmica de las resinas modificadas con boro: resinas novolaca y resinas epoxinovolaca, y de los polímeros estirénicos borados, genera ácido bórico a elevadas temperaturas formando un residuo intumescente que retarda el proceso de degradación y evita que ésta sea total. Las resinas novolaca organoboradas, con contenidos de boro entre 2 y 4%, presentan excelentes propiedades de retardancia a la llama. En cambio, los polímeros estirénicos borados necesitan contenidos de al menos el 3% para manifestar buenas propiedades retardantes a la llama.Although in the last decade there has been an increase in the number of heteroelementsused in flame retardants, the commercial market is still dominated by compounds containing halogens, notably chlorine and bromine. They are exceptionally efficient and may be incorporated as either additives or as reactives, but they do have such clear disadvantages as the generation of toxic and corrosive gases during thermal degradation. Recent developments in the chemistry of halogen-free flame retardant polymers involve polymers or reactive monomers that are inherently flame retarding such as those containing P, Si, B, N and other miscellaneous elements.Boric acid and borate salts have been used as flame retardant additives since the early1800s. Borates are effective flame retardants because impenetrable glass coatings form when they thermally degrade. The glass coatings form on the surface, and can contribute to the intumescent effect, because they exclude oxygen and prevent further propagation ofcombustion. The water of hydration is lost by endothermic decomposition and therefore both dilutes and cools, by absorbing the thermal energy from the flame. However, additives have the disadvantage that they have to be used in relatively high concentrations (typically 30% by weight, or more) and this may affect the physical and mechanical properties of the polymers.Also, additives may be leached, or may volatilise from the polymer during service. Thealternative strategy is to use reactive flame retardants, via copolymerization or some othertype of chemical modification (i.e. flame retardant groups that are inherently part of thepolymer backbone or that are covalently attached as side groups to the polymer).The main aim of the present thesis is to develop new environment friendly flameretardant thermosets, which are halogen free and have the good thermal and mechanicalproperties of some standard materials. Synthetic approaches introduce boron into thebackbone of various polymers, so this main aim can be divided into four subsidiary aims:− To synthesize and characterize boron-containing novolac resins obtained bymodifying novolac with organoboron compounds. These polymers were furthercrosslinked with HMTA and DGEBA− To synthesize and characterize epoxy-novolac resins, which are then further modifiedwith boron− To synthesize and characterize boron-containing styrene monomers, which are thenfurther polymerized and copolymerized with styrene− To evaluate the thermal, mechanical and flame retardancy properties of all thepolymeric systems synthesizedThe conclusions drawn from the various studies of the present thesis can be summarizedas follows:− The modification of the commercial novolac resin with organoboron compoundreaches a plateau at a modification degree of 65%− The crosslinking of boron-modified novolac resin with HMTA is slower and lessextensive than that of commercial novolac resin because of the nitrogen coordinationfrom intermediate species with boron− The crosslinking of commercial novolac resins with DGEBA needs a catalyst to beadded while the crosslinking of boron-containing novolac resins does not because theboron itself acts as a catalyst− The epoxy-novolac resins react with boron compounds mainly through the hydroxylic groups from halohydrin and opened glycidylic groups− The thermal degradation of boron-containing novolac resins, boron-containing epoxynovolac resins and boron-containing styrenic polymers generates boric acid at hightemperatures to give an intumescent char that slows down the degradation andprevents it from being total− Novolac resins modified with boron content between 2 and 4%, show high LOI values(above 38%)− Boron-containing styrenic polymers show LOI values that increase with boron contentbut boron contents need to be above 3% to achieve good flame retardant properties

Noise Sources, Effects and Countermeasures in Narrowband Power-Line Communications Networks: A Practical Approach

The integration of Distributed Generation, Electric Vehicles, and storage without compromising the quality of the power delivery requires the deployment of a communications overlay that allows monitoring and controlling low voltage networks in almost real time. Power Line Communications are gaining momentum for this purpose since they present a great trade-off between economic and technical features. However, the power lines also represent a harsh communications medium which presents different problems such as noise, which is indeed affected by Distributed Generation, Electric Vehicles, and storage. This paper provides a comprehensive overview of the types of noise that affects Narrowband Power Line Communications, including normative noises, noises coming from common electronic devices measured in actual operational power distribution networks, and noises coming from photovoltaic inverters and electric vehicle charging spots measured in a controlled environment. The paper also reviews several techniques to mitigate the effects of noise, paying special attention to passive filtering, as for being one of the most widely used solution to avoid this kind of problems in the field. In addition, the paper presents a set of tests carried out to evaluate the impact of some representative noises on Narrowband Power Line Communications network performance, as well as the effectiveness of different passive filter configurations to mitigate such an impact. In addition, the considered sources of noise can also bring value to further improve PLC communications in the new scenarios of the Smart Grid as an input to theoretical models or simulations.This work has been partly funded by the Spanish Ministry of Economy and Competitiveness through the National Program for Research Aimed at the Challenges of Society under the project OSIRIS (RTC-2014-1556-3) and through the network of excellence REDYD2050 (ENE2015-70032-REDT)

Noise Sources, Effects and Countermeasures in Narrowband Power-Line Communications Networks: A Practical Approach

The integration of Distributed Generation, Electric Vehicles, and storage without compromising the quality of the power delivery requires the deployment of a communications overlay that allows monitoring and controlling low voltage networks in almost real time. Power Line Communications are gaining momentum for this purpose since they present a great trade-off between economic and technical features. However, the power lines also represent a harsh communications medium which presents different problems such as noise, which is indeed affected by Distributed Generation, Electric Vehicles, and storage. This paper provides a comprehensive overview of the types of noise that affects Narrowband Power Line Communications, including normative noises, noises coming from common electronic devices measured in actual operational power distribution networks, and noises coming from photovoltaic inverters and electric vehicle charging spots measured in a controlled environment. The paper also reviews several techniques to mitigate the effects of noise, paying special attention to passive filtering, as for being one of the most widely used solution to avoid this kind of problems in the field. In addition, the paper presents a set of tests carried out to evaluate the impact of some representative noises on Narrowband Power Line Communications network performance, as well as the effectiveness of different passive filter configurations to mitigate such an impact. In addition, the considered sources of noise can also bring value to further improve PLC communications in the new scenarios of the Smart Grid as an input to theoretical models or simulations.This work has been partly funded by the Spanish Ministry of Economy and Competitiveness through the National Program for Research Aimed at the Challenges of Society under the project OSIRIS (RTC-2014-1556-3) and through the network of excellence REDYD2050 (ENE2015-70032-REDT)

Baseline to Evaluate Off-Site Suspended Sediment-Related Mining Effects in the Alto Tajo Natural Park, Spain

Mining is a human activity with considerable environmental impact. To evaluate such impacts, international laws require undertaking local studies based on direct sampling to establish baseline conditions of parameters modified by human activities. Mining takes place near the Alto Tajo Natural Park, where a suspended sediment concentration (SSC) baseline is required to determine whether mining affects water quality. To this end, we have monitored the Tajo River and its tributary the Tajuelo following Before–After Control-Impact (BACI) techniques, recommended by Australian and New Zealand laws, requiring a specific method based on continuous monitoring and sampling to enable evaluation of SSCs. An SSC baseline has been defined at stations situated upstream of the mining area and compared with those downstream. The highest detected SSC upstream of the Tajuelo mines was 24 g l−1 whereas the highest simultaneous downstream value was 391 g l−1, more than one order of magnitude higher than the supposed baseline (24 g l−1). Additionally, this value is 1000 times more than the average concentration of 25 mg l−1, used by the European Union until 2015, to guarantee the quality of salmonid waters. Following a BACI approach, a statistically significant SSC impact has been identified. The mined areas are the only source that can explain this increase. This is the first instance that such an increase and baseline have been found using this method. BACI is a simple and reliable method recommended for studying degraded areas rather than an irrelevant, fixed standard as included in most international laws. Copyright © 2016 John Wiley & Sons, Ltd.This study was funded by: (i) Research Project CGL2010-21754-C02-01 (Spanish Ministry of Science and Technology, and Ministry of Economy); (ii) the Department of Agriculture and Environment of Castile—La Mancha through its socalled “Fondos Verdes” (Green Funding); (iii) the research contract 249/2015 between CAOBAR and UCM; (iv) the Ecological Restoration Network REMEDINAL-3 of the Madrid Community (S2013/MAE-2719); (v) the Spanish National Research Council (CSIC) for Ph.D. Grant JAEPredoc to IZAPeer reviewe

Effects of Topography and Surface Soil Cover on Erosion for Mining Reclamation: The Experimental Spoil Heap at El Machorro Mine (Central Spain)

Mining reclamation tries to reduce environmental impacts, including accelerated runoff, erosion and sediment load in the nearby fluvial networks and their ecosystems. This study compares the effects of topography and surface soil cover on erosion on man-made slopes coming from surface mining reclamation in Central Spain. Two topographic profiles, linear and concave, with two surface soil covers, subsoil and topsoil, were monitored for two hydrologic years. Sediment load, rill development and plant colonization from the four profiles were measured under field conditions. The results show that, in the case of this experiment, a thick and non-compacted topsoil cover on a linear slope yielded less sediment than carbonate colluvium or topsoil cover on a concave slope. This study also shows that vegetation establishment, which plays an important role in erosion control, depends on topography. Plant cover was more widespread and more homogeneous on linear profiles with topsoil cover. On concave slopes, plant establishment was severely limited on the steepest upper part and favoured in the bottom. This study suggests that management of topography and surface soil cover should be approached systematically, taking three outcomes into consideration: (i) topsoil can lead to a successful mining reclamation regardless of topography, (ii) created concave slopes can lead to a successful mining reclamation and (iii) topography determines the vegetation colonization pattern.The experiment was funded by a research contract between the Spanish mining company 602 CAOBAR S.A. and the Department of Geodynamics of the Complutense University of Madrid 603 (research contract numbers 234/2007, 290/2008 261/2009). The data analyses and manuscript 604 production were developed within two Research Projects, CGL2009-14508-C02-01 and 605 CGL2010-21754-C02, of the Spanish Ministry of Science and Technology and by the 606 Ecological Restoration network REMEDINAL-2 (S2009/AMB-1783).Peer reviewe

Nonprofit good governance mechanisms: A systematic literature review

There is widespread acknowledgment of the importance of nonprofit good governance with a need for guidance on different effective mechanisms to increase ethical practices for the whole sector to assist professionals and researchers. This study explores two research questions: (1) What are the main reasons that inspire nonprofit organizations (NPOs) to implement good governance mechanisms? (2) What are the good governance mechanisms conducted by NPOs? The purpose is to serve as a reference and an instrument of reflection for interested NPOs exploring good governance mechanisms to make their accountability work more effective. We used a systematic literature review methodology for identification, selection, and analysis of published research on nonprofit good governance. A set of 89 articles published until 2021 was analyzed, and a new classification that identified 3 lines and 13 sublines of research was provided. Our results show that a variety of internal mechanisms and international third-party initiatives are underpinned by the need to adhere to standards of ethics and honesty.Grupo de Investigación “SEJ289: Information and Management Systems in the Andalusian Company” de la Universidad de Jaé

“Desayuna con la ciencia”: como acercar la ciencia a niños de forma amena

En la actualidad es primordial que los centros del conocimiento como las universidades divulguen y promuevan el acercamiento de todas las disciplinas científicas (entendiendo estas como arte y humanidades, ciencias, ciencias de la salud, ciencias sociales y jurídicas e ingeniería y arquitectura) a la ciudadanía a través de distintas metodologías. Este acercamiento es fundamental en el contexto escolar, mediante la aplicación de nuevas metodologías didácticas y prácticas que fomenten el interés de los estudiantes por el ámbito científico, de esta forma se conseguirá una mayor apertura de la sociedad hacia la ciencia. En la Universidad de Extremadura este acercamiento se realiza a través de las jornadas “Desayuna con la ciencia”, una actividad abierta a alumnos de 5º y 6º de primaria de los colegios de la comunidad autónoma de Extremadura y cuyos objetivos fundamentales son acercar y promover actividades de divulgación científica que motiven la ciencia y la tecnología como herramientas en el desarrollo intelectual, promover una cultura científica a niños y niñas de zonas rurales de la región, hacer visible la relación entre la ciencia y las actividades de la vida diaria permitiendo la aplicación del conocimiento científico a los problemas cotidianos, incorporar nuevas formas innovadoras de trabajo mediante demostraciones práctica de los contenidos y fijar capital humano a nuestra región. Además la importancia del programa está en consonancia con lo recogido en la Declaración sobre la Ciencia y el Uso del saber Científico aprobada por la UNESCO en 1999, y en la que se aboga por, “El fortalecimiento del papel de la ciencia en pro de un mundo más equitativo, próspero y sostenible requiere un compromiso a largo plazo de todas las partes interesadas, sean del sector público o privado, que incluya un aumento de las inversiones y el análisis correspondiente de las prioridades en materia de inversión, y el aprovechamiento compartido del saber científico”. Desayuna con la ciencia se desarrolla mediante Talleres didáctico- científicos, estos pueden ser desde un experimento, una demostración, o una exhibición que muestre los pasos del método científico que hay que seguir para estudiar un fenómeno. Estos talleres son eminentemente prácticos, de esta forma se introduce al alumnado en grandes conceptos científicos, valorando así sus propias observaciones. A través de esta comunicación, analizamos la relación entre ciencia y divulgación científica a niños de primaria a través de una actividad que aúna práctica y diversión, pero sin perder el rigor educativo y científico aprovechando de esta forma la curiosidad natural de los niños

Mitochondrial respiratory chain dysfunction: implications in neurodegeneration

The definitive version of this article is available at http://www.sciencedirect.com/science/journal/0891584

Mitochondrial complex I plays an essential role in human respirasome assembly

The assembly and function of the mitochondrial respiratory chain (RC) involve the organization of RC enzyme complexes in supercomplexes or respirasomes through an unknown biosynthetic process. This leads to structural interdependences between RC complexes, which are highly relevant from biological and biomedical perspectives, because RC defects lead to severe human disorders. We show that in human cells, respirasome biogenesis involves a complex I assembly intermediate acting as a scaffold for the combined incorporation of complexes III and IV subunits, rather than originating from the association of preassembled individual holoenzymes. The process ends with the incorporation of complex I NADH dehydrogenase catalytic module, which leads to the respirasome activation. While complexes III and IV assemble either as free holoenzymes or by incorporation of free subunits into supercomplexes, the respirasomes constitute the structural units where complex I is assembled and activated, thus explaining the functional significance of the respirasomes for RC function

Role of the LPA1 receptor in mood and emotional regulation

Depression is a debilitating psychiatric condition characterized by anhedonia and behavioural despair among others symptoms. Despite the high prevalence and devastating impact of depression, underlying neurobiological mechanisms of mood disorders are still not well known. Regardless its complexity, central features of this disease can be modelled in rodents in order to better understand the potential mechanisms underlying. On the other hand, the lack of LPA1 receptor compromises the morphological and functional integrity of the limbic circuit and the neurogenesis in hippocampus, induces cognitive alterations on hippocampal-dependent tasks and dysfunctional coping of chronic stress, provokes exaggerated endocrine responses to emotional stimuli and impairs adaptation of the hypothalamic-pituitary-adrenal axis after chronic stress. Factors, which all have been related with depression. Here, we sought to establish the involvement of the LPA1 receptor in regulation of mood and emotion. To this end, in wild-type and maLPA1-null mice active coping responses to stress were examined using the forced swimming test (FST). To assess hedonic behaviour saccharine preference test and female urine sniffing test were used. Our data indicated that the absence of the LPA1 receptor significantly affected to coping strategies. Thus, while null mice displayed less immobility than wt in FST, exhibited more climbing and less swimming behaviour, responses that could be interpreted as an emotional over-reaction (i.e., a panic-like response) to stress situations. Concerning hedonic behaviour, the lack of the LPA1 receptor diminished saccharin preference and female urine sniffing time. Overall, these data supports the role of LPA1 receptor in mood and emotional regulation. Specially, the lack of this receptor induced emotional dysregulation and anhedonic behaviour, a core symptom of depression.Universidad de Málaga, Campus de Excelencia Andalucía Tech. Andalusian Regional Ministries of Economy, Innovation, Science and Employment (SEJ-1863; CTS643) and of Health (PI-0234-2013; Nicolas Monardes Programme), MINECO (PSI2013-44901-P) and National Institute of Health Carlos III (Sara Borrel)