Numerical modeling of the failure mechanisms in Si thin film anode for Li-ion batteries

In recent times, the demand for the storage of electrical energy has grown rapidly for both static applications and the portable electronics enforcing the substantial improvement in battery systems, and Li-ion batteries have been proven to have maximum energy storage density in all rechargeable batteries. However, major breakthroughs are required to consummate the requirement of higher energy density with lower cost to penetrate new markets. Graphite anode having limited capacity has become a bottle neck in the process of developing next generation batteries and can be replaced by higher capacity metals such as Silicon. In the present study we are focusing on the mechanical behavior of the Si-thin film anode under various operating conditions. A numerical model is developed to simulate the intercalation induced stress and the failure mechanism of the complex anode structure. Effect of the various physical phenomena such as diffusion induced stress, plasticity and the crack propagation are investigated to predict better performance parameters for improved design.

Specimen specific parameter identification of ovine lumbar intervertebral discs: On the influence of fibre-matrix and fibre-fibre shear interactions.

Numerical models of the intervertebral disc, which address mechanical questions commonly make use of the difference in water content between annulus and nucleus, and thus fluid and solid parts are separated. Despite this simplification, models remain complex due to the anisotropy and nonlinearity of the annulus and regional variations of the collagen fibre density. Additionally, it has been shown that cross-links make a large contribution to the stiffness of the annulus. Because of this complex composite structure, it is difficult to reproduce several sets of experimental data with one single set of material parameters. This study addresses the question to which extent the ultrastructure of the intervertebral disc should be modelled so that its moment-angle behaviour can be adequately described. Therefore, a hyperelastic constitutive law, based on continuum mechanical principles was derived, which does not only consider the anisotropy from the collagen fibres, but also interactions among the fibres and between the fibres and the ground substance. Eight ovine lumbar intervertebral discs were tested on a custom made spinal loading simulator in flexion/extension, lateral bending and axial rotation. Specimen-specific geometrical models were generated using CT images and T2 maps to distinguish between annulus fibrosus and nucleus pulposus. For the identification of the material parameters the annulus fibrosus was described with two scenarios: with and without fibre-matrix and fibre-fibre interactions. Both scenarios showed a similar behaviour on a load displacement level. Comparing model predictions to the experimental data, the mean RMS of all specimens and all load cases was 0.54±0.15° without the interaction and 0.54±0.19° when the fibre-matrix and fibre-fibre interactions were included. However, due to the increased stiffness when cross-links effects were included, this scenario showed more physiological stress-strain relations in uniaxial and biaxial stress states. Thus, the present study suggests that fibre-matrix and fibre-fibre interactions should be considered in the constitutive law when the model addresses questions concerning the stress field of the annulus fibrosus.

INVESTIGATING THE ROLES OF THE p63 ISOFORMS IN THE MICRORNA BIOGENESIS PATHWAY

MicroRNAs play roles in various biological processes like development, tumorigenesis, metastasis and pluripotency. My thesis work has demonstrated roles for p63, a p53 family member, in the upstream regulation of microRNA biogenesis. The p63 gene has a complex gene structure and has multiple isoforms. The TAp63 isoforms contain an acidic transcription activation domain. The ΔNp63 isoforms, lack the TA domain, but have a proline rich region critical for gene transactivation. To understand the functions of these isoforms, the Flores lab generated TAp63 and ΔNp63 conditional knock out mice. Using these mice and tissues and cells from these mice we have found that TAp63 transcriptionally regulates Dicer while ΔNp63 transcriptionally regulates DGCR8. TAp63 -/- mice are highly tumor prone. These mice develop metastatic mammary adenocarcinomas, squamous cell carcinomas, and lung adenocarcinomas to distant sites including the liver, lungs, and brain. I found that TAp63 suppresses metastasis by transcriptionally activating Dicer. TAp63 and Dicer levels were very low or lost in high grade human tumors like mammary adenocarcinomas, squamous cell carcinomas, and lung adenocarcinomas. Expression of Dicer in these tumor cell lines reduced their invasiveness. Using ΔNp63 -/- mice, I found that ΔNp63 transcriptionally activates DGCR8, resulting in a miRNA profile that is critical to reprogram cells to pluripotency. Analysis of epidermal cells derived from ΔNp63 -/- mice revealed that these cells expressed markers of pluripotency, including Sox2, Oct 4 and Nanog; however, genome-wide analysis revealed a novel profile of genes that are common between ΔNp63 -/- epidermal cells and embryonic stem cells. I also found that mouse cells depleted of ΔNp63 form chimeric mice and teratomas in SCID mice, demonstrating that ΔNp63 deficient cells are pluripotent. Further, I found that restoration of DGCR8 in ΔNp63 -/- epidermal cells reduces their pluripotency and induces terminal differentiation. I also demonstrated that iMS (induced multipotent stem) cells could be generated using human keratinocytes by knockdown of ∆Np63 or DGCR8. Taken together, my work has placed p63 and its isoforms at a critical node in controlling miRNA biogenesis.

Preliminary ichthyolith biostratigraphy and age profiles at DSDP Sites 91-595 and 91-596

Seventy meters of Cenozoic and Mesozoic pelagic clay cored at DSDP Sites 595 and 596 provide the basis for a preliminary analysis of ichthyolith biostratigraphy in the southwest Pacific. A most likely order of the more reliable ichthyolith events is compared with a synthesis of ichthyolith biostratigraphy in the North Pacific and with dated composite ranges. The resultant preliminary ichthyolith stratigraphy suggests that the Cenozoic is represented by the upper 20 m at Site 596 and 16 to 22 m at Site 595. Mixing of taxa precludes a clear recognition of the Cretaceous/Tertiary boundary at Site 595. The occurrence of 13 newly described subtypes is recorded in Mesozoic sediments at Sites 595 and 596. These new subtypes and previously described Mesozoic forms may be useful for recognizing Mesozoic subdivisions when their occurrences in sequences dated by other microfossils are investigated.

Cretaceous-Tertiary ichthyoliths of brown clay intervals

The pattern of ichthyolith distribution established in sequences with stratigraphies based on calcareous or siliceous microfossils is used to provide age correlations for three deep-sea pelagic clay intervals that lack the better known microfossils. At Site 637, approximately 25 m of brown clay in Cores 103-637A-21R through 103-637A-23R underlies upper Miocene sediments and is of Paleocene to early Eocene age. At Site 639, 1.7 m of brown clay in Core 103-639C-2R is Eocene to Oligocene. At Site 640, 3.5 m of clay in Cores 103-640A-1R and 103-640A-2R contains a Cretaceous to Paleocene sequence, with the Cretaceous/Tertiary boundary between 84 and 103 cm in Section 103-640A-2R-1.

Results from field observations and in situ 13C feeding experiments in the Nazaré Canyon conducted during RRS James Cook 10 cruise Leg 2

Submarine canyon systems provide a heterogeneous habitat for deep-sea benthos in terms of topography, hydrography, and the quality and quantity of organic matter present. Enhanced meiofauna densities as found in organically enriched canyon sediments suggest that nematodes, as the dominant metazoan meiobenthic taxon, may play an important role in the benthic food web of these sediments. Very little is known about the natural diets and trophic biology of deep-sea nematodes, but enrichment experiments can shed light on nematode feeding selectivity and trophic position. An in-situ pulse-chase experiment (Feedex) was performed in the Nazaré Canyon on the Portuguese margin in summer 2007 to study nematode feeding behaviour. 13C-labelled diatoms and bacteria were added to sediment cores which were then sampled over a 14-day period. There was differential uptake by the nematode community of the food sources provided, indicating selective feeding processes. 13C isotope results revealed that selective feeding was less pronounced at the surface, compared to the sediment subsurface. This was supported by a higher trophic diversity in surface sediments compared to the subsurface, implying that more food items may be used by the nematode community at the sediment surface. Predatory and scavenging nematodes contributed relatively more to biomass than other feeding types and can be seen as key contributors to the nematode food web at the canyon site. Non-selective deposit feeding nematodes were the dominant trophic group in terms of abundance and contributed substantially to total nematode biomass. The high levels of 'fresh' (bioavailable) organic matter input and moderate hydrodynamic disturbance of the canyon environment lead to a more complex trophic structure in canyon nematode communities than that found on the open continental slope, and favours predator/scavengers and non-selective deposit feeders.

Métodos numéricos y estadísticos de caracterización de uniones tubulares soldadas para su aplicación en modelos de elementos finitos de estructuras de vehículos

El análisis de estructuras mediante modelos de elementos finitos representa una de las metodologías más utilizadas y aceptadas en la industria moderna. Para el análisis de estructuras tubulares de grandes dimensiones similares a las sobrestructuras de autobuses y autocares, los elementos de tipo viga son comúnmente utilizados y recomendados debido a que permiten obtener resultados satisfactorios con recursos computacionales reducidos. No obstante, los elementos de tipo viga presentan importante desventaja ya que las uniones modeladas presentan un comportamiento infinitamente rígido, esto determina un comportamiento mas rígido en las estructuras modeladas lo que se traduce en fuentes de error para las simulaciones estructurales (hasta un 60%). Mediante el modelado de uniones tubulares utilizando elementos de tipo área o volumen, se pueden obtener modelos más realistas, ya que las características topológicas de la unión propiamente dicha pueden ser reproducidas con un mayor nivel de detalle. Evitándose de esta manera los inconvenientes de los elementos de tipo viga. A pesar de esto, la modelización de estructuras tubulares de grandes dimensiones con elementos de tipo área o volumen representa una alternativa poco atractiva debido a la complejidad del proceso de modelados y al gran número de elementos resultantes lo que implica la necesidad de grandes recursos computacionales. El principal objetivo del trabajo de investigación presentado, fue el de obtener un nuevo tipo de elemento capaz de proporcionar estimaciones más exactas en el comportamiento de las uniones modeladas, al mismo tiempo manteniendo la simplicidad del procesos de modelado propio de los elementos de tipo viga regular. Con el fin de alcanzar los objetivos planteados, fueron realizadas diferentes metodologías e investigaciones. En base a las investigaciones realizadas, se obtuvo un modelo de unión viga alternativa en el cual se introdujeron un total seis elementos elásticos al nivel de la unión mediante los cuales es posible adaptar el comportamiento local de la misma. Adicionalmente, para la estimación de las rigideces correspondientes a los elementos elásticos se desarrollaron dos metodologías, una primera basada en la caracterización del comportamiento estático de uniones simples y una segunda basada en la caracterización del comportamiento dinámico a través de análisis modales. Las mejoras obtenidas mediante la implementación del modelo de unión alternativa fueron analizadas mediante simulaciones y validación experimental en una estructura tubular compleja representativa de sobrestructuras de autobuses y autocares. En base a los análisis comparativos realizados con la uniones simples modeladas y los experimentos de validación, se determinó que las uniones modeladas con elementos de tipo viga son entre un 5-60% más rígidas que uniones equivalentes modeladas con elementos área o volumen. También se determinó que las uniones área y volumen modeladas son entre un 5 a un 10% mas rígidas en comparación a uniones reales fabricadas. En los análisis realizados en la estructura tubular compleja, se obtuvieron mejoras importantes mediante la implementación del modelo de unión alternativa, las estimaciones del modelo viga se mejoraron desde un 49% hasta aproximadamente un 14%. ABSTRACT The analysis of structures with finite elements models represents one of the most utilized an accepted technique in the modern industry. For the analysis of large tubular structures similar to buses and coaches upper structures, beam type elements are utilized and recommended due to the fact that these elements provide satisfactory results at relatively reduced computational performances. However, the beam type elements have a main disadvantage determined by the fact that the modeled joints have an infinite rigid behavior, this shortcoming determines a stiffer behavior of the modeled structures which translates into error sources for the structural simulations (up to 60%). By modeling tubular junctions with shell and volume elements, more realistic models can be obtained, because the topological characteristics of the junction at the joint level can be reproduced more accurately. This way, the shortcoming that the beam type elements present can be solved. Despite this fact, modeling large tubular structures with shell or volume type elements represents an unattractive alternative due to the complexity of the modeling process and the large number of elements that result which imply the necessity of vast computational performances. The main objective of the research presented in this thesis was to develop a new beam type element that would be able to provide more accurate estimations for the local behavior of the modeled junctions at the same time maintaining the simplicity of the modeling process the regular beam type elements have. In order to reach the established objectives of the research activities, a series of different methodologies and investigations have been necessary. From these investigations an alternative beam T-junction model was obtained, in which a total of six elastic elements at the joint level were introduced, the elastic elements allowed us to adapt the local behavior of the modeled junctions. Additionally, for the estimation of the stiffness values corresponding to the elastic elements two methodologies were developed, one based on the T-junction’s static behavior and a second one based on the T-junction’s dynamic behavior by means of modal analysis. The improvements achieved throughout the implementation of this alternative T-junction model were analyzed though mechanical validation in a complex tubular structures that had a representative configuration for buses and coaches upper structures. From the comparative analyses of the finite element modeled T-junctions and mechanical experimental analysis, was determined that the beam type modeled T-junctions have a stiffer behavior compared to equivalent shell and volume modeled T-junctions with average differences ranging from 5-60% based on the profile configurations. It was also determined that the shell and volume models have a stiffer behavior compared to real T-junctions varying from 5 to 10% depending on the profile configurations. Based on the analysis of the complex tubular structure, significant improvements were obtained by the implementation of the alternative beam T-junction model, the model estimations were improved from a 49% to approximately 14%.

Diagnostics of classical and dusty plasmas w ith collecting and emissive langmuir probes = Diagnosis de plasmas clásicos y granulares mediante sondas colectoras y emisoras de Langmuir

Las sondas eléctricas se emplean habitualmente en la diagnosis de plasmas. La presente tesis aborda la operación de las sondas colectoras y emisoras de Langmuir en plasmas fríos de baja densidad. El estudio se ha centrado en la determinación del potencial de plasma, Vsp, mediante el potencial flotante de una sonda emisora. Esta técnica consiste en la medida del potencial de la sonda correspondiente a la condición de corriente neta igual a cero, el cual se denomina potencial flotante, VF. Este potencial se desplaza hacia el potencial del plasma según aumenta la emisión termoiónica de la sonda, hasta que se satura cerca de Vsp. Los experimentos llevados a cabo en la pluma de plasma de un motor iónico y en un plasma de descarga de glow muestran que la corriente de electrones termoiónicos es mayor que la corriente de electrones recogidos para una sonda polarizada por debajo del potencial del plasma, resultado inconsistente con la teoría tradicionalmente aceptada. Para investigar estos resultados se ha introducido el parámetro R, definido como el cociente entre la corriente de electrones emitidos y recogidos por la sonda. Este parámetro, que está relacionado con la diferencia de potencial VF - Vsp, también es útil para la descripción de los modos de operación de la sonda emisora (débil, fuerte y más allá del fuerte). Los resultados experimentales evidencian que, al contrario de lo que indica la teoría, R es mayor que la unidad. Esta discrepancia se puede solucionar introduciendo una población efectiva de electrones. Con dicha población, el nuevo modelo para la corriente total de la sonda reproduce los datos experimentales. El origen de este grupo electrónico es todavía una cuestión abierta, pero podría estar originada por una nueva estructura de potencial cerca de la sonda cuando ésta trabaja en el régimen de emisión fuerte. Para explicar dicha estructura de potencial, se propone un modelo unidimensional compuesto por un mínimo de potencial cerca de la superficie de la sonda. El análisis numérico indica que este pozo de potencial aparece para muy altas temperaturas de la sonda, reduciendo la cantidad de electrones emitidos que alcanzan el plasma y evitando así cualquier posible perturbación de éste. Los aspectos experimentales involucrados en el método del potencial flotante también se han estudiado, incluyendo cuestiones como las diferentes técnicas de obtención del VF, el cociente señal-ruido, el acoplamiento de la señal de los equipos utilizados para la obtención de las curvas I-V o la evidencia experimental de los diferentes modos de operación de la sonda. Estas evidencias empíricas se encuentran en todos los aspectos de operación de la sonda: la recolección de electrones, el potencial flotante, la precisión en las curvas I-V y la emisión electrónica. Ésta última también se estudia en la tesis, debido a que un fenómeno de super emisión tiene lugar en el régimen de emisión fuerte. En este modo de operación, las medidas experimentales indican que las corrientes termoiónicas de electrones son mayores que aquéllas predichas por la ecuación de Richardson-Dushman clásica. Por último, la diagnosis de plasmas usando sondas eléctrica bajo presencia de granos de polvo (plasmas granulares) en plasmas fríos de baja densidad también se ha estudiado, mediante la aplicación numérica de la técnica del potencial flotante de la sonda emisora en un plasma no convencional. Los resultados apuntan a que el potencial flotante de una sonda emisora se vería afectado por altas densidades de polvo o grandes partículas. ABSTRACT Electric probes are widely employed for plasma diagnostics. This dissertation concerns the operation of collecting and emissive Langmuir probes in low density cold plasmas. The study is focused on the determination of the plasma potential, Vsp, by means of the floating potential of emissive probes. This technique consists of the measurement of the probe potential, corresponding to the zero net probe current, which is the so-called floating potential, VF . This potential displaces towards the plasma potential as the thermionic electron emission increases, until it saturates near Vsp. Experiments carried out in the plasma plume of an ion thruster and in a glow discharge plasma show the thermionic electron current of the emissive Langmuir probe is higher than the collected electron current, for a probe with a bias potential below Vsp, which is inconsistent with the traditional accepted theory. To investigate these results, a parameter R is introduced as the ratio between the emitted and the collected electron current. This parameter, which is related to the difference VF - Vsp, is also useful for the description of the operation modes of the emissive Langmuir probe (weak, strong and beyond strong). The experimental results give an inconsistency of R > 1, which is solved by a modification of the theory for emissive probes, with the introduction of an effective electron population. With this new electron group, the new model for the total probe current agrees with the experimental data. The origin of this electron group remains an open question, but it might be originated by a new potential structure near the emissive probe when it operates in the strong emission regime. A simple one-dimension model composed by a minimum of potential near the probe surface is discussed for strongly emitting emissive probes. The results indicate that this complex potential structure appears for very high probe temperatures and the potential well might reduce the emitted electrons population reaching the plasma bulk. The experimental issues involved in the floating potential method are also studied, as the different obtaining techniques of VF, the signal-to-noise ratio, the signal coupling of the I-V curve measurement system or the experimental evidence of the probe operation modes. These empirical proofs concern all the probe operation aspects: the electron collection, the floating potential, the I-V curve accuracy as well as the electron emission. This last issue is also investigated in this dissertation, because a super emission takes place in the strong emission regime. In this operation mode, the experimental results indicate that the thermionic electron currents might be higher than those predicted by the classical Richardson-Dushman equation. Finally, plasma diagnosis using electric probes in the presence of dust grains (dusty plasmas) in low density cold plasmas is also addressed. The application of the floating potential technique of the emissive probe in a non-conventional complex plasma is numerically investigated, whose results point out the floating potential of the emissive probe might be shifted for high dust density or large dust particles.

Autonomous Acquisition of Natural Situated Communication

An important part of human intelligence, both historically and operationally, is our ability to communicate. We learn how to communicate, and maintain our communicative skills, in a society of communicators – a highly effective way to reach and maintain proficiency in this complex skill. Principles that might allow artificial agents to learn language this way are in completely known at present – the multi-dimensional nature of socio-communicative skills are beyond every machine learning framework so far proposed. Our work begins to address the challenge of proposing a way for observation-based machine learning of natural language and communication. Our framework can learn complex communicative skills with minimal up-front knowledge. The system learns by incrementally producing predictive models of causal relationships in observed data, guided by goal-inference and reasoning using forward-inverse models. We present results from two experiments where our S1 agent learns human communication by observing two humans interacting in a realtime TV-style interview, using multimodal communicative gesture and situated language to talk about recycling of various materials and objects. S1 can learn multimodal complex language and multimodal communicative acts, a vocabulary of 100 words forming natural sentences with relatively complex sentence structure, including manual deictic reference and anaphora. S1 is seeded only with high-level information about goals of the interviewer and interviewee, and a small ontology; no grammar or other information is provided to S1 a priori. The agent learns the pragmatics, semantics, and syntax of complex utterances spoken and gestures from scratch, by observing the humans compare and contrast the cost and pollution related to recycling aluminum cans, glass bottles, newspaper, plastic, and wood. After 20 hours of observation S1 can perform an unscripted TV interview with a human, in the same style, without making mistakes.

Low Work-Function Thermionic Emission and Orbital-Motion-Limited Ion Collection at Bare-Tether Cathodic Contact

Una amarra electrodinámica (electrodynamic tether) opera sobre principios electromagnéticos intercambiando momento con la magnetosfera planetaria e interactuando con su ionosfera. Es un subsistema pasivo fiable para desorbitar etapas de cohetes agotadas y satélites al final de su misión, mitigando el crecimiento de la basura espacial. Una amarra sin aislamiento captura electrones del plasma ambiente a lo largo de su segmento polarizado positivamente, el cual puede alcanzar varios kilómetros de longitud, mientras que emite electrones de vuelta al plasma mediante un contactor de plasma activo de baja impedancia en su extremo catódico, tal como un cátodo hueco (hollow cathode). En ausencia de un contactor catódico activo, la corriente que circula por una amarra desnuda en órbita es nula en ambos extremos de la amarra y se dice que ésta está flotando eléctricamente. Para emisión termoiónica despreciable y captura de corriente en condiciones limitadas por movimiento orbital (orbital-motion-limited, OML), el cociente entre las longitudes de los segmentos anódico y catódico es muy pequeño debido a la disparidad de masas entre iones y electrones. Tal modo de operación resulta en una corriente media y fuerza de Lorentz bajas en la amarra, la cual es poco eficiente como dispositivo para desorbitar. El electride C12A7 : e−, que podría presentar una función de trabajo (work function) tan baja como W = 0.6 eV y un comportamiento estable a temperaturas relativamente altas, ha sido propuesto como recubrimiento para amarras desnudas. La emisión termoiónica a lo largo de un segmento así recubierto y bajo el calentamiento de la operación espacial, puede ser más eficiente que la captura iónica. En el modo más simple de fuerza de frenado, podría eliminar la necesidad de un contactor catódico activo y su correspondientes requisitos de alimentación de gas y subsistema de potencia, lo que resultaría en un sistema real de amarra “sin combustible”. Con este recubrimiento de bajo W, cada segmento elemental del segmento catódico de una amarra desnuda de kilómetros de longitud emitiría corriente como si fuese parte de una sonda cilíndrica, caliente y uniformemente polarizada al potencial local de la amarra. La operación es similar a la de una sonda de Langmuir 2D tanto en los segmentos catódico como anódico. Sin embargo, en presencia de emisión, los electrones emitidos resultan en carga espacial (space charge) negativa, la cual reduce el campo eléctrico que los acelera hacia fuera, o incluso puede desacelerarlos y hacerlos volver a la sonda. Se forma una doble vainas (double sheath) estable con electrones emitidos desde la sonda e iones provenientes del plasma ambiente. La densidad de corriente termoiónica, variando a lo largo del segmento catódico, podría seguir dos leyes distintas bajo diferentes condiciones: (i) la ley de corriente limitada por la carga espacial (space-charge-limited, SCL) o (ii) la ley de Richardson-Dushman (RDS). Se presenta un estudio preliminar sobre la corriente SCL frente a una sonda emisora usando la teoría de vainas (sheath) formada por la captura iónica en condiciones OML, y la corriente electrónica SCL entre los electrodos cilíndricos según Langmuir. El modelo, que incluye efectos óhmicos y el efecto de transición de emisión SCL a emisión RDS, proporciona los perfiles de corriente y potencial a lo largo de la longitud completa de la amarra. El análisis muestra que en el modo más simple de fuerza de frenado, bajo condiciones orbitales y de amarras típicas, la emisión termoiónica proporciona un contacto catódico eficiente y resulta en una sección catódica pequeña. En el análisis anterior, tanto la transición de emisión SCL a RD como la propia ley de emisión SCL consiste en un modelo muy simplificado. Por ello, a continuación se ha estudiado con detalle la solución de vaina estacionaria de una sonda con emisión termoiónica polarizada negativamente respecto a un plasma isotrópico, no colisional y sin campo magnético. La existencia de posibles partículas atrapadas ha sido ignorada y el estudio incluye tanto un estudio semi-analítico mediante técnica asintóticas como soluciones numéricas completas del problema. Bajo las tres condiciones (i) alto potencial, (ii) R = Rmax para la validez de la captura iónica OML, y (iii) potencial monotónico, se desarrolla un análisis asintótico auto-consistente para la estructura de plasma compleja que contiene las tres especies de cargas (electrones e iones del plasma, electrones emitidos), y cuatro regiones espaciales distintas, utilizando teorías de movimiento orbital y modelos cinéticos de las especies. Aunque los electrones emitidos presentan carga espacial despreciable muy lejos de la sonda, su efecto no se puede despreciar en el análisis global de la estructura de la vaina y de dos capas finas entre la vaina y la región cuasi-neutra. El análisis proporciona las condiciones paramétricas para que la corriente sea SCL. También muestra que la emisión termoiónica aumenta el radio máximo de la sonda para operar dentro del régimen OML y que la emisión de electrones es mucho más eficiente que la captura iónica para el segmento catódico de la amarra. En el código numérico, los movimientos orbitales de las tres especies son modelados para potenciales tanto monotónico como no-monotónico, y sonda de radio R arbitrario (dentro o más allá del régimen de OML para la captura iónica). Aprovechando la existencia de dos invariante, el sistema de ecuaciones Poisson-Vlasov se escribe como una ecuación integro-diferencial, la cual se discretiza mediante un método de diferencias finitas. El sistema de ecuaciones algebraicas no lineal resultante se ha resuelto de con un método Newton-Raphson paralelizado. Los resultados, comparados satisfactoriamente con el análisis analítico, proporcionan la emisión de corriente y la estructura del plasma y del potencial electrostático. ABSTRACT An electrodynamic tether operates on electromagnetic principles and exchanges momentum through the planetary magnetosphere, by continuously interacting with the ionosphere. It is a reliable passive subsystem to deorbit spent rocket stages and satellites at its end of mission, mitigating the growth of orbital debris. A tether left bare of insulation collects electrons by its own uninsulated and positively biased segment with kilometer range, while electrons are emitted by a low-impedance active device at the cathodic end, such as a hollow cathode, to emit the full electron current. In the absence of an active cathodic device, the current flowing along an orbiting bare tether vanishes at both ends and the tether is said to be electrically floating. For negligible thermionic emission and orbital-motion-limited (OML) collection throughout the entire tether (electron/ion collection at anodic/cathodic segment, respectively), the anodic-to-cathodic length ratio is very small due to ions being much heavier, which results in low average current and Lorentz drag. The electride C12A7 : e−, which might present a possible work function as low as W = 0.6 eV and moderately high temperature stability, has been proposed as coating for floating bare tethers. Thermionic emission along a thus coated cathodic segment, under heating in space operation, can be more efficient than ion collection and, in the simplest drag mode, may eliminate the need for an active cathodic device and its corresponding gas-feed requirements and power subsystem, which would result in a truly “propellant-less” tether system. With this low-W coating, each elemental segment on the cathodic segment of a kilometers-long floating bare-tether would emit current as if it were part of a hot cylindrical probe uniformly polarized at the local tether bias, under 2D probe conditions that are also applied to the anodic-segment analysis. In the presence of emission, emitted electrons result in negative space charge, which decreases the electric field that accelerates them outwards, or even reverses it, decelerating electrons near the emitting probe. A double sheath would be established with electrons being emitted from the probe and ions coming from the ambient plasma. The thermionic current density, varying along the cathodic segment, might follow two distinct laws under different con ditions: i) space-charge-limited (SCL) emission or ii) full Richardson-Dushman (RDS) emission. A preliminary study on the SCL current in front of an emissive probe is presented using the orbital-motion-limited (OML) ion-collection sheath and Langmuir’s SCL electron current between cylindrical electrodes. A detailed calculation of current and bias profiles along the entire tether length is carried out with ohmic effects considered and the transition from SCL to full RDS emission is included. Analysis shows that in the simplest drag mode, under typical orbital and tether conditions, thermionic emission provides efficient cathodic contact and leads to a short cathodic section. In the previous analysis, both the transition between SCL and RDS emission and the current law for SCL condition have used a very simple model. To continue, considering an isotropic, unmagnetized, colissionless plasma and a stationary sheath, the probe-plasma contact is studied in detail for a negatively biased probe with thermionic emission. The possible trapped particles are ignored and this study includes both semianalytical solutions using asymptotic analysis and complete numerical solutions. Under conditions of i) high bias, ii) R = Rmax for ion OML collection validity, and iii) monotonic potential, a self-consistent asymptotic analysis is carried out for the complex plasma structure involving all three charge species (plasma electrons and ions, and emitted electrons) and four distinct spatial regions using orbital motion theories and kinetic modeling of the species. Although emitted electrons present negligible space charge far away from the probe, their effect cannot be neglected in the global analysis for the sheath structure and two thin layers in between the sheath and the quasineutral region. The parametric conditions for the current to be space-chargelimited are obtained. It is found that thermionic emission increases the range of probe radius for OML validity and is greatly more effective than ion collection for cathodic contact of tethers. In the numerical code, the orbital motions of all three species are modeled for both monotonic and non-monotonic potential, and for any probe radius R (within or beyond OML regime for ion collection). Taking advantage of two constants of motion (energy and angular momentum), the Poisson-Vlasov equation is described by an integro differential equation, which is discretized using finite difference method. The non-linear algebraic equations are solved using a parallel implementation of the Newton-Raphson method. The results, which show good agreement with the analytical results, provide the results for thermionic current, the sheath structure, and the electrostatic potential.

Polymer interaction with macroscopic carbon nanotube fibres and fabrication of nanostructured composites

El ensamblado de nanotubos de carbono (CNT) como una fibra macroscópica en la cual están orientados preferentemente paralelos entre sí y al eje de la fibra, ha dado como resultado un nuevo tipo de fibra de altas prestaciones derivadas de la explotación eficiente de las propiedades axiales de los CNTs, y que tiene un gran número de aplicaciones potenciales. Fibras continuas de CNTs se produjeron en el Instituto IMDEA Materiales mediante el proceso de hilado directo durante la reacción de síntesis por deposición química de vapores. Uno de los objetivos de esta tesis es el estudio de la estructura de estas fibras mediante técnicas del estado del arte de difracción de rayos X de sincrotrón y la elaboración de un modelo estructural de dicho material. Mediciones texturales de adsorción de gases, análisis de micrografías de electrones y dispersión de rayos X de ángulo alto y bajo (WAXS/SAXS) indican que el material tiene una estructura mesoporosa con una distribución de tamaño de poros ancha derivada del amplio rango de separaciones entre manojos de CNTs, así como una superficie específica de 170m2/g. Los valores de dimensión fractal obtenidos mediante SAXS y análisis Barrett-Joyner-Halenda (BJH) de mediciones texturales coinciden en 2.4 y 2.5, respectivamente, resaltando el carácter de red de la estructura de dichas fibras. La estructura mesoporosa y tipo hilo de las fibra de CNT es accesible a la infiltración de moléculas externas (líquidos o polímeros). En este trabajo se estudian los cambios en la estructura multiescala de las fibras de CNTs al interactuar con líquidos y polímeros. Los efectos de la densificación en la estructura de fibras secas de CNT son estudiados mediante WAXS/SAXS. El tratamiento de densificación junta los manojos de la fibra (los poros disminuyen de tamaño), resultando en un incremento de la densidad de la fibra. Sin embargo, los dominios estructurales correspondientes a la transferencia de esfuerzo mecánica y carga eléctrica en los nanotubos no son afectados durante este proceso de densificación; como consecuencia no se produce un efecto sustancial en las propiedades mecánicas y eléctricas. Mediciones de SAXS and fibra de CNT antes y después de infiltración de líquidos confirman la penetración de una gran cantidad de líquidos que llena los poros internos de la fibra pero no se intercalan entre capas de nanotubos adyacentes. La infiltración de cadenas poliméricas de bajo peso molecular tiende a expandir los manojos en la fibra e incrementar el ángulo de apertura de los poros. Los resultados de SAXS indican que la estructura interna de la fibra en términos de la organización de las capas de tubos y su orientación no es afectada cuando las muestras consisten en fibras infiltradas con polímeros de alto peso molecular. La cristalización de varios polímeros semicristalinos es acelerada por la presencia de fibras de CNTs alineados y produce el crecimiento de una capa transcristalina normal a la superficie de la fibra. Esto es observado directamente mediante microscopía óptica polarizada, y detectado mediante calorimetría DSC. Las lamelas en la capa transcristalina tienen orientación de la cadena polimérica paralela a la fibra y por lo tanto a los nanotubos, de acuerdo con los patrones de WAXS. Esta orientación preferencial se sugiere como parte de la fuerza impulsora en la nucleación. La nucleación del dominio cristalino polimérico en la superficie de los CNT no es epitaxial. Ocurre sin haber correspondencia entre las estructuras cristalinas del polímero y los nanotubos. Estas observaciones contribuyen a la compresión del fenómeno de nucleación en CNTs y otros nanocarbonos, y sientan las bases para el desarrollo de composites poliméricos de gran escala basados en fibra larga de CNTs alineados. ABSTRACT The assembly of carbon nanotubes into a macroscopic fibre material where they are preferentially aligned parallel to each other and to the fibre axis has resulted in a new class of high-performance fibres, which efficiently exploits the axial properties of the building blocks and has numerous applications. Long, continuous CNT fibres were produced in IMDEA Materials Institute by direct fibre spinning from a chemical vapour deposition reaction. These fibres have a complex hierarchical structure covering multiple length scales. One objective of this thesis is to reveal this structure by means of state-of-the-art techniques such as synchrotron X-ray diffraction, and to build a model to link the fibre structural elements. Texture and gas absorption measurements, using electron microscopy, wide angle and small angle X-ray scattering (WAXS/SAXS), and pore size distribution analysis by Barrett-Joyner-Halenda (BJH), indicate that the material has a mesoporous structure with a wide pore size distribution arising from the range of fibre bundle separation, and a high surface area _170m2/g. Fractal dimension values of 2.4_2.5 obtained from the SAXS and BJH measurements highlight the network structure of the fibre. Mesoporous and yarn-like structure of CNT fibres make them accessible to the infiltration of foreign molecules (liquid or polymer). This work studies multiscale structural changes when CNT fibres interact with liquids and polymers. The effects of densification on the structure of dry CNT fibres were measured by WAXS/SAXS. The densification treatment brings the fibre bundles closer (pores become smaller), leading to an increase in fibre density. However, structural domains made of the load and charge carrying nanotubes are not affected; consequently, it has no substantial effect on mechanical and electrical properties. SAXS measurements on the CNT fibres before and after liquid infiltration imply that most liquids are able to fill the internal pores but not to intercalate between nanotubes. Successful infiltration of low molecular weight polymer chains tends to expand the fibre bundles and increases the pore-opening angle. SAXS results indicate that the inner structure of the fibre, in terms of the nanotube layer arrangement and the fibre alignment, are not largely affected when infiltrated with polymers of relatively high molecular weight. The crystallisation of a variety of semicrystalline polymers is accelerated by the presence of aligned fibres of CNTs and results in the growth of a transcrystalline layer perpendicular to the fibre surface. This can be observed directly under polarised optical microscope, and detected by the exothermic peaks during differential scanning calorimetry. The discussion on the driving forces for the enhanced nucleation points out the preferential chain orientation of polymer lamella with the chain axis parallel to the fibre and thus to the nanotubes, which is confirmed by two-dimensional WAXS patterns. A non-epitaxial polymer crystal growth habit at the CNT-polymer interface is proposed, which is independent of lattice matching between the polymer and nanotubes. These findings contribute to the discussion on polymer nucleation on CNTs and other nanocarbons, and their implication for the development of large polymer composites based on long and aligned fibres of CNTs.

Paisaje de energías: conocimiento estético en el enfoque ambiental del proyecto

Desde hace ya varias décadas la praxis de la ecología ha venido reconociendo la necesidad de estudiar los múltiples sistemas de interacción del ser humano, como especie viva, y su entorno. Entidades espaciales como el paisaje geográfico son empleadas para delimitar sistemas territoriales operados por la sociedad, precisando campos concretos de su acción física, biológica y cultural. La ecología aborda así el conocimiento científico del territorio como asentamiento humano, rastrea sus patrones espaciales y analiza su compleja estructura funcional. En ese contexto, la transferencia de herramientas e instrumentos desde la ecología al ámbito proyectivo posee ya un bagaje de más de cinco décadas. Cada vez con más frecuencia el proyecto emplea parámetros, inventarios, fórmulas, indicadores y tecnologías que tratan de dar una respuesta ambientalmente adecuada a los condicionantes de contorno, por ejemplo aprovechando las condiciones climáticas en la optimización energética o proponiendo programas de usos del suelo que eviten perturbaciones en ecosistemas de interés. Con todo, en el momento presente surgen voces que, ante el dominio indiscutible de los enfoques netamente deterministas, tratan de recordar que los principios del pensamiento ecológico van más allá del mero control cuantitativo de los procesos biofísicos. Recuerdan que la etología demostró a principios del XX que el ser humano, como ser consciente, inviste una relación de intimidad con su entorno que supera tales perspectivas: a través de la correspondencia entre percepción y significación, entre lo físico y lo psíquico, entre interioridad y exterioridad, las personas abrazan la plenitud de aquello que les rodea en un acto de profunda conciliación afectiva. De tal ligadura de intimidad depende, sí o sí, y en toda su profundidad, la aceptación humana del entorno construido. A través de la noción de ambiente [Umwelt] se demuestra que la relación del hombre con su entorno es inseparable, bidireccional y coordinada y, por lo tanto, desde una posición coherente, la experiencia del espacio puede ser examinada a partir de la reciprocidad que constituyen, en continuidad, la persona y el lugar. De esta forma, la tesis dirige su objetivo principal a explorar y considerar, desde el proyecto, el significado y la influencia de la experiencia ambiental del espacio construido en la vida humana. Es más que probable que buena parte de los problemas de desafección del hombre con los paisajes transformados de su contemporaneidad tenga que ver con que tanto las intensidades de la experiencia y percepción humana, como la potestad interpretativa de sus productos culturales, incluyendo la arquitectura, han sido fuertemente reducidas. Ante este problema, la investigación toma como hipótesis la oportunidad que ofrece el pensamiento ecológico de reformular la experiencia estética como un acto de conocimiento, como un evento donde se da el encuentro físico y se construyen significados, donde se sancionan valores sociales y se mira hacia el futuro. Se ha de señalar que la presente tesis doctoral arranca en el Laboratorio de Paisaje del Grupo de Investigación Paisaje Cultural de la Universidad Politécnica de Madrid dirigido por Concha Lapayese y Darío Gazapo, y por tanto hace suyos para el estado del arte los principales conceptos e ideas bajo los que el trabajo teórico y práctico del grupo se viene orientando desde hace años: la consideración del paisaje como acontecimiento; la oscilación de la interpretación entre un paisaje específico y un paisaje genérico en un mundo globalizado; el reconocimiento de la experiencia estética del paisaje como una toma de conciencia social; y en definitiva, la reivindicación de la interioridad en el proyecto contemporáneo. La investigación profundiza en una línea de oportunidad que se abre al promover lo que se ha llamado un conocimiento por lo sentido como estrategia ambiental que permite contrarrestar mitos profundamente arraigados en las estructuras sociales. El primer paso en ese recorrido sería explorar ecológicamente el aporte de la experiencia estética; esto es, su consideración como forma de conocimiento específico. Resultaría pertinente impulsar la idea de la inmersión en el paisaje como fenómeno experiencial, sensual y corporal, y enfrentar, desde ahí, el problema de la aceptación social de lo nuevo y lo trasformado de acuerdo con el momento actual. La exploración sobre la afectividad en el ambiente no es, en cualquier caso, un asunto nuevo. Sin pretensiones de historiografía, dos momentos del siglo XX concentran el interés de la investigación. La primera se corresponde fundamentalmente con la segunda década del siglo, en relación a una serie de influencias que desde los avances científicos determinaron singulares aventuras del arte más experimental. La segunda se posiciona en el entorno de 1970, época en la que es conocido el interés que despertaron las cuestiones ambientales. En ambos casos se han estudiado aportaciones que desvelan conceptos determinantes en la definición de la experiencia estética como un evento de adquisición de conocimiento por lo sentido. Es conveniente adelantar el rol de centralidad que para la investigación tiene el concepto de energía, tal como el propio título subraya. La energía como realidad material y sensible es el sustrato que permite navegar por el principio de unidad epistemológica que subyace al pensamiento ecológico. Sus continuas referencias simbólicas, físicas y metafóricas entre los artistas estudiados no son un mero recurso iconográfico: mantienen inherente el principio de continuidad ambiental en el cual el ser humano y la inmensidad del cosmos navegan indisociables. Un discurso unificado y consistente sobre los aportes de la experiencia estética enfocada como forma de conocimiento por lo sentido hila la lectura histórica, conceptual y práctica de toda la investigación. Con ello se alcanza a hilvanar un diagrama conceptual, modelo de análisis proyectivo, que recoge ideas científicas, filosóficas y proyectivas. De alguna manera, el diagrama trata de dibujar, desde los principios del pensamiento ecológico, la correlación de continuidad que, vacilante, tensa, sutil y frágil se desplaza incesante e irresuelta entre interioridad y exterioridad. ABSTRACT Over the last few decades ecological practice has come to acknowledge a need for studying the multiple systems of interaction between the human being - inasmuch as it is a living species - and its environment. Spatial entities such as the geographic notion of landscape have been used to delimitate the territorial systems operated by society and to describe in detail specific fields of its physical, biological and cultural action. Ecology has thus managed to address the scientific knowledge of the territory as a human settlement, tracking its spatial patterns and analysing its complex functional structure. In this context, the transfer of tools and instruments from the field of ecology to that of design has a tradition already going back more than fifty years. Increasingly more often, design makes use of parameters, inventories, formulas, indicators and technologies to give an environmentally sound response to contour conditions: for instance, taking advantage of the local climate for the optimisation of energy consumption or proposing land uses that avoid disturbing valuable ecosystems. Yet in the present day some voices have arisen that, against the uncontested domination of purely positivistic approaches, are trying to draw attention to the fact that the principles of ecological thought go beyond mere quantitative control of biophysical processes. They point out that, in the early 20th century, ethology proved that the human being, as a conscious entity, invests itself into a relationship of intimacy with its environment that surpasses such perspectives: through the correspondences between perception and signification, between physical and psychological or between inside and outside, people embrace the entirety of their surroundings in an action of deep affective conciliation. It is on this link of intimacy that - fully and unquestionably - human acceptance of the built environment depends. Through the notion of environment [Umwelt] it can be proven that the relationship between the human being and its environment is inseparable, bidirectional and coordinated; and that, therefore, from a coherent position the experience of space can be examined through the reciprocity constituted continuously by person and place. Thus, the main goal in this thesis is to explore and acknowledge, from the standpoint of design, the meaning and influence of the environmental experience in human life. It is extremely likely that many of the issues with mankind’s alienation from the transformed landscapes of the present day arise from the fact that both the intensity of human perception and experience and the interpretive capacity of its cultural products –including architecture - have been greatly reduced. Facing this issue, research has taken as hypothesis the opportunity offered by ecological thought of reformulating aesthetic experience as an act of knowledge – as an event where physical encounter takes place and meanings are constructed; where social values are sanctioned and the path towards the future is drawn. This notwithstanding, the present thesis began in the Landscape Laboratory of the Technical University of Madrid Cultural Landscape Research Group (GIPC-UPM), led by Concha Lapayese and Darío Gazapo; and has therefore appropriated for its state of the art the main concepts and ideas that have been orienting the practical and theoretical work of the latter: the understanding of landscape as an event, the oscillation of interpretation between a specific and a generic landscape within a globalised world; the acknowledgement of the aesthetic experience of landscape as a way of acquiring social awareness; and, all in all, a vindication of interiority in contemporary design. An exploration has been made of the line of opportunity that is opened when promoting what has been termed knowledge through the senses as an environmental strategy allowing to counter myths deeply rooted in social structures. The first step in this path would be an ecological exploration of the contribution of the aesthetic experience; that is, its consideration as a type of specific knowledge. It would be pertinent to further the idea of immersion into the landscape as an experiential, sensual and corporeal phenomenon and, from that point, to face the issue of social acceptance of what is new and transformed according to the values of the present day. The exploration of affectivity in the environment is not, at any rate, a new topic. Without aspiring to make a history of it, we can mark two points in the 20th century that have concentrated the interest of this research. The first coincides with the second decade of the century and relates to a number of influences that, arising from scientific progress, determined the singular adventures of the more experimental tendencies in art. The second is centred around 1970: a period in which the interest drawn by environmental matters is well known. In both cases, contributions have been studied that reveal crucial concepts in defining the aesthetic experience as an event for the acquisition of knowledge through the senses. It is necessary to highlight the role of centrality that the concept of energy has throughout this research, as is evident even in its title. Energy as a material, sensitive reality is the substrate making it possible to navigate through the principle of epistemological unity underlying ecological thought. The continuous symbolic, physical and metaphorical references to it among the artists studied here are not a mere iconographic source: they remind of the inherency of the principle of environmental continuity within which the human being and the immensity of cosmos travel indissociably. A unified, consistent discourse on the contributions of the aesthetic experience addressed as knowledge through the senses weaves together the historic, conceptual and practical reading of the whole research. With it, a conceptual diagram is constructed – a model of design analysis – gathering together scientific, philosophical and design ideas. Somehow, the diagram tries to draw from the principles of ecological thought the correlation of continuity that, vacillating, tense, subtle and fragile, shifts incessantly and unresolved between interiority and exteriority.

Global instability analysis and control of three-dimensional long open cavity flow

The three-dimensional wall-bounded open cavity may be considered as a simplified geometry found in industrial applications such as leading gear or slotted flats on the airplane. Understanding the three-dimensional complex flow structure that surrounds this particular geometry is therefore of major industrial interest. At the light of the remarkable former investigations in this kind of flows, enough evidences suggest that the lateral walls have a great influence on the flow features and hence on their instability modes. Nevertheless, even though there is a large body of literature on cavity flows, most of them are based on the assumption that the flow is two-dimensional and spanwise-periodic. The flow over realistic open cavity should be considered. This thesis presents an investigation of three-dimensional wall-bounded open cavity with geometric ratio 6:2:1. To this aim, three-dimensional Direct Numerical Simulation (DNS) and global linear instability have been performed. Linear instability analysis reveals that the onset of the first instability in this open cavity is around Recr 1080. The three-dimensional shear layer mode with a complex structure is shown to be the most unstable mode. I t is noteworthy that the flow pattern of this high-frequency shear layer mode is similar to the observed unstable oscillations in supercritical unstable case. DNS of the cavity flow carried out at different Reynolds number from steady state until a nonlinear saturated state is obtained. The comparison of time histories of kinetic energy presents a clearly dominant energetic mode which shifts between low-frequency and highfrequency oscillation. A complete flow patterns from subcritical cases to supercritical case has been put in evidence. The flow structure at the supercritical case Re=1100 resembles typical wake-shedding instability oscillations with a lateral motion existed in the subcritical cases. Also, This flow pattern is similar to the observations in experiments. In order to validate the linear instability analysis results, the topology of the composite flow fields reconstructed by linear superposition of a three-dimensional base flow and its leading three-dimensional global eigenmodes has been studied. The instantaneous wall streamlines of those composited flows display distinguish influence region of each eigenmode. Attention has been focused on the leading high-frequency shear layer mode; the composite flow fields have been fully recognized with respect to the downstream wave shedding. The three-dimensional shear layer mode is shown to give rise to a typical wake-shedding instability with a lateral motions occurring downstream which is in good agreement with the experiment results. Moreover, the spanwise-periodic, open cavity with the same length to depth ratio has been also studied. The most unstable linear mode is different from the real three-dimensional cavity flow, because of the existence of the side walls. Structure sensitivity of the unstable global mode is analyzed in the flow control context. The adjoint-based sensitivity analysis has been employed to localized the receptivity region, where the flow is more sensible to momentum forcing and mass injection. Because of the non-normality of the linearized Navier-Stokes equations, the direct and adjoint field has a large spatial separation. The strongest sensitivity region is locate in the upstream lip of the three-dimensional cavity. This numerical finding is in agreement with experimental observations. Finally, a prototype of passive flow control strategy is applied.

Double-stranded RNA induces mRNA degradation in Trypanosoma brucei

Double-stranded RNA (dsRNA) recently has been shown to give rise to genetic interference in Caenorhabditis elegans and also is likely to be the basis for phenotypic cosuppression in plants in certain instances. While constructing a plasmid vector for transfection of trypanosome cells, we serendipitously discovered that in vivo expression of dsRNA of the α-tubulin mRNA 5′ untranslated region (5′ UTR) led to multinucleated cells with striking morphological alterations and a specific block of cytokinesis. Transfection of synthetic α-tubulin 5′ UTR dsRNA, but not of either strand individually, caused the same phenotype. On dsRNA transfection, tubulin mRNA, but not the corresponding pre-mRNA, was rapidly and specifically degraded, leading to a deficit of α-tubulin synthesis. The transfected cells were no longer capable of carrying out cytokinesis and eventually died. Analysis of cytoskeletal structures from these trypanosomes revealed defects in the microtubules of the flagellar axoneme and of the flagellar attachment zone, a complex cortical structure that we propose is essential for establishing the path of the cleavage furrow at cytokinesis. Last, dsRNA-mediated mRNA degradation is not restricted to α-tubulin mRNA but can be applied to other cellular mRNAs, thus establishing a powerful tool to genetically manipulate these important protozoan parasites.

Biosynthesis of vitamin B12: Factor IV, a new intermediate in the anaerobic pathway

The structure of a novel tetradehydrocorrin, factor IV, isolated from Propionibacterium shermanii has been established by multidimensional NMR spectroscopy. Incorporation of radiolabeled factor IV into cobyrinic acid established the biointermediacy of this cobalt complex, whose structure has implications for the mechanisms of the anaerobic pathway to B12.