On the Use of Matrix-Free Shift-Invert Strategies For Global Flow Instability Analysis

A novel time-stepping shift-invert algorithm for linear stability analysis of laminar flows in complex geometries is presented. This method, based on a Krylov subspace iteration, enables the solution of complex non-symmetric eigenvalue problems in a matrix-free framework. Validations and comparisons to the classical exponential method have been performed in three different cases: (i) stenotic flow, (ii) backward-facing step and (iii) lid-driven swirling flow. Results show that this new approach speeds up the required Krylov subspace iterations and has the capability of converging to specific parts of the global spectrum. It is shown that, although the exponential method remains the method of choice if leading eigenvalues are sought, the performance of the present method could be dramatically improved with the use of a preconditioner. In addition, as opposed to other methods, this strategy can be directly applied to any time-stepper, regardless of the temporal or spatial discretization of the latter.

Direct and adjoint global stability analysis of turbulent transonic flows over a NACA0012 profile

In this work, various turbulent solutions of the two-dimensional (2D) and three-dimensional compressible Reynolds averaged Navier?Stokes equations are analyzed using global stability theory. This analysis is motivated by the onset of flow unsteadiness (Hopf bifurcation) for transonic buffet conditions where moderately high Reynolds numbers and compressible effects must be considered. The buffet phenomenon involves a complex interaction between the separated flow and a shock wave. The efficient numerical methodology presented in this paper predicts the critical parameters, namely, the angle of attack and Mach and Reynolds numbers beyond which the onset of flow unsteadiness appears. The geometry, a NACA0012 profile, and flow parameters selected reproduce situations of practical interest for aeronautical applications. The numerical computation is performed in three steps. First, a steady baseflow solution is obtained; second, the Jacobian matrix for the RANS equations based on a finite volume discretization is computed; and finally, the generalized eigenvalue problem is derived when the baseflow is linearly perturbed. The methodology is validated predicting the 2D Hopf bifurcation for a circular cylinder under laminar flow condition. This benchmark shows good agreement with the previous published computations and experimental data. In the transonic buffet case, the baseflow is computed using the Spalart?Allmaras turbulence model and represents a mean flow where the high frequency content and length scales of the order of the shear-layer thickness have been averaged. The lower frequency content is assumed to be decoupled from the high frequencies, thus allowing a stability analysis to be performed on the low frequency range. In addition, results of the corresponding adjoint problem and the sensitivity map are provided for the first time for the buffet problem. Finally, an extruded three-dimensional geometry of the NACA0012 airfoil, where all velocity components are considered, was also analyzed as a Triglobal stability case, and the outcoming results were compared to the previous 2D limited model, confirming that the buffet onset is well detected.

Global Stability Analysis of Turbulent Transonic Flows on Airfoil geometries

La aparición de inestabilidades en un flujo es un problema importante que puede afectar a algunas aplicaciones aerodinámicas. De hecho existen diferentes tipos de fenómenos no-estacionarios que actualmente son tema de investigación; casos como la separación a altos ángulos de ataque o el buffet transónico son dos ejemplos de cierta relevancia. El análisis de estabilidad global permite identificar la aparición de dichas condiciones inestables, proporcionando información importante sobre la región donde la inestabilidad es dominante y sobre la frecuencia del fenómeno inestable. La metodología empleada es capaz de calcular un flujo base promediado mediante una discretización con volúmenes finitos y posteriormente la solución de un problema de autovalores asociado a la linealización que aparece al perturbar el flujo base. El cálculo numérico se puede dividir en tres pasos: primero se calcula una solución estacionaria para las ecuaciones RANS, luego se extrae la matriz del Jacobiano que representa el problema linealizado y finalmente se deriva y se resuelve el problema de autovalores generalizado mediante el método iterativo de Arnoldi. Como primer caso de validación, la técnica descrita ha sido aplicada a un cilindro circular en condiciones laminares para detectar el principio de las oscilaciones de los vórtices de von Karman, y se han comparado los resultados con experimentos y cálculos anteriores. La parte más importante del estudio se centra en el análisis de flujos compresibles en régimen turbulento. La predicción de la aparición y la progresión de flujo separado a altos ángulos de ataque se han estudiado en el perfil NACA0012 en condiciones tanto subsónicas como supersónicas y en una sección del ala del A310 en condiciones de despegue. Para todas las geometrías analizadas, se ha podido observar que la separación gradual genera la aparición de un modo inestable específico para altos ángulos de ataque siempre mayores que el ángulo asociado al máximo coeficiente de sustentación. Además, se ha estudiado el problema adjunto para obtener información sobre la zona donde una fuerza externa provoca el máximo cambio en el campo fluido. El estudio se ha completado calculando el mapa de sensibilidad estructural y localizando el centro de la inestabilidad. En el presente trabajo de tesis se ha analizado otro importante fenómeno: el buffet transónico. En condiciones transónicas, la interacción entre la onda de choque y la capa límite genera una oscilación de la posición de la onda de choque y, por consiguiente, de las fuerzas aerodinámicas. El conocimiento de las condiciones críticas y su origen puede ayudar a evitar la oscilación causada por estas fuerzas. Las condiciones para las cuales comienza la inestabilidad han sido calculadas y comparadas con trabajos anteriores. Por otra parte, los resultados del correspondiente problema adjunto y el mapa de sensibilidad se han obtenido por primera vez para el buffet, indicando la región del dominio que sera necesario modificar para crear el mayor cambio en las propiedades del campo fluido. Dado el gran consumo de memoria requerido para los casos 3D, se ha realizado un estudio sobre la reducción del domino con la finalidad de reducirlo a la región donde está localizada la inestabilidad. La eficacia de dicha reducción de dominio ha sido evaluada investigando el cambio en la dimensión de la matriz del Jacobiano, no resultando muy eficiente en términos del consumo de memoria. Dado que el buffet es un problema en general tridimensional, el análisis TriGlobal de una geometría 3D podría considerarse el auténtico reto futuro. Como aproximación al problema, un primer estudio se ha realizado empleando una geometría tridimensional extruida del NACA00f2. El cálculo del flujo 3D y, por primera vez en casos tridimensionales compresibles y turbulentos, el análisis de estabilidad TriGlobal, se han llevado a cabo. La comparación de los resultados obtenidos con los resultados del anterior modelo 2D, ha permitido, primero, verificar la exactitud del cálculo 2D realizado anteriormente y también ha proporcionado una estimación del consumo de memoria requerido para el caso 3D. ABSTRACT Flow unsteadiness is an important problem in aerodynamic applications. In fact, there are several types of unsteady phenomena that are still at the cutting edge of research in the field; separation at high angles of attack and transonic buffet are two important examples. Global Stability Analysis can identify the unstable onset conditions, providing important information about the instability location in the domain and the frequency of the unstable phenomenon. The methodology computes a base flow averaged state based on a finite volume discretization and a solution for a generalized eigenvalue problem corresponding to the perturbed linearized equations. The numerical computation is then performed in three steps: first, a steady solution for the RANS equation is computed; second, the Jacobian matrix that represents the linearized problem is obtained; and finally, the generalized eigenvalue problem is derived and solved with an Arnoldi iterative method. As a first validation test, the technique has been applied on a laminar circular cylinder in order to detect the von Karman vortex shedding onset, comparing the results with experiments and with previous calculations. The main part of the study focusses on turbulent and compressible cases. The prediction of the origin and progression of separated flows at high angles of attack has been studied on the NACA0012 airfoil at subsonic and transonic conditions and for the A310 airfoil in take-off configuration. For all the analyzed geometries, it has been found that gradual separation generates the appearance of one specific unstable mode for angles of attack always greater than the ones related to the maximum lift coefficient. In addition, the adjoint problem has been studied to suggest the location of an external force that results in the largest change to the flow field. From the direct and the adjoint analysis the structural sensitivity map has been computed and the core of the instability has been located. The other important phenomenon analyzed in this work is the transonic buffet. In transonic conditions, the interaction between the shock wave and the boundary layer leads to an oscillation of the shock location and, consequently, of the aerodynamic forces. Knowing the critical operational conditions and its origin can be helpful in preventing such fluctuating forces. The instability onset has then been computed and compared with the literature. Moreover, results of the corresponding adjoint problem and a sensitivity map have been provided for the first time for the buffet problem, indicating the region that must be modified to create the biggest change in flow field properties. Because of the large memory consumption required when a 3D case is approached, a domain reduction study has been carried out with the aim of limiting the domain size to the region where the instability is located. The effectiveness of the domain reduction has been evaluated by investigating the change in the Jacobian matrix size, not being very efficient in terms of memory consumption. Since buffet is a three-dimensional problem, TriGlobal stability analysis can be seen as a future challenge. To approximate the problem, a first study has been carried out on an extruded three-dimensional geometry of the NACA0012 airfoil. The 3D flow computation and the TriGlobal stability analysis have been performed for the first time on a compressible and turbulent 3D case. The results have been compared with a 2D model, confirming that the buffet onset evaluated in the 2D case is well detected. Moreover, the computation has given an indication about the memory consumption for a 3D case.

Motivación, flow e intención de práctica físico-deportiva en estudiantes de educación física de España y Latinoamérica

A pesar de los innegables beneficios físicos y psicosociales que la práctica de actividad física tiene para la población en las últimas décadas se observa un importante descenso en el nivel de práctica de actividad física durante la adolescencia. La Educación Física (EF) es una asignatura presente en las primeras etapas educativas de los currículums de todos los países y supone para la población infantil y adolescente, durante el periodo de escolarización obligatoria, un entorno de contacto cotidiano con la actividad física y deportiva lo que explica el creciente interés que existe por investigar en este contexto y extraer conclusiones que puedan ayudar a revertir el proceso de progresivo abandono de la práctica en estas edades. El presente trabajo se centra en un periodo, la adolescencia, especialmente sensible al abandono de la práctica de actividad física. Apoyándonos en tres de los marcos teóricos más importantes de los últimos años - Teoría de Metas de Logro, Teoría de la Autodeterminación y Teoría del Flow - hemos realizado un diseño con tres estudios complementarios que nos permitan avanzar en el conocimiento de las variables que afectan a esta realidad. En el primero de los estudios, en el que participaron 3990 estudiantes de EF de España, Argentina, Colombia y Ecuador con edades comprendidas entre 12 y 18 años, se fijaron como objetivos el establecimiento de perfiles motivacionales en estudiantes de EF considerando las orientaciones motivacionales, la motivación intrínseca y el flow disposicional; la comprobación de la posible estabilidad de los perfiles establecidos en cuatro países diferentes; y el análisis de la relación entre los perfiles motivacionales establecidos con la práctica de actividad física realizada en la actualidad y la intención de ser activo en el futuro. Los resultados revelaron la existencia de tres perfiles motivacionales en los estudiantes: perfil de motivación baja-moderada, perfil de motivación de alta motivación con bajo ego y perfil de alta motivación. Se encontraron similitudes en los perfiles motivacionales obtenidos en los cuatro países analizados, sugiriéndose la posibilidad de que la lengua materna compartida pueda ser una variable de influencia en la existencia de patrones conductuales similares. La orientación al ego resultó ser un elemento diferenciador en la relación de los dos perfiles que mostraron niveles más altos de motivación intrínseca, flow disposicional y orientación a la tarea con las variables de práctica. Mayores niveles de orientación al ego determinaron mayores valores de práctica e intención de práctica. En el segundo estudio, en el que participaron 365 estudiantes de EF de España, Argentina y Colombia con edades comprendidas entre 12 y 16 años, se testó un modelo explicativo de la intención de ser físicamente activo en el futuro en estudiantes de EF poco motivados introduciendo el flow disposicional como variable explicativa junto a las orientaciones motivacionales y la motivación intrínseca. El modelo de ecuaciones estructurales testado muestra que tanto la orientación al ego como la orientación a la tarea y la motivación intrínseca predijeron el flow disposicional. No se encontró un efecto significativo de la orientación a la tarea sobre la motivación intrínseca, ni de esta sobre la intención de práctica de AFD en el futuro. El flow disposicional resultó ser un mediador entre ambas orientaciones motivacionales y dicha intención, adquiriendo un papel relevante en la predicción de la intención de realizar actividad física en el futuro en los sujetos con poca motivación hacia la clase de EF. En el último estudio, con una muestra de 53 estudiantes de EF pertenecientes a dos clases de segundo curso de ESO con edades comprendidas entre 13 y 15 años, se analizó el efecto de una intervención de apoyo a las NPB sobre la satisfacción de las mismas, la motivación intrínseca, la disposición a experimentar flow y la intención de ser físicamente activo en el futuro; estudiándose también el efecto de la misma sobre ciertas variables presentes en el proceso de enseñanza-aprendizaje tales como la diversión, el aprendizaje y el gusto hacia el contenido y la metodología empleada. La intervención resultó efectiva en la mejora de todas las variables motivacionales analizadas a excepción de la satisfacción de la necesidad de relaciones sociales, variable que podría ser más difícilmente modificable en tanto que los grupos de clase suelen permanecer estables a lo largo de esta etapa educativa. Los alumnos de la condición experimental presentaron niveles más elevados de diversión, aprendizaje y gusto hacia el contenido y la metodología empleada. ABSTRACT Despite the undeniable physical and psychological benefits that physical activity has on health, a significant drop in the level of physical activity during adolescence has been observed over the last few decades. Physical education (PE) is present in the early stages of educational curricula of all countries, creating an environment in which children and adolescents can maintain daily contact with sport and physical activity during the period of compulsory education. There is thus a growing interest in research within this context, helping to draw conclusions aimed at reversing the progressive decline of physical activity in this age bracket. The work presented here focuses on adolescence – a period particularly sensitive when faced with declining rates of physical activity. Relying on three of the most important recent theoretical frameworks – Achievement Goal Theory, Self-Determination Theory and Flow Theory – we have carried out a design using three complementary studies that allow us to advance the understanding of variables affecting this reality. The first two studies employ a correlational methodology while the third follows a quasi-experimental design. The objectives of the first study, with the participation of 3990 PE students aged 12 to 18 from Spain, Argentina, Colombia and Ecuador, were: a) to establish motivational profiles in physical education students taking into consideration motivational orientations, intrinsic motivation and dispositional flow; b) to check the possible stability of the established profiles in the four countries; and c) to analyze the relationship between motivational profiles and both current levels of physical activity and intention to be physically active in the future. Results revealed the existence of three motivational profiles: low-moderate motivation profile, high motivation and low ego profile and high motivation profile. Similarities were found across the four countries, which presents the possibility that sharing the same mother tongue might influence the existence of similar behavioral patterns. Amongst the profiles that showed the highest levels of intrinsic motivation, dispositional flow and task orientation with practice variables, ego orientation became apparent as a differentiating element. Higher levels of ego orientation correlated with higher levels both in current level of physical activity and intention to be physically active in the future. In the second study, with the participation of 365 PE students aged 12 to 16 from Spain, Argentina and Colombia, an explanatory model of the intention to be physically active within the low-moderate motivation profile was tested, including dispositional flow as an influence variable together with motivational orientations and intrinsic motivation. The structural model equation in the low-moderate motivation profile shows some differences with respect to findings of similar studies using heterogeneous samples in motivational profiles. It was found that ego orientation, task orientation and intrinsic motivation predicted dispositional flow. No significant effects of task orientation on intrinsic motivation, or of intrinsic motivation on intention to be physically active in the future were found. Dispositional flow emerged as a mediator between both motivational orientations and intention, acquiring an important role in the prediction of future intentions to be physically active in adolescents who show low levels of motivation towards physical education. In the last of the three studies, with the participation of 53 PE students drawn from two classes in the second year of secondary education aged 13 to 15, the effect of an intervention to support basic psychological needs was tested against the satisfaction of these needs, intrinsic motivation, disposition to experience flow and intention to be physically active in the future. Alongside this, the aforementioned intervention was tested on certain variables present in the teaching-learning process such as fun, learning and taste for the activity and methodology. Supportive intervention was effective in improving all the motivational variables, except for the satisfaction of the relatedness variable, which may be more difficult to modify as class groups tend to remain stable throughout this educational state. Students in the experimental condition showed higher levels of fun, learning and taste for the content and methodology.

Aeroelastic effects in a traffic sign panel induced by a passing vehicle

Here, a simple theoretical model of the vehicle induced flow and its effects on traffic sign panels is presented. The model is a continuation of a previous one by Sanz-Andrés and coworkers, now including the flexibility of the panel (and, therefore, the flow effects associated to the motion of the panel). Through the paper an aeroelastic one-degree-of-freedom model is developed and the flow effects are computed from unsteady potential theory. The influence of panel's mechanical properties (mass, damping ratio, and stiffness) in the motion induced forces are numerically analyzed.

Discrete linear stability and sensitivity analysis of fluid flows

Este trabajo presenta un método discreto para el cálculo de estabilidad hidrodinámica y análisis de sensibilidad a perturbaciones externas para ecuaciones diferenciales y en particular para las ecuaciones de Navier-Stokes compressible. Se utiliza una aproximación con variable compleja para obtener una precisión analítica en la evaluación de la matriz Jacobiana. Además, mapas de sensibilidad para la sensibilidad a las modificaciones del flujo de base y a una fuerza constante permiten identificar las regiones del campo fluido donde una modificacin (ej. fuerza puntual) tiene un efecto estabilizador del flujo. Se presentan cuatro casos de prueba: (1) un caso analítico para comprobar la derivación discreta, (2) una cavidad cerrada a bajo Reynolds para mostrar la mayor precisión en el cálculo de los valores propios con la aproximación de paso complejo, (3) flujo 2D en un cilindro circular para validar la metodología, y (4) flujo en un cavidad abierta, presentado para validar el método en casos de inestabilidades convectivamente inestables. Los tres últimos casos mencionados (2-4) se resolvieron con las ecuaciones de Navier-Stokes compresibles, utilizando un método Discontinuous Galerkin Spectral Element Method. Se obtuvo una buena concordancia para el caso de validación (3), cuando se comparó el nuevo método con resultados de la literatura. Además, este trabajo muestra que para el cálculo de los modos propios directos y adjuntos, así como para los mapas de sensibilidad, el uso de variables complejas es de suprema importancia para obtener una predicción precisa. El método descrito es aplicado al análisis para la estabilización de la estela generada por un disco actuador, que representa un modelo sencillo para hélices, rotores de helicópteros o turbinas eólicas. Se explora la primera bifurcación del flujo para un disco actuador, y se sugiere que está asociada a una inestabilidad de tipo Kelvin-Helmholtz, cuya estabilidad se controla con en el número de Reynolds y en la resistencia del disco actuador (o fuerza resistente). En primer lugar, se verifica que la disminución de la resistencia del disco tiene un efecto estabilizador parecido a una disminución del Reynolds. En segundo lugar, el análisis hidrodinmico discreto identifica dos regiones para la colocación de una fuerza puntual que controle las inestabilidades, una cerca del disco y otra en una zona aguas abajo. En tercer lugar, se muestra que la inclusión de un forzamiento localizado cerca del actuador produce una estabilización más eficiente que al forzar aguas abajo. El análisis de los campos de flujo controlados confirma que modificando el gradiente de velocidad cerca del actuador es más eficiente para estabilizar la estela. Estos resultados podrían proporcionar nuevas directrices para la estabilización de la estela de turbinas de viento o de marea cuando estén instaladas en un parque eólico y minimizar las interacciones no estacionarias entre turbinas. ABSTRACT A discrete framework for computing the global stability and sensitivity analysis to external perturbations for any set of partial differential equations is presented. In particular, a complex-step approximation is used to achieve near analytical accuracy for the evaluation of the Jacobian matrix. Sensitivity maps for the sensitivity to base flow modifications and to a steady force are computed to identify regions of the flow field where an input could have a stabilising effect. Four test cases are presented: (1) an analytical test case to prove the theory of the discrete framework, (2) a lid-driven cavity at low Reynolds case to show the improved accuracy in the calculation of the eigenvalues when using the complex-step approximation, (3) the 2D flow past a circular cylinder at just below the critical Reynolds number is used to validate the methodology, and finally, (4) the flow past an open cavity is presented to give an example of the discrete method applied to a convectively unstable case. The latter three (2–4) of the aforementioned cases were solved with the 2D compressible Navier–Stokes equations using a Discontinuous Galerkin Spectral Element Method. Good agreement was obtained for the validation test case, (3), with appropriate results in the literature. Furthermore, it is shown that for the calculation of the direct and adjoint eigenmodes and their sensitivity maps to external perturbations, the use of complex variables is paramount for obtaining an accurate prediction. An analysis for stabilising the wake past an actuator disc, which represents a simple model for propellers, helicopter rotors or wind turbines is also presented. We explore the first flow bifurcation for an actuator disc and it suggests that it is associated to a Kelvin- Helmholtz type instability whose stability relies on the Reynolds number and the flow resistance applied through the disc (or actuator forcing). First, we report that decreasing the disc resistance has a similar stabilising effect to an decrease in the Reynolds number. Second, a discrete sensitivity analysis identifies two regions for suitable placement of flow control forcing, one close to the disc and one far downstream where the instability originates. Third, we show that adding a localised forcing close to the actuator provides more stabilisation that forcing far downstream. The analysis of the controlled flow fields, confirms that modifying the velocity gradient close to the actuator is more efficient to stabilise the wake than controlling the sheared flow far downstream. An interesting application of these results is to provide guidelines for stabilising the wake of wind or tidal turbines when placed in an energy farm to minimise unsteady interactions.

Role of Dynactin in Endocytic Traffic: Effects of Dynamitin Overexpression and Colocalization with CLIP-170

The flow of material from peripheral, early endosomes to late endosomes requires microtubules and is thought to be facilitated by the minus end-directed motor cytoplasmic dynein and its activator dynactin. The microtubule-binding protein CLIP-170 may also play a role by providing an early link to endosomes. Here, we show that perturbation of dynactin function in vivo affects endosome dynamics and trafficking. Endosome movement, which is normally bidirectional, is completely inhibited. Receptor-mediated uptake and recycling occur normally, but cells are less susceptible to infection by enveloped viruses that require delivery to late endosomes, and they show reduced accumulation of lysosomally targeted probes. Dynactin colocalizes at microtubule plus ends with CLIP-170 in a way that depends on CLIP-170’s putative cargo-binding domain. Overexpression studies using p150Glued, the microtubule-binding subunit of dynactin, and mutant and wild-type forms of CLIP-170 indicate that CLIP-170 recruits dynactin to microtubule ends. These data suggest a new model for the formation of motile complexes of endosomes and microtubules early in the endocytic pathway.

Ribonucleoprotein infrastructure regulating the flow of genetic information between the genome and the proteome

Following transcription and splicing, each mRNA of a mammalian cell passes into the cytoplasm where its fate is in the hands of a complex network of ribonucleoproteins (mRNPs). The success or failure of a gene to be expressed depends on the performance of this mRNP infrastructure. The entry, gating, processing, and transit of each mRNA through an mRNP network helps determine the composition of a cell's proteome. The machinery that regulates storage, turnover, and translational activation of mRNAs is not well understood, in part, because of the heterogeneous nature of mRNPs. Recently, subsets of cellular mRNAs clustered as members of mRNP complexes have been identified by using antibodies reactive with RNA-binding proteins, including ELAV/Hu, eIF-4E, and poly(A)-binding proteins. Cytoplasmic ELAV/Hu proteins are involved in the stability and translation of early response gene (ERG) transcripts and are expressed predominately in neurons. mRNAs recovered from ELAV/Hu mRNP complexes were found to have similar sequence elements, suggesting a common structural linkage among them. This approach opens the possibility of identifying transcripts physically clustered in vivo that may have similar fates or functions. Moreover, the proteins encoded by physically organized mRNAs may participate in the same biological process or structural outcome, not unlike operons and their polycistronic mRNAs do in prokaryotic organisms. Our goal is to understand the organization and flow of genetic information on an integrative systems level by analyzing the collective properties of proteins and mRNAs associated with mRNPs in vivo.

Least activation path for protein folding: investigation of staphylococcal nuclease folding by stopped-flow circular dichroism.

Is the pathway of protein folding determined by the relative stability of folding intermediates, or by the relative height of the activation barriers leading to these intermediates? This is a fundamental question for resolving the Levinthal paradox, which stated that protein folding by a random search mechanism would require a time too long to be plausible. To answer this question, we have studied the guanidinium chloride (GdmCl)-induced folding/unfolding of staphylococcal nuclease [(SNase, formerly EC 3.1.4.7; now called microbial nuclease or endonuclease, EC 3.1.31.1] by stopped-flow circular dichroism (CD) and differential scanning microcalorimetry (DSC). The data show that while the equilibrium transition is a quasi-two-state process, kinetics in the 2-ms to 500-s time range are triphasic. Data support the sequential mechanism for SNase folding: U3 <--> U2 <--> U1 <--> N0, where U1, U2, and U3 are substates of the unfolded protein and N0 is the native state. Analysis of the relative population of the U1, U2, and U3 species in 2.0 M GdmCl gives delta-G values for the U3 --> U2 reaction of +0.1 kcal/mol and for the U2 --> U1 reaction of -0.49 kcal/mol. The delta-G value for the U1 --> N0 reaction is calculated to be -4.5 kcal/mol from DSC data. The activation energy, enthalpy, and entropy for each kinetic step are also determined. These results allow us to make the following four conclusions. (i) Although the U1, U2, and U3 states are nearly isoenergetic, no random walk occurs among them during the folding. The pathway of folding is unique and sequential. In other words, the relative stability of the folding intermediates does not dictate the folding pathway. Instead, the folding is a descent toward the global free-energy minimum of the native state via the least activation path in the vast energy landscape. Barrier avoidance leads the way, and barrier height limits the rate. Thus, the Levinthal paradox is not applicable to the protein-folding problem. (ii) The main folding reaction (U1 --> N0), in which the peptide chain acquires most of its free energy (via van der Waals' contacts, hydrogen bonding, and electrostatic interactions), is a highly concerted process. These energy-acquiring events take place in a single kinetic phase. (iii) U1 appears to be a compact unfolded species; the rate of conversion of U2 to U1 depends on the viscosity of solution. (iv) All four relaxation times reported here depend on GdmCl concentrations: it is likely that none involve the cis/trans isomerization of prolines. Finally, a mechanism is presented in which formation of sheet-like chain conformations and a hydrophobic condensation event precede the main-chain folding reaction.

Continuous flow nanocatalysis: reaction pathways in the conversion of levulinic acid to valuable chemicals

The selective production of 2-methyltetrahydrofuran from levulinic acid has been effectively conducted using designed Cu based catalysts and compared with a commercial Pd/C system under microwave irradiation. Optimised conditions for the most active catalysts Cu-MINT (>90% conversion, 75% selectivity to MTHF) and Pd/C (78% conversion, 92% selectivity to MTHF) were further translated into a continuous flow process using the proposed catalysts to find out the deactivation of Cu-MINT under flow conditions (79 vs. 13% conversion with a switch in selectivity to products after 30 min in flow), the high stability of Pd/C (73 vs. 70% conversion at stable selectivity under analogous conditions to those of Cu-MINT) but, most importantly, different relevant pathways to valuable products from levulinic acid depending on the type of catalyst employed.

Vehicle handling and stability.

Mode of access: Internet.

Investigation of the flow over simple bodies at Mach numbers of the order of 20 /

"It is shown that adequate means are available for calculating inviscid direct and induced pressures on simple axisymmetric bodies at zero angle of attack. The extent to which viscous effects can alter these predictions is indicated. It is also shown that inviscid induced pressures can significantly affect the stability of blunt, two-dimensional flat wings at low angles of attack. However, at high angles of attack, the inviscid induced pressure effects are negligible."

A study of the aerodynamic effects and stability characteristics of buses. Summary report. Volume 1. Final report.

National Highway Traffic Safety Administration, Washington, D.C.

A study of the aerodynamic effects and stability characteristics of buses. Technical report. Volume 2. Final report.

National Highway Traffic Safety Administration, Washington, D.C.

Guidelines for improving the stability of headlamp aim. Final report.

National Highway Traffic Safety Administration, Washington, D.C.