Oxygen photo-adsorption related quenching of photoluminescence in group-III nitride nanocolumns

GaN and InGaN nanocolumns of various compositions are studied by room-temperature photoluminescence (PL) under different ambient conditions. GaN nanocolumns exhibit a reversible quenching upon exposure to air under constant UV excitation, following a t−1/2 time dependence and resulting in a total reduction of intensity by 85–90%, as compared to PL measured in vacuum, with no spectral change. This effect is not observed when exposing the samples to pure nitrogen. We attribute this effect to photoabsorption and photodesorption of oxygen that modifies the surface potential bending. InGaN nanocolumns, under the same experimental conditions do not show the same quenching features: The high-energy part of the broad PL line is not modified by exposure to air, whereas a lower-energy part, which does quench by 80–90%, can now be distinguished. We discuss the different behaviors in terms of carrier localization and possible composition or strain gradients in the InGaN nanocolumns.

Problem-based learning supported by semantic techniques

Problem-based learning has been applied over the last three decades to a diverse range of learning environments. In this educational approach, different problems are posed to the learners so that they can develop different solutions while learning about the problem domain. When applied to conceptual modelling, and particularly to Qualitative Reasoning, the solutions to problems are models that represent the behaviour of a dynamic system. The learner?s task then is to bridge the gap between their initial model, as their first attempt to represent the system, and the target models that provide solutions to that problem. We propose the use of semantic technologies and resources to help in bridging that gap by providing links to terminology and formal definitions, and matching techniques to allow learners to benefit from existing models.

Wheel-Rail Contact Forces in High-Speed Simply Supported Bridges at Resonance

The response of high-speed bridges at resonance, particularly under flexural vibrations, constitutes a subject of research for many scientists and engineers at the moment. The topic is of great interest because, as a matter of fact, such kind of behaviour is not unlikely to happen due to the elevated operating speeds of modern rains, which in many cases are equal to or even exceed 300 km/h ( [1,2]). The present paper addresses the subject of the evolution of the wheel-rail contact forces during resonance situations in simply supported bridges. Based on a dimensionless formulation of the equations of motion presented in [4], very similar to the one introduced by Klasztorny and Langer in [3], a parametric study is conducted and the contact forces in realistic situations analysed in detail. The effects of rail and wheel irregularities are not included in the model. The bridge is idealised as an Euler-Bernoulli beam, while the train is simulated by a system consisting of rigid bodies, springs and dampers. The situations such that a severe reduction of the contact force could take place are identified and compared with typical situations in actual bridges. To this end, the simply supported bridge is excited at resonace by means of a theoretical train consisting of 15 equidistant axles. The mechanical characteristics of all axles (unsprung mass, semi-sprung mass, and primary suspension system) are identical. This theoretical train permits the identification of the key parameters having an influence on the wheel-rail contact forces. In addition, a real case of a 17.5 m bridges traversed by the Eurostar train is analysed and checked against the theoretical results. The influence of three fundamental parameters is investigated in great detail: a) the ratio of the fundamental frequency of the bridge and natural frequency of the primary suspension of the vehicle; b) the ratio of the total mass of the bridge and the semi-sprung mass of the vehicle and c) the ratio between the length of the bridge and the characteristic distance between consecutive axles. The main conclusions derived from the investigation are: The wheel-rail contact forces undergo oscillations during the passage of the axles over the bridge. During resonance, these oscillations are more severe for the rear wheels than for the front ones. If denotes the span of a simply supported bridge, and the characteristic distance between consecutive groups of loads, the lower the value of , the greater the oscillations of the contact forces at resonance. For or greater, no likelihood of loss of wheel-rail contact has been detected. The ratio between the frequency of the primary suspension of the vehicle and the fundamental frequency of the bridge is denoted by (frequency ratio), and the ratio of the semi-sprung mass of the vehicle (mass of the bogie) and the total mass of the bridge is denoted by (mass ratio). For any given frequency ratio, the greater the mass ratio, the greater the oscillations of the contact forces at resonance. The oscillations of the contact forces at resonance, and therefore the likelihood of loss of wheel-rail contact, present a minimum for approximately between 0.5 and 1. For lower or higher values of the frequency ratio the oscillations of the contact forces increase. Neglecting the possible effects of torsional vibrations, the metal or composite bridges with a low linear mass have been found to be the ones where the contact forces may suffer the most severe oscillations. If single-track, simply supported, composite or metal bridges were used in high-speed lines, and damping ratios below 1% were expected, the minimum contact forces at resonance could drop to dangerous values. Nevertheless, this kind of structures is very unusual in modern high-speed railway lines.

AALUMO: a user model ontology for ambient assisted living services supported in next-generation networks

Ambient Assisted Living (AAL) services are emerging as context-awareness solutions to support elderly people?s autonomy. The context-aware paradigm makes applications more user-adaptive. In this way, context and user models expressed in ontologies are employed by applications to describe user and environment characteristics. The rapid advance of technology allows creating context server to relieve applications of context reasoning techniques. Specifically, the Next Generation Networks (NGN) provides by means of the presence service a framework to manage the current user's state as well as the user's profile information extracted from Internet and mobile context. This paper propose a user modeling ontology for AAL services which can be deployed in a NGN environment with the aim at adapting their functionalities to the elderly's context information and state.

A pedagogically-supported TEL solution for learning nontechnical minimally invasive surgical skills across Europe

Residents learning nontechnical skills in Europe face two problems: (1) the difficulty to fit learning time in their overloaded schedules; and (2) the lack of standard pedagogical models for all countries. Online video-based repositories such as WeBSurg or WebOP provide ubiquitous access to surgical contents. However, their pedagogical facets have not been fully exploited and they are often seen as quick-reference repositories rather than full e-learning alternatives. We present a new pedagogically-supported Technology Enhanced Learning (TEL) solution, MISTELA, designed by surgeons, pedagogical experts and engineers. MISTELA aims at building a common European pedagogical model supported by ICT technologies and elearning. The solution proposes a pedagogical model based on a framework for pedagogically-informed design of e-learning platforms. It is composed of (1) an authoring tool for editing and augmenting videos; (2) a media asset management system; and (3) a virtual learning environment. Support of the European Association for Endoscopic Surgery (EAES) and validation of the solution, will help to determine its full potential.

Advances on MBE selective area growth of III-nitride nanostructures: from nanoLEDs to pseudo substrates

The aim of this work is to provide an overview on the recent advances in the selective area growth (SAG) of (In)GaN nanostructures by plasma assisted molecular beam epitaxy, focusing on their potential as building blocks for next generation LEDs. The first three sections deal with the basic growth mechanisms of GaN SAG and the emission control in the entire ultraviolet to infrared range, including approaches for white light emission, using InGaN disks and thick segments on axial nanocolumns. SAG of axial nanostructures is eveloped on both GaN/sapphire templates and GaN-buffered Si(111). As an alternative to axial nanocolumns, section 4 reports on the growth and characterization of InGaN/GaN core-shell structures on an ordered array of top-down patterned GaN microrods. Finally, section 5 reports on the SAG of GaN, with and without InGaN insertion, on semi-polar (11-22) and non-polar (11-20) templates. Upon SAG the high defect density present in the templates is strongly reduced as indicated by a dramatic improvement of the optical properties. In the case of SAG on nonpolar (11-22) templates, the formation of nanostructures with a low aspect ratio took place allowing for the fabrication of high-quality, non-polar GaN pseudo-templates by coalescence of these nanostructures.

Self assembled and ordered group III nitride nanocolumnar structures for light emitting applications

El objetivo de este trabajo es un estudio profundo del crecimiento selectivo de nanoestructuras de InGaN por epitaxia de haces moleculares asistido por plasma, concentrandose en el potencial de estas estructuras como bloques constituyentes en LEDs de nueva generación. Varias aproximaciones al problema son discutidas; desde estructuras axiales InGaN/GaN, a estructuras core-shell, o nanoestructuras crecidas en sustratos con orientaciones menos convencionales (semi polar y no polar). La primera sección revisa los aspectos básicos del crecimiento auto-ensamblado de nanocolumnas de GaN en sustratos de Si(111). Su morfología y propiedades ópticas son comparadas con las de capas compactas de GaN sobre Si(111). En el caso de las columnas auto-ensambladas de InGaN sobre Si(111), se presentan resultados sobre el efecto de la temperatura de crecimiento en la incorporación de In. Por último, se discute la inclusión de nanodiscos de InGaN en las nanocolumnas de GaN. La segunda sección revisa los mecanismos básicos del crecimiento ordenado de nanoestructuras basadas en GaN, sobre templates de GaN/zafiro. Aumentando la relación III/V localmente, se observan cambios morfológicos; desde islas piramidales, a nanocolumnas de GaN terminadas en planos semipolares, y finalmente, a nanocolumnas finalizadas en planos c polares. Al crecer nanodiscos de InGaN insertados en las nanocolumnas de GaN, las diferentes morfologias mencionadas dan lugar a diferentes propiedades ópticas de los nanodiscos, debido al diferente carácter (semi polar o polar) de los planos cristalinos involucrados. La tercera sección recoge experimentos acerca de los efectos que la temperatura de crecimiento y la razón In/Ga tienen en la morfología y emisión de nanocolumnas ordenadas de InGaN crecidas sobre templates GaN/zafiro. En el rango de temperaturas entre 650 y 750 C, la incorporacion de In puede modificarse bien por la temperatura de crecimiento, o por la razón In/Ga. Controlar estos factores permite la optimización de la longitud de onda de emisión de las nanocolumnas de InGaN. En el caso particular de la generación de luz blanca, se han seguidos dos aproximaciones. En la primera, se obtiene emisión amarilla-blanca a temperatura ambiente de nanoestructuras donde la región de InGaN consiste en un gradiente de composiciones de In, que se ha obtenido a partir de un gradiente de temperatura durante el crecimiento. En la segunda, el apilamiento de segmentos emitiendo en azul, verde y rojo, consiguiendo la integración monolítica de estas estructuras en cada una de las nanocolumnas individuales, da lugar a emisores ordenados con un amplio espectro de emisión. En esta última aproximación, la forma espectral puede controlarse con la longitud (duración del crecimiento) de cada uno de los segmentos de InGaN. Más adelante, se presenta el crecimiento ordenado, por epitaxia de haces moleculares, de arrays de nanocolumnas que son diodos InGaN/GaN cada una de ellas, emitiendo en azul (441 nm), verde (502 nm) y amarillo (568 nm). La zona activa del dispositivo consiste en una sección de InGaN, de composición constante nominalmente y longitud entre 250 y 500 nm, y libre de defectos extendidos en contraste con capas compactas de InGaN de similares composiciones y espesores. Los espectros de electroluminiscencia muestran un muy pequeño desplazamiento al azul al aumentar la corriente inyectada (desplazamiento casi inexistente en el caso del dispositivo amarillo), y emisiones ligeramente más anchas que en el caso del estado del arte en pozos cuánticos de InGaN. A continuación, se presenta y discute el crecimiento ordenado de nanocolumnas de In(Ga)N/GaN en sustratos de Si(111). Nanocolumnas ordenadas emitiendo desde el ultravioleta (3.2 eV) al infrarrojo (0.78 eV) se crecieron sobre sustratos de Si(111) utilizando una capa compacta (“buffer”) de GaN. La morfología y eficiencia de emisión de las nanocolumnas emitiendo en el rango espectral verde pueden ser mejoradas ajustando las relaciones In/Ga y III/N, y una eficiencia cuántica interna del 30% se deriva de las medidas de fotoluminiscencia en nanocolumnas optimizadas. En la siguiente sección de este trabajo se presenta en detalle el mecanismo tras el crecimiento ordenado de nanocolumnas de InGaN/GaN emitiendo en el verde, y sus propiedades ópticas. Nanocolumnas de InGaN/GaN con secciones largas de InGaN (330-830 nm) se crecieron tanto en sustratos GaN/zafiro como GaN/Si(111). Se encuentra que la morfología y la distribución espacial del In dentro de las nanocolumnas dependen de las relaciones III/N e In/Ga locales en el frente de crecimiento de las nanocolumnas. La dispersión en el contenido de In entre diferentes nanocolumnas dentro de la misma muestra es despreciable, como indica las casi identicas formas espectrales de la catodoluminiscencia de una sola nanocolumna y del conjunto de ellas. Para las nanocolumnas de InGaN/GaN crecidas sobre GaN/Si(111) y emitiendo en el rango espectral verde, la eficiencia cuántica interna aumenta hasta el 30% al disminuir la temperatura de crecimiento y aumentar el nitrógeno activo. Este comportamiento se debe probablemente a la formación de estados altamente localizados, como indica la particular evolución de la energía de fotoluminiscencia con la temperatura (ausencia de “s-shape”) en muestras con una alta eficiencia cuántica interna. Por otro lado, no se ha encontrado la misma dependencia entre condiciones de crecimiento y efiencia cuántica interna en las nanoestructuras InGaN/GaN crecidas en GaN/zafiro, donde la máxima eficiencia encontrada ha sido de 3.7%. Como alternativa a las nanoestructuras axiales de InGaN/GaN, la sección 4 presenta resultados sobre el crecimiento y caracterización de estructuras core-shell de InGaN/GaN, re-crecidas sobre arrays de micropilares de GaN fabricados por ataque de un template GaN/zafiro (aproximación top-down). El crecimiento de InGaN/GaN es conformal, con componentes axiales y radiales en el crecimiento, que dan lugar a la estructuras core-shell con claras facetas hexagonales. El crecimiento radial (shell) se ve confirmado por medidas de catodoluminiscencia con resolución espacial efectuadas en un microscopio electrónico de barrido, asi como por medidas de microscopía de transmisión de electrones. Más adelante, el crecimiento de micro-pilares core-shell de InGaN se realizó en pilares GaN (cores) crecidos selectivamente por epitaxia de metal-orgánicos en fase vapor. Con el crecimiento de InGaN se forman estructuras core-shell con emisión alrededor de 3 eV. Medidas de catodoluminiscencia resuelta espacialmente indican un aumento en el contenido de indio del shell en dirección a la parte superior del pilar, que se manifiesta en un desplazamiento de la emisión de 3.2 eV en la parte inferior, a 3.0 eV en la parte superior del shell. Este desplazamiento está relacionado con variaciones locales de la razón III/V en las facetas laterales. Finalmente, se demuestra la fabricación de una estructura pin basada en estos pilares core-shell. Medidas de electroluminiscencia resuelta espacialmente, realizadas en pilares individuales, confirman que la electroluminiscencia proveniente del shell de InGaN (diodo lateral) está alrededor de 3.0 eV, mientras que la emisión desde la parte superior del pilar (diodo axial) está alrededor de 2.3 eV. Para finalizar, se presentan resultados sobre el crecimiento ordenado de GaN, con y sin inserciones de InGaN, en templates semi polares (GaN(11-22)/zafiro) y no polares (GaN(11-20)/zafiro). Tras el crecimiento ordenado, gran parte de los defectos presentes en los templates originales se ven reducidos, manifestándose en una gran mejora de las propiedades ópticas. En el caso de crecimiento selectivo sobre templates con orientación GaN(11-22), no polar, la formación de nanoestructuras con una particular morfología (baja relación entre crecimiento perpedicular frente a paralelo al plano) permite, a partir de la coalescencia de estas nanoestructuras, la fabricación de pseudo-templates no polares de GaN de alta calidad. ABSTRACT The aim of this work is to gain insight into the selective area growth of InGaN nanostructures by plasma assisted molecular beam epitaxy, focusing on their potential as building blocks for next generation LEDs. Several nanocolumn-based approaches such as standard axial InGaN/GaN structures, InGaN/GaN core-shell structures, or InGaN/GaN nanostructures grown on semi- and non-polar substrates are discussed. The first section reviews the basics of the self-assembled growth of GaN nanocolumns on Si(111). Morphology differences and optical properties are compared to those of GaN layer grown directly on Si(111). The effects of the growth temperature on the In incorporation in self-assembled InGaN nanocolumns grown on Si(111) is described. The second section reviews the basic growth mechanisms of selectively grown GaNbased nanostructures on c-plane GaN/sapphire templates. By increasing the local III/V ratio morphological changes from pyramidal islands, to GaN nanocolumns with top semi-polar planes, and further to GaN nanocolumns with top polar c-planes are observed. When growing InGaN nano-disks embedded into the GaN nanocolumns, the different morphologies mentioned lead to different optical properties, due to the semipolar and polar nature of the crystal planes involved. The third section reports on the effect of the growth temperature and In/Ga ratio on the morphology and light emission characteristics of ordered InGaN nanocolumns grown on c-plane GaN/sapphire templates. Within the growth temperature range of 650 to 750oC the In incorporation can be modified either by the growth temperature, or the In/Ga ratio. Control of these factors allows the optimization of the InGaN nanocolumns light emission wavelength. In order to achieve white light emission two approaches are used. First yellow-white light emission can be obtained at room temperature from nanostructures where the InGaN region is composition-graded by using temperature gradients during growth. In a second approach the stacking of red, green and blue emitting segments was used to achieve the monolithic integration of these structures in one single InGaN nanocolumn leading to ordered broad spectrum emitters. With this approach, the spectral shape can be controlled by changing the thickness of the respective InGaN segments. Furthermore the growth of ordered arrays of InGaN/GaN nanocolumnar light emitting diodes by molecular beam epitaxy, emitting in the blue (441 nm), green (502 nm), and yellow (568 nm) spectral range is reported. The device active region, consisting of a nanocolumnar InGaN section of nominally constant composition and 250 to 500 nm length, is free of extended defects, which is in strong contrast to InGaN layers (planar) of similar composition and thickness. Electroluminescence spectra show a very small blue shift with increasing current, (almost negligible in the yellow device) and line widths slightly broader than those of state-of-the-art InGaN quantum wells. Next the selective area growth of In(Ga)N/GaN nanocolumns on Si(111) substrates is discussed. Ordered In(Ga)N/GaN nanocolumns emitting from ultraviolet (3.2 eV) to infrared (0.78 eV) were then grown on top of GaN-buffered Si substrates. The morphology and the emission efficiency of the In(Ga)N/GaN nanocolumns emitting in the green could be substantially improved by tuning the In/Ga and total III/N ratios, where an estimated internal quantum efficiency of 30 % was derived from photoluminescence data. In the next section, this work presents a study on the selective area growth mechanisms of green-emitting InGaN/GaN nanocolumns and their optical properties. InGaN/GaN nanocolumns with long InGaN sections (330-830nm) were grown on GaN/sapphire and GaN-buffered Si(111). The nanocolumn’s morphology and spatial indium distribution is found to depend on the local group (III)/N and In/Ga ratios at the nanocolumn’s top. A negligible spread of the average indium incorporation among different nanostructures is found as indicated by similar shapes of the cathodoluminescence spectra taken from single nanocolumns and ensembles of nanocolumns. For InGaN/GaN nanocolumns grown on GaN-buffered Si(111), all emitting in the green spectral range, the internal quantum efficiency increases up to 30% when decreasing growth temperature and increasing active nitrogen. This behavior is likely due to the formation of highly localized states, as indicated by the absence of a complete s-shape behavior of the PL peak position with temperature (up to room temperature) in samples with high internal quantum efficiency. On the other hand, no dependence of the internal quantum efficiency on the growth conditions is found for InGaN/GaN nanostructures grown on GaN/sapphire, where the maximum achieved efficiency is 3.7%. As alternative to axial InGaN/GaN nanostructures, section 4 reports on the growth and characterization of InGaN/GaN core-shell structures on an ordered array of top-down patterned GaN microrods etched from a GaN/sapphire template. Growth of InGaN/GaN is conformal, with axial and radial growth components leading to core-shell structures with clear hexagonal facets. The radial InGaN growth (shell) is confirmed by spatially resolved cathodoluminescence performed in a scanning electron microscopy as well as in scanning transmission electron microscopy. Furthermore the growth of InGaN core-shell micro pillars using an ordered array of GaN cores grown by metal organic vapor phase epitaxy as a template is demonstrated. Upon InGaN overgrowth core-shell structures with emission at around 3.0 eV are formed. With spatially resolved cathodoluminescence, an increasing In content towards the pillar top is found to be present in the InGaN shell, as indicated by a shift of CL peak position from 3.2 eV at the shell bottom to 3.0 eV at the shell top. This shift is related to variations of the local III/V ratio at the side facets. Further, the successful fabrication of a core-shell pin diode structure is demonstrated. Spatially resolved electroluminescence measurements performed on individual micro LEDs, confirm emission from the InGaN shell (lateral diode) at around 3.0 eV, as well as from the pillar top facet (axial diode) at around 2.3 eV. Finally, this work reports on the selective area growth of GaN, with and without InGaN insertion, on semi-polar (11-22) and non-polar (11-20) templates. Upon SAG the high defect density present in the GaN templates is strongly reduced as indicated by TEM and a dramatic improvement of the optical properties. In case of SAG on non-polar (11-22) templates the formation of nanostructures with a low aspect ratio took place allowing for the fabrication of high-quality, non-polar GaN pseudo-templates by coalescence of the nanostructures.

Evaluation of configurations of supply networks supported by it systems

Los sistemas transaccionales tales como los programas informáticos para la planificación de recursos empresariales (ERP software) se han implementado ampliamente mientras que los sistemas analíticos para la gestión de la cadena de suministro (SCM software) no han tenido el éxito deseado por la industria de tecnología de información (TI). Aunque se documentan beneficios importantes derivados de las implantaciones de SCM software, las empresas industriales son reacias a invertir en este tipo de sistemas. Por una parte esto es debido a la falta de métodos que son capaces de detectar los beneficios por emplear esos sistemas, y por otra parte porque el coste asociado no está identificado, detallado y cuantificado suficientemente. Los esquemas de coordinación basados únicamente en sistemas ERP son alternativas válidas en la práctica industrial siempre que la relación coste-beneficio esta favorable. Por lo tanto, la evaluación de formas organizativas teniendo en cuenta explícitamente el coste debido a procesos administrativos, en particular por ciclos iterativos, es de gran interés para la toma de decisiones en el ámbito de inversiones en TI. Con el fin de cerrar la brecha, el propósito de esta investigación es proporcionar métodos de evaluación que permitan la comparación de diferentes formas de organización y niveles de soporte por sistemas informáticos. La tesis proporciona una amplia introducción, analizando los retos a los que se enfrenta la industria. Concluye con las necesidades de la industria de SCM software: unas herramientas que facilitan la evaluación integral de diferentes propuestas de organización. A continuación, la terminología clave se detalla centrándose en la teoría de la organización, las peculiaridades de inversión en TI y la tipología de software de gestión de la cadena de suministro. La revisión de la literatura clasifica las contribuciones recientes sobre la gestión de la cadena de suministro, tratando ambos conceptos, el diseño de la organización y su soporte por las TI. La clasificación incluye criterios relacionados con la metodología de la investigación y su contenido. Los estudios empíricos en el ámbito de la administración de empresas se centran en tipologías de redes industriales. Nuevos algoritmos de planificación y esquemas de coordinación innovadoras se desarrollan principalmente en el campo de la investigación de operaciones con el fin de proponer nuevas funciones de software. Artículos procedentes del área de la gestión de la producción se centran en el análisis de coste y beneficio de las implantaciones de sistemas. La revisión de la literatura revela que el éxito de las TI para la coordinación de redes industriales depende en gran medida de características de tres dimensiones: la configuración de la red industrial, los esquemas de coordinación y las funcionalidades del software. La literatura disponible está enfocada sobre todo en los beneficios de las implantaciones de SCM software. Sin embargo, la coordinación de la cadena de suministro, basándose en el sistema ERP, sigue siendo la práctica industrial generalizada, pero el coste de coordinación asociado no ha sido abordado por los investigadores. Los fundamentos de diseño organizativo eficiente se explican en detalle en la medida necesaria para la comprensión de la síntesis de las diferentes formas de organización. Se han generado varios esquemas de coordinación variando los siguientes parámetros de diseño: la estructura organizativa, los mecanismos de coordinación y el soporte por TI. Las diferentes propuestas de organización desarrolladas son evaluadas por un método heurístico y otro basado en la simulación por eventos discretos. Para ambos métodos, se tienen en cuenta los principios de la teoría de la organización. La falta de rendimiento empresarial se debe a las dependencias entre actividades que no se gestionan adecuadamente. Dentro del método heurístico, se clasifican las dependencias y se mide su intensidad basándose en factores contextuales. A continuación, se valora la idoneidad de cada elemento de diseño organizativo para cada dependencia específica. Por último, cada forma de organización se evalúa basándose en la contribución de los elementos de diseño tanto al beneficio como al coste. El beneficio de coordinación se refiere a la mejora en el rendimiento logístico - este concepto es el objeto central en la mayoría de modelos de evaluación de la gestión de la cadena de suministro. Por el contrario, el coste de coordinación que se debe incurrir para lograr beneficios no se suele considerar en detalle. Procesos iterativos son costosos si se ejecutan manualmente. Este es el caso cuando SCM software no está implementada y el sistema ERP es el único instrumento de coordinación disponible. El modelo heurístico proporciona un procedimiento simplificado para la clasificación sistemática de las dependencias, la cuantificación de los factores de influencia y la identificación de configuraciones que indican el uso de formas organizativas y de soporte de TI más o menos complejas. La simulación de eventos discretos se aplica en el segundo modelo de evaluación utilizando el paquete de software ‘Plant Simulation’. Con respecto al rendimiento logístico, por un lado se mide el coste de fabricación, de inventario y de transporte y las penalizaciones por pérdida de ventas. Por otro lado, se cuantifica explícitamente el coste de la coordinación teniendo en cuenta los ciclos de coordinación iterativos. El método se aplica a una configuración de cadena de suministro ejemplar considerando diversos parámetros. Los resultados de la simulación confirman que, en la mayoría de los casos, el beneficio aumenta cuando se intensifica la coordinación. Sin embargo, en ciertas situaciones en las que se aplican ciclos de planificación manuales e iterativos el coste de coordinación adicional no siempre conduce a mejor rendimiento logístico. Estos resultados inesperados no se pueden atribuir a ningún parámetro particular. La investigación confirma la gran importancia de nuevas dimensiones hasta ahora ignoradas en la evaluación de propuestas organizativas y herramientas de TI. A través del método heurístico se puede comparar de forma rápida, pero sólo aproximada, la eficiencia de diferentes formas de organización. Por el contrario, el método de simulación es más complejo pero da resultados más detallados, teniendo en cuenta parámetros específicos del contexto del caso concreto y del diseño organizativo. ABSTRACT Transactional systems such as Enterprise Resource Planning (ERP) systems have been implemented widely while analytical software like Supply Chain Management (SCM) add-ons are adopted less by manufacturing companies. Although significant benefits are reported stemming from SCM software implementations, companies are reluctant to invest in such systems. On the one hand this is due to the lack of methods that are able to detect benefits from the use of SCM software and on the other hand associated costs are not identified, detailed and quantified sufficiently. Coordination schemes based only on ERP systems are valid alternatives in industrial practice because significant investment in IT can be avoided. Therefore, the evaluation of these coordination procedures, in particular the cost due to iterations, is of high managerial interest and corresponding methods are comprehensive tools for strategic IT decision making. The purpose of this research is to provide evaluation methods that allow the comparison of different organizational forms and software support levels. The research begins with a comprehensive introduction dealing with the business environment that industrial networks are facing and concludes highlighting the challenges for the supply chain software industry. Afterwards, the central terminology is addressed, focusing on organization theory, IT investment peculiarities and supply chain management software typology. The literature review classifies recent supply chain management research referring to organizational design and its software support. The classification encompasses criteria related to research methodology and content. Empirical studies from management science focus on network types and organizational fit. Novel planning algorithms and innovative coordination schemes are developed mostly in the field of operations research in order to propose new software features. Operations and production management researchers realize cost-benefit analysis of IT software implementations. The literature review reveals that the success of software solutions for network coordination depends strongly on the fit of three dimensions: network configuration, coordination scheme and software functionality. Reviewed literature is mostly centered on the benefits of SCM software implementations. However, ERP system based supply chain coordination is still widespread industrial practice but the associated coordination cost has not been addressed by researchers. Fundamentals of efficient organizational design are explained in detail as far as required for the understanding of the synthesis of different organizational forms. Several coordination schemes have been shaped through the variation of the following design parameters: organizational structuring, coordination mechanisms and software support. The different organizational proposals are evaluated using a heuristic approach and a simulation-based method. For both cases, the principles of organization theory are respected. A lack of performance is due to dependencies between activities which are not managed properly. Therefore, within the heuristic method, dependencies are classified and their intensity is measured based on contextual factors. Afterwards the suitability of each organizational design element for the management of a specific dependency is determined. Finally, each organizational form is evaluated based on the contribution of the sum of design elements to coordination benefit and to coordination cost. Coordination benefit refers to improvement in logistic performance – this is the core concept of most supply chain evaluation models. Unfortunately, coordination cost which must be incurred to achieve benefits is usually not considered in detail. Iterative processes are costly when manually executed. This is the case when SCM software is not implemented and the ERP system is the only available coordination instrument. The heuristic model provides a simplified procedure for the classification of dependencies, quantification of influence factors and systematic search for adequate organizational forms and IT support. Discrete event simulation is applied in the second evaluation model using the software package ‘Plant Simulation’. On the one hand logistic performance is measured by manufacturing, inventory and transportation cost and penalties for lost sales. On the other hand coordination cost is explicitly considered taking into account iterative coordination cycles. The method is applied to an exemplary supply chain configuration considering various parameter settings. The simulation results confirm that, in most cases, benefit increases when coordination is intensified. However, in some situations when manual, iterative planning cycles are applied, additional coordination cost does not always lead to improved logistic performance. These unexpected results cannot be attributed to any particular parameter. The research confirms the great importance of up to now disregarded dimensions when evaluating SCM concepts and IT tools. The heuristic method provides a quick, but only approximate comparison of coordination efficiency for different organizational forms. In contrast, the more complex simulation method delivers detailed results taking into consideration specific parameter settings of network context and organizational design.

Diversity and phylogeny of gephyrin: Tissue-specific splice variants, gene structure, and sequence similarities to molybdenum cofactor-synthesizing and cytoskeleton-associated proteins

Gephyrin is essential for both the postsynaptic localization of inhibitory neurotransmitter receptors in the central nervous system and the biosynthesis of the molybdenum cofactor (Moco) in different peripheral organs. Several alternatively spliced gephyrin transcripts have been identified in rat brain that differ in their 5′ coding regions. Here, we describe gephyrin splice variants that are differentially expressed in non-neuronal tissues and different regions of the adult mouse brain. Analysis of the murine gephyrin gene indicates a highly mosaic organization, with eight of its 29 exons corresponding to the alternatively spliced regions identified by cDNA sequencing. The N- and C-terminal domains of gephyrin encoded by exons 3–7 and 16–29, respectively, display sequence similarities to bacterial, invertebrate, and plant proteins involved in Moco biosynthesis, whereas the central exons 8, 13, and 14 encode motifs that may mediate oligomerization and tubulin binding. Our data are consistent with gephyrin having evolved from a Moco biosynthetic protein by insertion of protein interaction sequences.

Electric field-induced reorganization of two-component supported bilayer membranes

Application of electric fields tangent to the plane of a confined patch of fluid bilayer membrane can create lateral concentration gradients of the lipids. A thermodynamic model of this steady-state behavior is developed for binary systems and tested with experiments in supported lipid bilayers. The model uses Flory’s approximation for the entropy of mixing and allows for effects arising when the components have different molecular areas. In the special case of equal area molecules the concentration gradient reduces to a Fermi–Dirac distribution. The theory is extended to include effects from charged molecules in the membrane. Calculations show that surface charge on the supporting substrate substantially screens electrostatic interactions within the membrane. It also is shown that concentration profiles can be affected by other intermolecular interactions such as clustering. Qualitative agreement with this prediction is provided by comparing phosphatidylserine- and cardiolipin-containing membranes.

The chaperone GroEL is required for the final assembly of the molybdenum-iron protein of nitrogenase

It is known that an E146D site-directed variant of the Azotobacter vinelandii iron protein (Fe protein) is specifically defective in its ability to participate in iron-molybdenum cofactor (FeMoco) insertion. Molybdenum-iron protein (MoFe protein) from the strain expressing the E146D Fe protein is partially (≈45%) FeMoco deficient. The “free” FeMoco that is not inserted accumulates in the cell. We were able to insert this “free” FeMoco into the partially pure FeMoco-deficient MoFe protein. This insertion reaction required crude extract of the ΔnifHDK A. vinelandii strain CA12, Fe protein and MgATP. We used this as an assay to purify a required “insertion” protein. The purified protein was identified as GroEL, based on the molecular mass of its subunit (58.8 kDa), crossreaction with commercially available antibodies raised against E. coli GroEL, and its NH2-terminal polypeptide sequence. The NH2-terminal polypeptide sequence showed identity of up to 84% to GroEL from various organisms. Purified GroEL of A. vinelandii alone or in combination with MgATP and Fe protein did not support the FeMoco insertion into pure FeMoco-deficient MoFe protein, suggesting that there are still other proteins and/or factors missing. By using GroEL-containing extracts from a ΔnifHDK strain of A. vinelandii CA12 along with FeMoco, Fe protein, and MgATP, we were able to supply all required proteins and/or factors and obtained a fully active reconstituted E146D nifH MoFe protein. The involvement of the molecular chaperone GroEL in the insertion of a metal cluster into an apoprotein may have broad implications for the maturation of other metalloenzymes.

Formation of a Normal Epidermis Supported by Increased Stability of Keratins 5 and 14 in Keratin 10 Null Mice

The expression of distinct keratin pairs during epidermal differentiation is assumed to fulfill specific and essential cytoskeletal functions. This is supported by a great variety of genodermatoses exhibiting tissue fragility because of keratin mutations. Here, we show that the loss of K10, the most prominent epidermal protein, allowed the formation of a normal epidermis in neonatal mice without signs of fragility or wound-healing response. However, there were profound changes in the composition of suprabasal keratin filaments. K5/14 persisted suprabasally at elevated protein levels, whereas their mRNAs remained restricted to the basal keratinocytes. This indicated a novel mechanism regulating keratin turnover. Moreover, the amount of K1 was reduced. In the absence of its natural partner we observed the formation of a minor amount of novel K1/14/15 filaments as revealed by immunogold electron microscopy. We suggest that these changes maintained epidermal integrity. Furthermore, suprabasal keratinocytes contained larger keratohyalin granules similar to our previous K10T mice. A comparison of profilaggrin processing in K10T and K10−/− mice revealed an accumulation of filaggrin precursors in the former but not in the latter, suggesting a requirement of intact keratin filaments for the processing. The mild phenotype of K10−/− mice suggests that there is a considerable redundancy in the keratin gene family.

Dendrimer-supported combinatorial chemistry.

A new methodology for the construction of combinatorial libraries is described. The approach, termed dendrimer-supported combinatorial chemistry (DCC), centers on the use of dendrimers as soluble supports. Salient features of DCC include solution phase chemistry, homogeneous purification, routine characterization of intermediates, and high support loadings. To demonstrate the feasibility of DCC, single compounds and a small combinatorial library were prepared via the Fischer indole synthesis. Excellent product yields and purities were obtained, and dendrimer-protected intermediates could be routinely analyzed by 1H and 13C NMR and by mass spectrometry. The results indicate that DCC is a general and efficient strategy for the generation of combinatorial libraries.

A structure-based catalytic mechanism for the xanthine oxidase family of molybdenum enzymes.

The crystal structure of the xanthine oxidase-related molybdenum-iron protein aldehyde oxido-reductase from the sulfate reducing anaerobic Gram-negative bacterium Desulfovibrio gigas (Mop) was analyzed in its desulfo-, sulfo-, oxidized, reduced, and alcohol-bound forms at 1.8-A resolution. In the sulfo-form the molybdenum molybdopterin cytosine dinucleotide cofactor has a dithiolene-bound fac-[Mo, = O, = S, ---(OH2)] substructure. Bound inhibitory isopropanol in the inner compartment of the substrate binding tunnel is a model for the Michaelis complex of the reaction with aldehydes (H-C = O,-R). The reaction is proposed to proceed by transfer of the molybdenum-bound water molecule as OH- after proton transfer to Glu-869 to the carbonyl carbon of the substrate in concert with hydride transfer to the sulfido group to generate [MoIV, = O, -SH, ---(O-C = O, -R)). Dissociation of the carboxylic acid product may be facilitated by transient binding of Glu-869 to the molybdenum. The metal-bound water is replenished from a chain of internal water molecules. A second alcohol binding site in the spacious outer compartment may cause the strong substrate inhibition observed. This compartment is the putative binding site of large inhibitors of xanthine oxidase.

Síntese de óxidos metálicos binários suportados em carbono amorfo (printex 6L) para a produção eletroquímica de peróxido de hidrogênio (H2O2)

O presente trabalho visa o estudo da eletrossíntese de H2O2 a partir da reação de redução de oxigênio (RRO) utilizando carbono Printex 6L modificado com óxidos binários compostos de nióbio, molibdênio e paládio, síntetizados pelo método dos precursores poliméricos. A análise dos materiais preparados foi feita a partir de experimentos de análise termogravimétrica (do inglês, TGA), fluorescência de raios X (FRX) e também de difração de raios X (DRX). As temperaturas de síntese foram escolhidas a partir dos resultados de TGA e tendo como temperatura máxima de 400 °C. As análises dos espectros de emissão de FRX mostraram a eficiência na incorporação dos materiais na matriz de carbono. Experimentos de DRX mostraram a presença de fases cristalinas de MoO2 e Nb2 O5 e PdO, e em comparação aos resultados da técnica de voltametria cíclica, existem pares redox que podem ser associados as transições dos metais nos estados de oxidação de +4 e +5, para molibdênio e nióbio, respectivamente e do estado +2 para o paládio. Nos experimentos de voltametria de varredura linear pode-se observar a tendência de maior geração de H2O2 pelo material com teor de 1% NbMo quando comparado com o carbono Printex 6L, de modo que foram calculadas as eficiências de geração de H2O2 , obtendo um resultado de 55,5% para o modificador de 1% NbMo comparado com 47,4% para o Printex 6L, e também de número de elétrons envolvidos na reação com um valor de 2,9 para o material de 1% e 3,1 para o carbono Printex. As análises das curvas de Koutechy-Levich confirmam os resultados anteriores. Análises em condições reduzidas na síntese orgânica corroboraram a melhor eficiência do material de 1% para o material com nióbio e molibdênio e revelaram a também a melhora eletrocatalítica do carbono quando incorporado com óxidos mistos de nióbio e paládio, sendo o melhor resultado expresso no material contendo 5% de nióbio e paládio, na proporção molar de 95 para 5% de cada elemento, respectivamente.