Computation of turbulent-flow in a square duct - aspects of the secondary flow and its origin

A numerical study of turbulent flow in a straight duct of square cross-section is made. An order-of-magnitude analysis of the 3-D, time-averaged Navier-Stokes equations resulted in a parabolic form of the Navier-Stokes equations. The governing equations, expressed in terms of a new vector-potential formulation, are expanded as a multi-deck structure with each deck characterized by its dominant physical forces. The resulting equations are solved using a finite-element approach with a bicubic element representation on each cross-sectional plane. The numerical integration along the streamwise direction is carried out with finite-difference approximations until a fully-developed state is reached. The computed results agree well with other numerical studies and compare very favorably with the available experimental data. One important outcome of the current investigation is the interpretation analytically that the driving force of the secondary flow in a square duct comes mainly from the second-order terms of the difference in the gradients of the normal and transverse Reynolds stresses in the axial vorticity equation.

Relación entre la globalización y la internacionalización financiera: el caso de las empresas vascas

[ES] Cada vez es mayor el número de empresas que optan por acudir a mercados financieros exteriores, tanto al objeto de obtener financiación en mejores condiciones, como para realizar inversiones más atractivas que las disponibles dentro de las fronteras nacionales. La decisión de internacionalizar el área financiera de la empresa puede ser el resultado de una estrategia específica orientada al aprovechamiento de las oportunidades que ofrece el proceso de globalización financiera, que se está desarrollando de forma vertiginosa los últimos años.

Caso práctico: La Planificación Estratégica del Museo Guggenheim Bilbao desde una perspectiva de Marketing

[ES] La dimensión del mercado turístico y dentro de éste el mercado turístico cultural no deja de crecer y desarrollarse. En algunas regiones su importancia ha sido vital al servir como motor al propio desarrollo económico de la zona. Éste ha sido el caso del fenómeno conocido como Museo Guggenheim que ha contribuido de una forma clara e importante al desarrollo económico de la zona del Gran Bilbao y ha servido de ejemplo para intentar el mismo modelo con mayor o menor éxito en diferentes zonas de España.

A Finite Element Analysis of a Crack Penetrating or Deflecting into an Interface in a Thin Laminate

The crack tip driving force of a crack growing from a pre-crack that is perpendicular to and terminating at an interface between two materials is investigated using a linear fracture mechanics theory. The analysis is performed both for a crack penetrating the interface, growing straight ahead, and for a crack deflecting into the interface. The results from finite element calculations are compared with asymptotic solutions for infinitesimally small crack extensions. The solution is found to be accurate even for fairly large amounts of crack growth. Further, by comparing the crack tip driving force of the deflected crack with that of the penetrating crack, it is shown how to control the path of the crack by choosing the adhesion of the interface relative to the material toughness.

A Mechanical Model For The Quantification Of The Effect Of Laser Quenching On Ctod In Steels

The technology of laser quenching is widely used to improve the surface properties of steels in surface engineering. Generally, laser quenching of steels can lead to two important results. One is the generation of residual stress in the surface layer. In general, the residual stress varies from the surface to the interior along the quenched track depth direction, and the residual stress variation is termed as residual stress gradient effect in this work. The other is the change of mechanical properties of the surface layer, such as the increases of the micro-hardness, resulting from the changes of the microstructure of the surface layer. In this work, a mechanical model of a laser-quenched specimen with a crack in the middle of the quenched layer is developed to quantify the effect of residual stress gradient and the average micro-hardness over the crack length on crack tip opening displacement (CTOD). It is assumed that the crack in the middle of the quenched layer is created after laser quenching, and the crack can be a pre-crack or a defect due to some reasons, such as a void, cavity or a micro-crack. Based on the elastic-plastic fracture mechanics theory and using the relationship between the micro-hardness and yield strength, a concise analytical solution, which can be used to quantify the effect of residual stress gradient and the average micro-hardness over the crack length resulting from laser quenching on CTOD, is obtained. The concise analytical solution obtained in this work, cannot only be used as a means to predict the crack driving force in terms of the CTOD, but also serve as a baseline for further experimental investigation of the effect after laser-quenching treatment on fracture toughness in terms of the critical CTOD of a specimen, accounting for the laser-quenching effect. A numerical example presented in this work shows that the CTOD of the quenched can be significantly decreased in comparison with that of the unquenched. (C) 2008 Elsevier B.V. All rights reserved.

Applying Habermas's critical theory to public administration and policy: A case study of Florida Everglades restoration program

The foundation of Habermas's argument, a leading critical theorist, lies in the unequal distribution of wealth across society. He states that in an advanced capitalist society, the possibility of a crisis has shifted from the economic and political spheres to the legitimation system. Legitimation crises increase the more government intervenes into the economy (market) and the "simultaneous political enfranchisement of almost the entire adult population" (Holub, 1991, p. 88). The reason for this increase is because policymakers in advanced capitalist democracies are caught between conflicting imperatives: they are expected to serve the interests of their nation as a whole, but they must prop up an economic system that benefits the wealthy at the expense of most workers and the environment. Habermas argues that the driving force in history is an expectation, built into the nature of language, that norms, laws, and institutions will serve the interests of the entire population and not just those of a special group. In his view, policy makers in capitalist societies are having to fend off this expectation by simultaneously correcting some of the inequities of the market, denying that they have control over people's economic circumstances, and defending the market as an equitable allocator of income. (deHaven-Smith, 1988, p. 14). Critical theory suggests that this contradiction will be reflected in Everglades policy by communicative narratives that suppress and conceal tensions between environmental and economic priorities. Habermas’ Legitimation Crisis states that political actors use various symbols, ideologies, narratives, and language to engage the public and avoid a legitimation crisis. These influences not only manipulate the general population into desiring what has been manufactured for them, but also leave them feeling unfulfilled and alienated. Also known as false reconciliation, the public's view of society as rational, and "conductive to human freedom and happiness" is altered to become deeply irrational and an obstacle to the desired freedom and happiness (Finlayson, 2005, p. 5). These obstacles and irrationalities give rise to potential crises in the society. Government's increasing involvement in Everglades under advanced capitalism leads to Habermas's four crises: economic/environmental, rationality, legitimation, and motivation. These crises are occurring simultaneously, work in conjunction with each other, and arise when a principle of organization is challenged by increased production needs (deHaven-Smith, 1988). Habermas states that governments use narratives in an attempt to rationalize, legitimize, obscure, and conceal its actions under advanced capitalism. Although there have been many narratives told throughout the history of the Everglades (such as the Everglades was a wilderness that was valued as a wasteland in its natural state), the most recent narrative, “Everglades Restoration”, is the focus of this paper.(PDF contains 4 pages)

Synthesis, structure, and photophysics of polypyridophenazine transition-metal complexes

The condensation of phenanthroline-5,6-dione (phendione) with polyamines is a versatile synthetic route to a wide variety of chelating ligands. Condensation with 2,3- napthalene diamine gives benzo[i]dipyrido[3,2-a:2',3'-c]phenazine (bdppz) a ligand containing weakly-coupled orbitals of benzophenazine (bpz) and 2,2' -bipyridinde(bpy) character. The bpy character gives Re and Ru complexes excited-state redox properties; intramolecular electron transfer (ET) takes place to the bpz portion of the ligand. The charge-separated state so produced has an extraordinarily-long 50 µs lifetime. The slow rate of charge recombination arises from a combination of extremely weak coupling between the metal center and the bpz acceptor orbital and Marcus "inverted region" behavior. Molecular orbital calculations show that only 3% the electron density in the lowest unoccupied molecular orbital lies on the bpy atoms of bdppz, effectively trapping the transferred electron on the bpz portion. The rate of charge recombination decreases with increasing driving force, showing that these rates lie in the inverted region. Comparison of forward and back ET rates shows that donor-acceptor coupling is four orders of magnitude greater for photoinduced electron transfer than it is for thermal charge recombination.

Condensation of phendione with itself or tetramines gives a series of binucleating tetrapyridophenazine ligands of incrementally-varying coordination-site separation. When a photoredox-active metal center is attached, excited-state energy and electron transfer to an acceptor metal center at the other coordination site can be studied as a function of distance. A variety of monometallic and homo- and heterodimetallic tetrapyridophenazine complexes has been synthesized. Electro- and magnetochemistry show that no ground-state interaction exists between the metals in bimetallic complexes. Excited-state energy and electron transfer, however, takes place at rates which are invariant with increasing donor-acceptor separation, indicating that a very efficient coupling mechanism is at work. Theory and experiment have suggested that such behavior might exist in extended π-systems like those presented by these ligands.

Condensation of three equivalents of 4,5-dimethyl-1,2-phenylenediamine with hexaketocyclohexane gives the trinucleating ligand hexaazahexamethyltrinapthalene (hhtn). Attaching two photredox-active metal centers and a third catalytic center to hhtn provides means by which multielectron photocatalyzed reactions might be carried out. The coordination properties of hhtn have been examined; X-ray crystallographic structure determination shows that the ligand's constricted coordination pocket leads to distorted geometries in its mono- and dimetallic derivatives.

Fracture of materials undergoing solid-solid phase transformation

A large number of technologically important materials undergo solid-solid phase transformations. Examples range from ferroelectrics (transducers and memory devices), zirconia (Thermal Barrier Coatings) to nickel superalloys and (lithium) iron phosphate (Li-ion batteries). These transformations involve a change in the crystal structure either through diffusion of species or local rearrangement of atoms. This change of crystal structure leads to a macroscopic change of shape or volume or both and results in internal stresses during the transformation. In certain situations this stress field gives rise to cracks (tin, iron phosphate etc.) which continue to propagate as the transformation front traverses the material. In other materials the transformation modifies the stress field around cracks and effects crack growth behavior (zirconia, ferroelectrics). These observations serve as our motivation to study cracks in solids undergoing phase transformations. Understanding these effects will help in improving the mechanical reliability of the devices employing these materials.

In this thesis we present work on two problems concerning the interplay between cracks and phase transformations. First, we consider the directional growth of a set of parallel edge cracks due to a solid-solid transformation. We conclude from our analysis that phase transformations can lead to formation of parallel edge cracks when the transformation strain satisfies certain conditions and the resulting cracks grow all the way till their tips cross over the phase boundary. Moreover the cracks continue to grow as the phase boundary traverses into the interior of the body at a uniform spacing without any instabilities. There exists an optimal value for the spacing between the cracks. We ascertain these conclusion by performing numerical simulations using finite elements.

Second, we model the effect of the semiconducting nature and dopants on cracks in ferroelectric perovskite materials, particularly barium titanate. Traditional approaches to model fracture in these materials have treated them as insulators. In reality, they are wide bandgap semiconductors with oxygen vacancies and trace impurities acting as dopants. We incorporate the space charge arising due the semiconducting effect and dopant ionization in a phase field model for the ferroelectric. We derive the governing equations by invoking the dissipation inequality over a ferroelectric domain containing a crack. This approach also yields the driving force acting on the crack. Our phase field simulations of polarization domain evolution around a crack show the accumulation of electronic charge on the crack surface making it more permeable than was previously believed so, as seen in recent experiments. We also discuss the effect the space charge has on domain formation and the crack driving force.

Laser-driven coherent betatron oscillation in a laser-wakefield cavity

The origin of beam disparity in emittance and betatron oscillation orbits, in and out of the polarization plane of the drive laser of laser-plasma accelerators, is explained in terms of betatron oscillations driven by the laser field. As trapped electrons accelerate, they move forward and interact with the laser pulse. For the bubble regime, a simple model is presented to describe this interaction in terms of a harmonic oscillator with a driving force from the laser and a restoring force from the plasma wake field. The resulting beam oscillations in the polarization plane, with period approximately the wavelength of the driving laser, increase emittance in that plane and cause microbunching of the beam. These effects are observed directly in 3D particle-in-cell simulations.

Preparation and characterization of an intramolecular electron transfer in a pentaammineruthenium derivative of Candida krisei cytochrome c

A semisynthetic binuclear metalloprotein has been prepared by appending the pentaammineruthenium moiety to histidine 39 of the cytochrome c from the yeast Candida krusei. The site of ruthenium binding was identified by peptide mapping. Spectroscopic and electrochemical properties of the derivative indicate the protein conformation is unperturbed by the modification. A preliminary (minimum) rate constant of 170s^(-1) has been determined for the intramolecular electron transfer from ruthenium(II) to iron(III), which occurs over a distance of at least 13Å (barring major conformational changes). Electrochemical studies indicate that this reaction should proceed with a driving force of ~170mV. The rate constant is an order of magnitude faster than that observed in horse heart cytochrome c for intramolecular electron transfer from pentaammineruthenium(II)(histidine 33) to iron(III) (over a similar distance, and with a similar driving force), suggesting a medium or orientation effect makes the Candida intramolecular electron transfer more favorable.

Detection of constitutive homomeric associations of the integrins Mac-1 subunits by fluorescence resonance energy transfer in living cells

Integrins alpha(M)beta(2) plays important role on leukocytes, such as adhesion, migration, phagocytosis, and apoptosis. It was hypothesized that homomeric associations of integrin subunits provide a driving force for integrins activation, and simultaneously inducing the formation of integrins clusters. However, experimental reports on homomeric associations between integrin subunits are still controversial. Here, we proved the homomeric associations of the isolated Mac-1 subunits in living cells using three-channel fluorescence resonance energy transfer (FRET) microscopy and FRET spectra methods. We found that the extent of homomeric associations between beta(2) subunits is higher than alpha(M) subunits. Furthermore, FRET imaging indicated that the extent of homomeric associations of the Mac-1 subunits is higher along the plasma membrane than in the cytoplasm. Finally, we suggested that homomeric associations of the transmernbrane domains or/and cytoplasmic domains may provide the driving force for the formation of constitutive homomeric associations between alpha(M) or beta(2) subunits. (c) 2006 Elsevier Inc. All rights reserved.

Investigations of charge-carrier dynamics at semiconductor/liquid interfaces

Theoretical and experimental investigations of charge-carrier dynamics at semiconductor/liquid interfaces, specifically with respect to interfacial electron transfer and surface recombination, are presented.

Fermi's golden rule has been used to formulate rate expressions for charge transfer of delocalized carriers in a nondegenerately doped semiconducting electrode to localized, outer-sphere redox acceptors in an electrolyte phase. The treatment allows comparison between charge-transfer kinetic data at metallic, semimetallic, and semiconducting electrodes in terms of parameters such as the electronic coupling to the electrode, the attenuation of coupling with distance into the electrolyte, and the reorganization energy of the charge-transfer event. Within this framework, rate constant values expected at representative semiconducting electrodes have been determined from experimental data for charge transfer at metallic electrodes. The maximum rate constant (i.e., at optimal exoergicity) for outer-sphere processes at semiconducting electrodes is computed to be in the range 10^-17-10^-16 cm⁴ s^-1, which is in excellent agreement with prior theoretical models and experimental results for charge-transfer kinetics at semiconductor/liquid interfaces.

Double-layer corrections have been evaluated for semiconductor electrodes in both depletion and accumulation conditions. In conjuction with the Gouy-Chapman-Stern model, a finite difference approach has been used to calculate potential drops at a representative solid/liquid interface. Under all conditions that were simulated, the correction to the driving force used to evaluate the interfacial rate constant was determined to be less than 2% of the uncorrected interfacial rate constant.

Photoconductivity decay lifetimes have been obtained for Si(111) in contact with solutions of CH₃OH or tetrahydrofuran containing one-electron oxidants. Silicon surfaces in contact with electrolyte solutions having Nernstian redox potentials > 0 V vs. SCE exhibited low effective surface recombination velocities regardless of the different surface chemistries. The formation of an inversion layer, and not a reduced density of electrical trap sites on the surface, is shown to be responsible for the long charge-carrier lifetimes observed for these systems. In addition, a method for preparing an air-stable, low surface recombination velocity Si surface through a two-step, chlorination/alkylation reaction is described.

The Get3 ATPase drives unidirectional targeting of tail-anchored membrane proteins

Efficient and accurate localization of membrane proteins is essential to all cells and requires a complex cascade of interactions between protein machineries. This is exemplified in the recently discovered Guided Entry of Tail-anchored protein pathway, in which the central targeting factor Get3 must sequentially interact with three distinct binding partners (Get4, Get1 and Get2) to ensure the targeted delivery of Tail-anchored proteins to the endoplasmic reticulum membrane. To understand the molecular and energetic principles that provide the vectorial driving force of these interactions, we used a quantitative fluorescence approach combined with mechanistic enzymology to monitor the effector interactions of Get3 at each stage of Tail-anchored protein targeting. We show that nucleotide and membrane protein substrate generate a gradient of interaction energies that drive the cyclic and ordered transit of Get3 from Get4 to Get2 and lastly to Get1. These data also define how the Get3/Tail-anchored complex is captured, handed over, and disassembled by the Get1/2 receptor at the membrane, and reveal a novel role for Get4/5 in recycling Get3 from the endoplasmic reticulum membrane at the end of the targeting reaction. These results provide general insights into how complex cascades of protein interactions are coordinated and coupled to energy inputs in biological systems.

Self-assembly of brush polymers

The unique structure and properties of brush polymers have led to increased interest in them within the scientific community. This thesis describes studies on the self-assembly of these brush polymers.

Chapter 2 describes a study on the rapid self-assembly of brush block copolymers into nanostructures with photonic bandgaps spanning the entire visible spectrum, from ultraviolet to near infrared. Linear relationships are observed between the peak wavelengths of reflection and polymer molecular weights. This work enables "bottom-up" fabrication of photonic crystals with application-tailored bandgaps, through synthetic control of the polymer molecular weight and the method of self-assembly.

Chapter 3 details the analysis of the self-assembly of symmetrical brush block copolymers in bulk and thin films. Highly ordered lamellae with domain spacing ranging from 20 to 240 nm are obtained by varying molecular weight of the backbone. The relationship between degree of polymerization and the domain spacing is reported, and evidence is provided for how rapidly the brush block copolymers self-assemble and achieve thermodynamic equilibrium.

Chapter 4 describes investigations into where morphology transitions take place as the volume fraction of each block is varied in asymmetrical brush block copolymers. Imaging techniques are used to observe a transition from lamellar to a cylindrical morphology as the volume fraction of one of the blocks exceeds 70%. It is also shown that the asymmetric brush block copolymers can be kinetically trapped into undulating lamellar structures by drop casting the samples.

Chapter 5 explores the capability of macromolecules to interdigitate into densely grafted molecular brush copolymers using stereocomplex formation as a driving force. The stereocomplex formation between complementary linear polymers and brush copolymers is demonstrated, while the stereocomplex formation between complementary brush copolymers is shown to be restricted.

Transcription factor occupancy in differentiating skeletal muscle

With recent advances in high-throughput sequencing, mapping of genome-wide transcription factor occupancy has become feasible. To advance the understanding of skeletal muscle differentiation specifically and transcriptional regulation in general, I determined the genome-wide occupancy map for myogenin in differentiating C2C12 myocyte cells. I then analyzed the myogenin map for underlying sequence content and the association between occupied elements and expression trajectories of adjacent genes. Having determined that myogenin primarily associates with expressed genes, I performed a similar analysis on occupancy maps of other transcription factors active during skeletal muscle differentiation, including an extensive analysis of co-occupancy. This analysis provided strong motif evidence for protein-protein interactions as the primary driving force in the formation of Myogenin / Mef2 and MyoD / AP-1 complexes at jointly-occupied sites. Finally, factor occupancy analysis was extended to include bHLH transcription factors in tissues other than skeletal muscle. The cross-tissue analysis led to the emergence of a motif structure used by bHLH TFs to encode either tissue-specific or "general" (public) access in a variety of lineages.