Geochemistry of lavas from the Lau-Tonga arc and back-arc system

Detailed comparison of mineralogy, and major and trace geochemistry are presented for the modern Lau Basin spreading centers, the Sites 834-839 lavas, the modern Tonga-Kermadec arc volcanics, the northern Tongan boninites, and the Lau Ridge volcanics. The data clearly confirm the variations from near normal mid-ocean-ridge basalt (N-MORB) chemistries (e.g., Site 834, Central Lau Spreading Center) to strongly arc-like (e.g., Site 839, Valu Fa), the latter closely comparable to the modern arc volcanoes. Sites 835 and 836 and the East Lau Spreading Center represent transitional chemistries. Bulk compositions range from andesitic to basaltic, but lavas from Sites 834 and 836 and the Central Lau Spreading Center extend toward more silica-undersaturated compositions. The Valu Fa and modern Tonga-Kermadec arc lavas, in contrast, are dominated by basaltic andesites. The phenocryst and groundmass mineralogies show the strong arc-like affinities of the Site 839 lavas, which are also characterized by the existence of very magnesian olivines (up to Fo90-92) and Cr-rich spinels in Units 3 and 6, and highly anorthitic plagioclases in Units 2 and 9. The regional patterns of mineralogical and geochemical variations are interpreted in terms of two competing processes affecting the inferred magma sources: (1) mantle depletion processes, caused by previous melt extractions linked to backarc magmatism, and (2) enrichment in large-ion-lithophile elements, caused by a subduction contribution. A general trend of increasing depletion is inferred both eastward across the Lau Basin toward the modern arc, and northward along the Tongan (and Kermadec) Arc. Numerical modeling suggests that multistage magma extraction can explain the low abundances (relative to N-MORB) of elements such as Nb, Ta, and Ti, known to be characteristic of island arc magmas. It is further suggested that a subduction jump following prolonged slab rollback could account for the initiation of the Lau Basin opening, plausibly allowing a later influx of new mantle, as required by the recognition of a two-stage opening of the Lau Basin.

Chemical composition of East Pacific Rise basal sediments

Analyses by atomic absorption spectrophotometry and spark-source mass spectrography of 25 basal metalliferous sediment units from widely spaced locations on the western flank of the East Pacific Rise show that the deposits are enriched relative to normal pelagic sediment in Fe, Mn, Ni, Cu, Pb, Zn, and many trace elements. The elements are partitioned differently between the various mineralogic constituents of the sediment, with Fe and Mn largely in separate phases and many of the remaining elements primarily associated with reducible ferromanganese oxide minerals but also with iron minerals and other phases. Most of the iron in the deposits is probably of volcanic origin, and much of the manganese and minor elements is derived from sea water. The bulk composition of the deposits varies with age; this is thought to be due to variations in the incidence of volcanic activity at the East Pacific Rise crest where the deposits were formed.

Hydrodynamic stability theory of double ablation front structures in inertial confinement fusion.

The aim of inertial confinement fusion is the production of energy by the fusion of thermonuclear fuel (deuterium-tritium) enclosed in a spherical target due to its implosion. In the direct-drive approach, the energy needed to spark fusion reactions is delivered by the irradiation of laser beams that leads to the ablation of the outer shell of the target (the so-called ablator). As a reaction to this ablation process, the target is accelerated inwards, and, provided that this implosion is sufficiently strong a symmetric, the requirements of temperature and pressure in the center of the target are achieved leading to the ignition of the target (fusion). One of the obstacles capable to prevent appropriate target implosions takes place in the ablation region where any perturbation can grow even causing the ablator shell break, due to the ablative Rayleigh-Taylor instability. The ablative Rayleigh-Taylor instability has been extensively studied throughout the last 40 years in the case where the density/temperature profiles in the ablation region present a single front (the ablation front). Single ablation fronts appear when the ablator material has a low atomic number (deuterium/tritium ice, plastic). In this case, the main mechanism of energy transport from the laser energy absorption region (low density plasma) to the ablation region is the electron thermal conduction. However, recently, the use of materials with a moderate atomic number (silica, doped plastic) as ablators, with the aim of reducing the target pre-heating caused by suprathermal electrons generated by the laser-plasma interaction, has demonstrated an ablation region composed of two ablation fronts. This fact appears due to increasing importance of radiative effects in the energy transport. The linear theory describing the Rayleigh-Taylor instability for single ablation fronts cannot be applied for the stability analysis of double ablation front structures. Therefore, the aim of this thesis is to develop, for the first time, a linear stability theory for this type of hydrodynamic structures.

Aspectos de la medición dinámica instantánea de emisiones de motores. Aplicación al desarrollo de un equipo portátil y una metodología para estudios de contaminación de vehículos en tráfico real.

Esta Tesis Doctoral se encuadra en el ámbito de la medida de emisiones contaminantes y de consumo de combustible en motores de combustión interna alternativos cuando se utilizan como plantas de potencia para propulsión de vehículos ligeros de carretera, y más concretamente en las medidas dinámicas con el vehículo circulando en tráfico real. En este ámbito, el objetivo principal de la Tesis es estudiar los problemas asociados a la medición en tiempo real con equipos embarcados de variables medioambientales, energéticas y de actividad, de vehículos ligeros propulsados por motores térmicos en tráfico real. Y como consecuencia, desarrollar un equipo y una metodología apropiada para este objetivo, con el fin de realizar consiguientemente un estudio sobre los diferentes factores que influyen sobre las emisiones y el consumo de combustible de vehículos turismo en tráfico real. La Tesis se comienza realizando un estudio prospectivo sobre los trabajos de otros autores relativos al desarrollo de equipos portátiles de medida de emisiones (Portable Emission Measurement Systems – PEMS), problemas asociados a la medición dinámica de emisiones y estudios de aplicación en tráfico real utilizando este tipo de equipos. Como resultado de este estudio se plantea la necesidad de disponer de un equipo específicamente diseñado para ser embarcado en un vehículo que sea capaz de medir en tiempo real las concentraciones de emisiones y el caudal de gases de escape, al mismo tiempo que se registran variables del motor, del vehículo y del entorno como son la pendiente y los datos meteorológicos. De esta forma se establecen las especificaciones y condiciones de diseño del equipo PEMS. Aunque al inicio de esta Tesis ya existían en el mercado algunos sistemas portátiles de medida de emisiones (PEMS: Portable Emissions Measurement Systems), en esta Tesis se investiga, diseña y construye un nuevo sistema propio, denominado MIVECO – PEMS. Se exponen, discuten y justifican todas las soluciones técnicas incorporadas en el sistema que incluyen los subsistema de análisis de gases, subsistemas de toma de muestra incluyendo caudalímetro de gases de escape, el subsistema de medida de variables del entorno y actividad del vehículo y el conjunto de sistemas auxiliares. El diseño final responde a las hipótesis y necesidades planteadas y se valida en uso real, en banco de rodillos y en comparación con otro equipos de medida de emisiones estacionarios y portátiles. En esta Tesis se presenta también toda la investigación que ha conducido a establecer la metodología de tratamiento de las señales registradas en tiempo real que incluye la sincronización, cálculos y propagación de errores. La metodología de selección y caracterización de los recorridos y circuitos y de las pautas de conducción, preparación del vehículo y calibración de los equipos forma también parte del legado de esta Tesis. Para demostrar la capacidad de medida del equipo y el tipo de resultados que pueden obtenerse y que son útiles para la comunidad científica, y las autoridades medioambientales en la parte final de esta Tesis se plantean y se presentan los resultados de varios estudios de variables endógenas y exógenas que afectan a las emisiones instantáneas y a los factores de emisión y consumo (g/km) como: el estilo de conducción, la infraestructura vial, el nivel de congestión del tráfico, tráfico urbano o extraurbano, el contenido de biocarburante, tipo de motor (diesel y encendido provocado), etc. Las principales conclusiones de esta Tesis son que es posible medir emisiones másicas y consumo de motores de vehículos en uso real y que los resultados permiten establecer políticas de reducción de impacto medio ambiental y de eficiencia energética, pero, se deben establecer unas metodologías precisas y se debe tener mucho cuidado en todo el proceso de calibración, medida y postratamientos de los datos. Abstract This doctoral thesis is in the field of emissions and fuel consumption measurement of reciprocating internal combustion engines when are used as power-trains for light-duty road vehicles, and especially in the real-time dynamic measurements procedures when the vehicle is being driven in real traffic. In this context, the main objective of this thesis is to study the problems associated with on-board real-time measuring systems of environmental, energy and activity variables of light vehicles powered by internal combustion engines in real traffic, and as a result, to develop an instrument and an appropriate methodology for this purpose, and consequently to make a study of the different factors which influence the emissions and the fuel consumption of passenger cars in real traffic. The thesis begins developing a prospective study on other authors’ works about development of Portable Emission Measurement Systems (PEMS), problems associated with dynamic emission measurements and application studies on actual traffic using PEMS. As a result of this study, it was shown that a measuring system specifically designed for being on-board on a vehicle, which can measure in real time emission concentrations and exhaust flow, and at the same time to record motor vehicle and environment variables as the slope and atmospheric data, is needed; and the specifications and design parameters of the equipment are proposed. Although at the beginning of this research work there were already on the market some PEMS, in this Thesis a new system is researched, designed and built, called MIVECO – PEMS, in order to meet such measurements needs. Following that, there are presented, discussed and justify all technical solutions incorporated in the system, including the gas analysis subsystem, sampling and exhaust gas flowmeter subsystem, the subsystem for measurement of environment variables and of the vehicle activity and the set of auxiliary subsystems. The final design meets the needs and hypotheses proposed, and is validated in real-life use and chassis dynamometer testing and is also compared with other stationary and on-board systems. This thesis also presents all the research that has led to the methodology of processing the set of signals recorded in real time including signal timing, calculations and error propagation. The methodology to select and characterize of the routes and circuits, the driving patterns, and the vehicle preparation and calibration of the instruments and sensors are part of the legacy of this thesis. To demonstrate the measurement capabilities of the system and the type of results that can be obtained and that are useful for the scientific community and the environmental authorities, at the end of this Thesis is presented the results of several studies of endogenous and exogenous variables that affect the instantaneous and averaged emissions and consumption factors (g/km), as: driving style, road infrastructure, the level of traffic congestion, urban and extra-urban traffic, biofuels content, type of engine (diesel or spark ignition) etc. The main conclusions of this thesis are that it is possible to measure mass emissions and consumption of vehicle engines in actual use and that the results allow us to establish policies to reduce environmental impact and improve energy efficiency, but, to establish precise methodologies and to be very careful in the entire process of calibration, measurement and data post-treatment is necessary.

Analysis of the Iberian Power Forward Price Formation

The price formation of the Iberian Energy Derivatives Market-the power futures market-starting in July 2006, is assessed until November 2011, through the evolution of the difference between forward and spot prices in the delivery period (“ex-post forward risk premium”) and the comparison with the forward generation costs from natural gas (“clean spark spread”). The premium tends to be positive in all existing mechanisms (futures, Over-the-Counter and auctions for catering part of the last resort supplies). Since year 2011, the values are smaller due to regulatorily recognized prices for coal power plants. The power futures are strongly correlated with European gas prices. The spreads built with prompt contracts tend also to be positive. The biggest ones are for the month contract, followed by the quarter contract and then by the year contract. Therefore, gas fired generation companies can maximize profits trading with contracts of shorter maturity.

Propuestas regulatorias para el diseño de un mercado ibérico a plazo eficiente de la energía = Regulatory proposals for the development of an efficient iberian energy forward market

El mercado ibérico de futuros de energía eléctrica gestionado por OMIP (“Operador do Mercado Ibérico de Energia, Pólo Português”, con sede en Lisboa), también conocido como el mercado ibérico de derivados de energía, comenzó a funcionar el 3 de julio de 2006. Se analiza la eficiencia de este mercado organizado, por lo que se estudia la precisión con la que sus precios de futuros predicen el precio de contado. En dicho mercado coexisten dos modos de negociación: el mercado continuo (modo por defecto) y la contratación mediante subasta. En la negociación en continuo, las órdenes anónimas de compra y de venta interactúan de manera inmediata e individual con órdenes contrarias, dando lugar a operaciones con un número indeterminado de precios para cada contrato. En la negociación a través de subasta, un precio único de equilibrio maximiza el volumen negociado, liquidándose todas las operaciones a ese precio. Adicionalmente, los miembros negociadores de OMIP pueden liquidar operaciones “Over-The-Counter” (OTC) a través de la cámara de compensación de OMIP (OMIClear). Las cinco mayores empresas españolas de distribución de energía eléctrica tenían la obligación de comprar electricidad hasta julio de 2009 en subastas en OMIP, para cubrir parte de sus suministros regulados. De igual manera, el suministrador de último recurso portugués mantuvo tal obligación hasta julio de 2010. Los precios de equilibrio de esas subastas no han resultado óptimos a efectos retributivos de tales suministros regulados dado que dichos precios tienden a situarse ligeramente sesgados al alza. La prima de riesgo ex-post, definida como la diferencia entre los precios a plazo y de contado en el periodo de entrega, se emplea para medir su eficiencia de precio. El mercado de contado, gestionado por OMIE (“Operador de Mercado Ibérico de la Energía”, conocido tradicionalmente como “OMEL”), tiene su sede en Madrid. Durante los dos primeros años del mercado de futuros, la prima de riesgo media tiende a resultar positiva, al igual que en otros mercados europeos de energía eléctrica y gas natural. En ese periodo, la prima de riesgo ex-post tiende a ser negativa en los mercados de petróleo y carbón. Los mercados de energía tienden a mostrar niveles limitados de eficiencia de mercado. La eficiencia de precio del mercado de futuros aumenta con el desarrollo de otros mecanismos coexistentes dentro del mercado ibérico de electricidad (conocido como “MIBEL”) –es decir, el mercado dominante OTC, las subastas de centrales virtuales de generación conocidas en España como Emisiones Primarias de Energía, y las subastas para cubrir parte de los suministros de último recurso conocidas en España como subastas CESUR– y con una mayor integración de los mercados regionales europeos de energía eléctrica. Se construye un modelo de regresión para analizar la evolución de los volúmenes negociados en el mercado continuo durante sus cuatro primeros años como una función de doce indicadores potenciales de liquidez. Los únicos indicadores significativos son los volúmenes negociados en las subastas obligatorias gestionadas por OMIP, los volúmenes negociados en el mercado OTC y los volúmenes OTC compensados por OMIClear. El número de creadores de mercado, la incorporación de agentes financieros y compañías de generación pertenecientes a grupos integrados con suministradores de último recurso, y los volúmenes OTC compensados por OMIClear muestran una fuerte correlación con los volúmenes negociados en el mercado continuo. La liquidez de OMIP está aún lejos de los niveles alcanzados por los mercados europeos más maduros (localizados en los países nórdicos (Nasdaq OMX Commodities) y Alemania (EEX)). El operador de mercado y su cámara de compensación podrían desarrollar acciones eficientes de marketing para atraer nuevos agentes activos en el mercado de contado (p.ej. industrias consumidoras intensivas de energía, suministradores, pequeños productores, compañías energéticas internacionales y empresas de energías renovables) y agentes financieros, captar volúmenes del opaco OTC, y mejorar el funcionamiento de los productos existentes aún no líquidos. Resultaría de gran utilidad para tales acciones un diálogo activo con todos los agentes (participantes en el mercado, operador de mercado de contado, y autoridades supervisoras). Durante sus primeros cinco años y medio, el mercado continuo presenta un crecimento de liquidez estable. Se mide el desempeño de sus funciones de cobertura mediante la ratio de posición neta obtenida al dividir la posición abierta final de un contrato de derivados mensual entre su volumen acumulado en la cámara de compensación. Los futuros carga base muestran la ratio más baja debido a su buena liquidez. Los futuros carga punta muestran una mayor ratio al producirse su menor liquidez a través de contadas subastas fijadas por regulación portuguesa. Las permutas carga base liquidadas en la cámara de compensación ubicada en Madrid –MEFF Power, activa desde el 21 de marzo de 2011– muestran inicialmente valores altos debido a bajos volúmenes registrados, dado que esta cámara se emplea principalmente para vencimientos pequeños (diario y semanal). Dicha ratio puede ser una poderosa herramienta de supervisión para los reguladores energéticos cuando accedan a todas las transacciones de derivados en virtud del Reglamento Europeo sobre Integridad y Transparencia de los Mercados de Energía (“REMIT”), en vigor desde el 28 de diciembre de 2011. La prima de riesgo ex-post tiende a ser positiva en todos los mecanismos (futuros en OMIP, mercado OTC y subastas CESUR) y disminuye debido a la curvas de aprendizaje y al efecto, desde el año 2011, del precio fijo para la retribución de la generación con carbón autóctono. Se realiza una comparativa con los costes a plazo de generación con gas natural (diferencial “clean spark spread”) obtenido como la diferencia entre el precio del futuro eléctrico y el coste a plazo de generación con ciclo combinado internalizando los costes de emisión de CO2. Los futuros eléctricos tienen una elevada correlación con los precios de gas europeos. Los diferenciales de contratos con vencimiento inmediato tienden a ser positivos. Los mayores diferenciales se dan para los contratos mensuales, seguidos de los trimestrales y anuales. Los generadores eléctricos con gas pueden maximizar beneficios con contratos de menor vencimiento. Los informes de monitorización por el operador de mercado que proporcionan transparencia post-operacional, el acceso a datos OTC por el regulador energético, y la valoración del riesgo regulatorio pueden contribuir a ganancias de eficiencia. Estas recomendaciones son también válidas para un potencial mercado ibérico de futuros de gas, una vez que el hub ibérico de gas –actualmente en fase de diseño, con reuniones mensuales de los agentes desde enero de 2013 en el grupo de trabajo liderado por el regulador energético español– esté operativo. El hub ibérico de gas proporcionará transparencia al atraer más agentes y mejorar la competencia, incrementando su eficiencia, dado que en el mercado OTC actual no se revela precio alguno de gas. ABSTRACT The Iberian Power Futures Market, managed by OMIP (“Operador do Mercado Ibérico de Energia, Pólo Português”, located in Lisbon), also known as the Iberian Energy Derivatives Market, started operations on 3 July 2006. The market efficiency, regarding how well the future price predicts the spot price, is analysed for this energy derivatives exchange. There are two trading modes coexisting within OMIP: the continuous market (default mode) and the call auction. In the continuous trading, anonymous buy and sell orders interact immediately and individually with opposite side orders, generating trades with an undetermined number of prices for each contract. In the call auction trading, a single price auction maximizes the traded volume, being all trades settled at the same price (equilibrium price). Additionally, OMIP trading members may settle Over-the-Counter (OTC) trades through OMIP clearing house (OMIClear). The five largest Spanish distribution companies have been obliged to purchase in auctions managed by OMIP until July 2009, in order to partly cover their portfolios of end users’ regulated supplies. Likewise, the Portuguese last resort supplier kept that obligation until July 2010. The auction equilibrium prices are not optimal for remuneration purposes of regulated supplies as such prices seem to be slightly upward biased. The ex-post forward risk premium, defined as the difference between the forward and spot prices in the delivery period, is used to measure its price efficiency. The spot market, managed by OMIE (Market Operator of the Iberian Energy Market, Spanish Pool, known traditionally as “OMEL”), is located in Madrid. During the first two years of the futures market, the average forward risk premium tends to be positive, as it occurs with other European power and natural gas markets. In that period, the ex-post forward risk premium tends to be negative in oil and coal markets. Energy markets tend to show limited levels of market efficiency. The price efficiency of the Iberian Power Futures Market improves with the market development of all the coexistent forward contracting mechanisms within the Iberian Electricity Market (known as “MIBEL”) – namely, the dominant OTC market, the Virtual Power Plant Auctions known in Spain as Energy Primary Emissions, and the auctions catering for part of the last resort supplies known in Spain as CESUR auctions – and with further integration of European Regional Electricity Markets. A regression model tracking the evolution of the traded volumes in the continuous market during its first four years is built as a function of twelve potential liquidity drivers. The only significant drivers are the traded volumes in OMIP compulsory auctions, the traded volumes in the OTC market, and the OTC cleared volumes by OMIClear. The amount of market makers, the enrolment of financial members and generation companies belonging to the integrated group of last resort suppliers, and the OTC cleared volume by OMIClear show strong correlation with the traded volumes in the continuous market. OMIP liquidity is still far from the levels reached by the most mature European markets (located in the Nordic countries (Nasdaq OMX Commodities) and Germany (EEX)). The market operator and its clearing house could develop efficient marketing actions to attract new entrants active in the spot market (e.g. energy intensive industries, suppliers, small producers, international energy companies and renewable generation companies) and financial agents as well as volumes from the opaque OTC market, and to improve the performance of existing illiquid products. An active dialogue with all the stakeholders (market participants, spot market operator, and supervisory authorities) will help to implement such actions. During its firs five and a half years, the continuous market shows steady liquidity growth. The hedging performance is measured through a net position ratio obtained from the final open interest of a month derivatives contract divided by its accumulated cleared volume. The base load futures in the Iberian energy derivatives exchange show the lowest ratios due to good liquidity. The peak futures show bigger ratios as their reduced liquidity is produced by auctions fixed by Portuguese regulation. The base load swaps settled in the clearing house located in Spain – MEFF Power, operating since 21 March 2011, with a new denomination (BME Clearing) since 9 September 2013 – show initially large values due to low registered volumes, as this clearing house is mainly used for short maturity (daily and weekly swaps). The net position ratio can be a powerful oversight tool for energy regulators when accessing to all the derivatives transactions as envisaged by European regulation on Energy Market Integrity and Transparency (“REMIT”), in force since 28 December 2011. The ex-post forward risk premium tends to be positive in all existing mechanisms (OMIP futures, OTC market and CESUR auctions) and diminishes due to the learning curve and the effect – since year 2011 – of the fixed price retributing the indigenous coal fired generation. Comparison with the forward generation costs from natural gas (“clean spark spread”) – obtained as the difference between the power futures price and the forward generation cost with a gas fired combined cycle plant taking into account the CO2 emission rates – is also performed. The power futures are strongly correlated with European gas prices. The clean spark spreads built with prompt contracts tend to be positive. The biggest clean spark spreads are for the month contract, followed by the quarter contract and then by the year contract. Therefore, gas fired generation companies can maximize profits trading with contracts of shorter maturity. Market monitoring reports by the market operator providing post-trade transparency, OTC data access by the energy regulator, and assessment of the regulatory risk can contribute to efficiency gains. The same recommendations are also valid for a potential Iberian gas futures market, once an Iberian gas hub – currently in a design phase, with monthly meetings amongst the stakeholders in a Working Group led by the Spanish energy regulatory authority since January 2013 – is operating. The Iberian gas hub would bring transparency attracting more shippers and improving competition and thus its efficiency, as no gas price is currently disclosed in the existing OTC market.

Estudio y evaluación de sistemas “BIG Data” de tratamiento de información

En estos tiempos toma un papel fundamental poder analizar toda la información que circula por la red de una manera rápida y sencilla para poder obtener un gran valor de ella. La denominada Big Data es cada día más importante para las empresas y es por ello por lo que en este trabajo se va a estudiar una solución novedosa para su manejo. Apache Spark es una herramienta creada para el manejo de esas cantidades de información y a lo largo de este trabajo se van a mostrar sus puntos fuertes, así como diferentes casos de uso donde aporta una gran ventaja sobre sus alternativas.

Voltage dependence of the pattern and frequency of discrete Ca2+ release events after brief repriming in frog skeletal muscle

Applying a brief repolarizing pre-pulse to a depolarized frog skeletal muscle fiber restores a small fraction of the transverse tubule membrane voltage sensors from the inactivated state. During a subsequent depolarizing test pulse we detected brief, highly localized elevations of myoplasmic Ca2+ concentration (Ca2+ “sparks”) initiated by restored voltage sensors in individual triads at all test pulse voltages. The latency histogram of these events gives the gating pattern of the sarcoplasmic reticulum (SR) calcium release channels controlled by the restored voltage sensors. Both event frequency and clustering of events near the start of the test pulse increase with test pulse depolarization. The macroscopic SR calcium release waveform, obtained from the spark latency histogram and the estimated open time of the channel or channels underlying a spark, exhibits an early peak and rapid marked decline during large depolarizations. For smaller depolarizations, the release waveform exhibits a smaller peak and a slower decline. However, the mean use time and mean amplitude of the individual sparks are quite similar at all test depolarizations and at all times during a given depolarization, indicating that the channel open times and conductances underlying sparks are essentially independent of voltage. Thus, the voltage dependence of SR Ca2+ release is due to changes in the frequency and pattern of occurrence of individual, voltage-independent, discrete release events.

Design of compounds that increase the absorption of polar molecules

Hydrophilic drugs are often poorly absorbed when administered orally. There has been considerable interest in the possibility of using absorption enhancers to promote absorption of polar molecules across membrane surfaces. The bile acids are one of the most widely investigated classes of absorption enhancers, but there is disagreement about what features of bile acid enhancers are responsible for their efficacy. We have designed a class of glycosylated bile acid derivatives to evaluate how increasing the hydrophilicity of the steroid nucleus affects the ability to transport polar molecules across membranes. Some of the glycosylated molecules are significantly more effective than taurocholate in promoting the intestinal absorption of a range of drugs, showing that hydrophobicity is not a critical parameter in transport efficacy, as previously suggested. Furthermore, the most effective glycosylated compound is also far less damaging to membranes than the best bile acid absorption promoters, presumably because it is more hydrophilic. The results reported here show that it is possible to decouple absorption-promoting activity from membrane damage, a finding that should spark interest in the design of new compounds to facilitate the delivery of polar drugs.

Investigação da estabilidade de fases da zircônia-escândia

Nesse trabalho foi proposto investigar a estabilidade de fases do sistema zircônia-escândia (ScSZ) por meio do estudo termodinâmico de nanopartículas, na faixa de 0 a 20% em mol de Sc2O3, e a partir da introdução de um segundo aditivo (Dy2O3 e Nb2O5) ao ZrO2 contendo 10% em mol de Sc2O3 (10ScSZ). A estabilidade de fases do ScSZ foi avaliada com base em dados termodinâmicos determinados pelas técnicas de microcalorimetria de adsorção de água e calorimetria de dissolução à alta temperatura. As soluções sólidas foram sintetizadas pelo método de coprecipitação de hidróxidos. Dados termodinâmicos foram determinados para as formas polimórficas encontradas (monoclínica, tetragonal, cúbica, romboédrica β e γ) por difração de raios X no ScSZ. Esse trabalho resultou no diagrama de fases em nanoescala de tamanho de partícula-composição. Os efeitos produzidos pela introdução de aditivos na matriz de 10ScSZ foram investigados visando obter a possível estabilização da estrutura cúbica (c) e a supressão da transformação de fase c-β, característica do sistema binário. As composições foram sintetizadas por coprecipitação de hidróxidos e por reações em estado sólido para fins comparativos. Os materiais foram sinterizados convencionalmente e por sinterização assistida por campo elétrico. A estabilização completa da fase cúbica ocorreu a partir de teores molares de 1% de Dy2O3 e 0,5% de Nb2O5. O menor teor de Nb2O5 necessário para a estabilização da fase foi atribuído à provável formação da fase líquida durante a sinterização e ao menor tamanho do íon Nb5+. Os resultados de difratometria de raios X em alta temperatura e análise térmica mostraram que houve supressão da transição c-β. As amostras contendo 0,5% mol de Nb2O5 apresentaram valores de condutividade iônica similares aos do 10ScSZ sem aditivos em uma ampla faixa de temperatura com elevada estabilidade em um período de 170 h a 600 °C.