O presente trabalho apresenta o conceito de portal urbano rodoviário como a porta de entrada de uma cidade. Analisa portais de seis cidades: Londrina (PR), Jaú (SP), Vitória (ES), Brasília (DF), Cuiabá (MT), e Goiânia (GO), projetados por arquitetos de renome, como Vilanova Artigas, Carlos Maximiliano Fayet, Lucio Costa e Paulo Mendes da Rocha, sua importância para o desenvolvimento da cidade em que se encontra e sua possível descaracterização, pois estudos a respeito dessa apropriação espacial nas edificações públicas projetadas com o cuidado de fornecer ambientes agradáveis ao usuário, merecem destaque entre as publicações da área de arquiteturae urbanismo. Essas análises têm início à luz de um contexto histórico sociocultural em que se ergueram tais portais, no glamour do modernismo e influências das escolas paulista e carioca, envolvendo questões de tipologia entre outras, evoluindo para a realidade atual, na qual algumas edificações se encontram em funcionamento, de acordo com a atividade proposta ainda em projeto, sem deixar de levar em consideração a recente possibilidade de transformação do espaço oferecido por esses edifícios, em razão da ocupação de um centro de lojas e lanchonetes. / The present work introduces the concept of an urban road gate as the main entrance of a city. Therefore, it analyses the gates present in six cities: Londrina(PR), Jaú (SP), Vitória (ES), Brasília (DF), Cuiabá (MT), and Goiânia (GO) which all of them have been designed by famous architects, such as: Vilanova Artigas, Carlos Maximiliano Fayet, Lucio Costa e Paulo Mendes da Rocha. The present study, analyses the importance of the gates to the development of the city in which it was built and its possible mischaracterizing, once it is important that studies are carried regarding the present usage of this typology of building, which was conceived with the purpose of providing pleasurable public spaces to the general population and due to that, these gates deserve distinction among the publications about architecture and urbanism. The studies about the gates start with the understanding of the social cultural context in which they were designed and built, the glamour of modernism and the influences of the architectural production of Rio de Janeiro (RJ) and São Paulo (SP) concerning subjects as typology and others, evolving until the actual situation, where some of the buildings still working and functioning, following the activities proposed in the original design, as well as the recent possibility of transformation of these spaces, due to the creation of a commercial center and food chains.

O presente trabalho apresenta o conceito de portal urbano rodoviário como a porta de entrada de uma cidade. Analisa portais de seis cidades: Londrina (PR), Jaú (SP), Vitória (ES), Brasília (DF), Cuiabá (MT), e Goiânia (GO), projetados por arquitetos de renome, como Vilanova Artigas, Carlos Maximiliano Fayet, Lucio Costa e Paulo Mendes da Rocha, sua importância para o desenvolvimento da cidade em que se encontra e sua possível descaracterização, pois estudos a respeito dessa apropriação espacial nas edificações públicas projetadas com o cuidado de fornecer ambientes agradáveis ao usuário, merecem destaque entre as publicações da área de arquiteturae urbanismo. Essas análises têm início à luz de um contexto histórico sociocultural em que se ergueram tais portais, no glamour do modernismo e influências das escolas paulista e carioca, envolvendo questões de tipologia entre outras, evoluindo para a realidade atual, na qual algumas edificações se encontram em funcionamento, de acordo com a atividade proposta ainda em projeto, sem deixar de levar em consideração a recente possibilidade de transformação do espaço oferecido por esses edifícios, em razão da ocupação de um centro de lojas e lanchonetes. / The present work introduces the concept of an urban road gate as the main entrance of a city. Therefore, it analyses the gates present in six cities: Londrina(PR), Jaú (SP), Vitória (ES), Brasília (DF), Cuiabá (MT), and Goiânia (GO) which all of them have been designed by famous architects, such as: Vilanova Artigas, Carlos Maximiliano Fayet, Lucio Costa e Paulo Mendes da Rocha. The present study, analyses the importance of the gates to the development of the city in which it was built and its possible mischaracterizing, once it is important that studies are carried regarding the present usage of this typology of building, which was conceived with the purpose of providing pleasurable public spaces to the general population and due to that, these gates deserve distinction among the publications about architecture and urbanism. The studies about the gates start with the understanding of the social cultural context in which they were designed and built, the glamour of modernism and the influences of the architectural production of Rio de Janeiro (RJ) and São Paulo (SP) concerning subjects as typology and others, evolving until the actual situation, where some of the buildings still working and functioning, following the activities proposed in the original design, as well as the recent possibility of transformation of these spaces, due to the creation of a commercial center and food chains.

In ischaemic stroke a disruption of cerebral blood flow leads to impaired metabolism and the formation of an ischaemic penumbra in which tissue at risk of infarction is sought for clinical intervention. In stroke trials, therapeutic intervention has largely been based on perfusion-weighted measures, but these have not been shown to be good predictors of tissue outcome. The aim of this thesis was to develop analysis techniques for magnetic resonance imaging (MRI) of chemical exchange saturation transfer (CEST) in order to quantify metabolic signals associated with tissue fate in patients with acute ischaemic stroke. This included addressing robustness for clinical application, and developing quantitative tools that allow exploration of the in-vivo complexity. Tissue-level analyses were performed on a dataset of 12 patients who had been admitted to the John Radcliffe Hospital in Oxford with acute ischaemic stroke and recruited into a clinical imaging study. Further characterisation of signals was performed on stroke models and tissue phantoms. A comparative study of CEST analysis techniques established a model-based approach, Bloch-McConnell model analysis, as the most robust for measuring pH-weighted signals in a clinical setting. Repeatability was improved by isolating non-CEST effects which attenuate signals of interest. The Bloch-McConnell model was developed further to explore whether more biologically-precise quantification of CEST effects was both possible and necessary. The additional model complexity, whilst more reflective of tissue biology, diminished contrast that distinguishes tissue fate, implying the biology is more complex than pH alone. The same model complexity could be used reveal signal patterns associated with tissue outcome that were otherwise obscured by competing CEST processes when observed through simpler models. Improved quantification techniques were demonstrated which were sufficiently robust to be used on clinical data, but also provided insight into the different biological processes at work in ischaemic tissue in the early stages of the disease. The complex array of competing processes in pathological tissue has underscored a need for analysis tools adequate for investigating these effects in the context of human imaging. The trends herein identified at the tissue level support the use of quantitative CEST MRI analysis as a clinical metabolic imaging tool in the investigation of ischaemic stroke.

O presente trabalho apresenta o conceito de portal urbano rodoviário como a porta de entrada de uma cidade. Analisa portais de seis cidades: Londrina (PR), Jaú (SP), Vitória (ES), Brasília (DF), Cuiabá (MT), e Goiânia (GO), projetados por arquitetos de renome, como Vilanova Artigas, Carlos Maximiliano Fayet, Lucio Costa e Paulo Mendes da Rocha, sua importância para o desenvolvimento da cidade em que se encontra e sua possível descaracterização, pois estudos a respeito dessa apropriação espacial nas edificações públicas projetadas com o cuidado de fornecer ambientes agradáveis ao usuário, merecem destaque entre as publicações da área de arquiteturae urbanismo. Essas análises têm início à luz de um contexto histórico sociocultural em que se ergueram tais portais, no glamour do modernismo e influências das escolas paulista e carioca, envolvendo questões de tipologia entre outras, evoluindo para a realidade atual, na qual algumas edificações se encontram em funcionamento, de acordo com a atividade proposta ainda em projeto, sem deixar de levar em consideração a recente possibilidade de transformação do espaço oferecido por esses edifícios, em razão da ocupação de um centro de lojas e lanchonetes. / The present work introduces the concept of an urban road gate as the main entrance of a city. Therefore, it analyses the gates present in six cities: Londrina(PR), Jaú (SP), Vitória (ES), Brasília (DF), Cuiabá (MT), and Goiânia (GO) which all of them have been designed by famous architects, such as: Vilanova Artigas, Carlos Maximiliano Fayet, Lucio Costa e Paulo Mendes da Rocha. The present study, analyses the importance of the gates to the development of the city in which it was built and its possible mischaracterizing, once it is important that studies are carried regarding the present usage of this typology of building, which was conceived with the purpose of providing pleasurable public spaces to the general population and due to that, these gates deserve distinction among the publications about architecture and urbanism. The studies about the gates start with the understanding of the social cultural context in which they were designed and built, the glamour of modernism and the influences of the architectural production of Rio de Janeiro (RJ) and São Paulo (SP) concerning subjects as typology and others, evolving until the actual situation, where some of the buildings still working and functioning, following the activities proposed in the original design, as well as the recent possibility of transformation of these spaces, due to the creation of a commercial center and food chains.

<p><a></a><a></a><a></a><a></a><a></a><a></a><a></a><a></a><a></a><a></a><a>ABSTRACT</a></p> <p>Phenols are ubiquitous in our surroundings including biological molecules such as L-Dopa metabolites, food components, such as whiskey and liquid smoke, etc. This dissertation describes a new method for detecting phenols, by reaction with Gibbs reagent to form indophenols, followed by mass spectrometric detection. Unlike the standard Gibbs reaction which uses a colorimetric approach, the use of mass spectrometry allows for simultaneous detection of differently substituted phenols. The procedure is demonstrated to work for a large variety of phenols without <i>para</i>‐substitution. With <i>para</i>‐substituted phenols, Gibbs products are still often observed, but the specific product depends on the substituent. For <i>para</i> groups with high electronegativity, such as methoxy or halogens, the reaction proceeds by displacement of the substituent. For groups with lower electronegativity, such as amino or alkyl groups, Gibbs products are observed that retain the substituent, indicating that the reaction occurs at the <i>ortho</i> or <i>meta</i> position. In mixtures of phenols, the relative intensities of the Gibbs products are proportional to the relative concentrations, and concentrations as low as 1 μmol/L can be detected. The method is applied to the qualitative analysis of commercial liquid smoke, and it is found that hickory and mesquite flavors have significantly different phenolic composition.</p> <p>In the course of this study, we used this technique to quantify major phenol derivatives in commercial products such as liquid smoke (catechol, guaiacol and syringol) and whiskey (<i>o</i>-cresol, guaiacol and syringol) as the phenol derivatives are a significant part of the aroma of foodstuffs and alcoholic beverages. For instance, phenolic compounds are partly responsible for the taste, aroma and the smokiness in Liquid Smokes and Scotch whiskies. </p> <p>In the analysis of Liquid Smokes, we have carried out an analysis of phenols in commercial liquid smoke by using the reaction with Gibbs reagent followed by analysis using electrospray ionization mass spectrometry (ESI-MS). This analysis technique allows us to avoid any separation and/or solvent extraction steps before MS analysis. With this analysis, we are able to determine and compare the phenolic compositions of hickory, mesquite, pecan and apple wood flavors of liquid smoke. </p> <p>In the analysis of phenols in whiskey, we describe the detection of the Gibbs products from the phenols in four different commercial Scotch whiskies by using simple ESI-MS. In addition, by addition of an internal standard, 5,6,7,8-tetrahydro-1-napthol (THN), concentrations of the major phenols in the whiskies are readily obtained. With this analysis we are able to determine and compare the composition of phenols in them and their contribution in the taste, smokey, and aroma to the whiskies.</p> <p>Another important class of phenols are found in biological samples, such as L-Dopa and its metabolites, which are neurotransmitters and play important roles in living systems. In this work, we describe the detection of Gibbs products formed from these neurotransmitters after reaction with Gibbs reagent and analysis by using simple ESI‐MS. This technique would be an alternative method for the detection and simultaneous quantification of these neurotransmitters. </p> <p>Finally, in the course of this work, we found that the positive Gibbs tests are obtained for a wide range of <i>para</i>-substituted phenols, and that, in most cases, substitution occurs by displacement of the <i>para</i>-substituent. In addition, there is generally an additional unique second-phenol-addition product, which conveniently can be used from an analytical perspective to distinguish <i>para</i>-substituted phenols from the unsubstituted versions. In addition to using the methodology for phenol analysis, we are examining the mechanism of indophenol formation, particularly with the <i>para</i>-substituted phenols. </p> <p>The importance of peptides to the scientific world is enormous and, therefore, their structures, properties, and reactivity are exceptionally well-characterized by mass spectrometry and electrospray ionization. In the dipeptide work, we have used mass spectrometry to examine the dissociation of dipeptides of phenylalanine (Phe), containing sulfonated tag as a charge carrier (Phe*), proline (Pro) to investigate their gas phase dissociation. The presence of sulfonated tag (SO₃^-) on the Phe amino acid serves as the charge carrier such that the dipeptide backbone has a canonical structure and is not protonated. Phe-Pro dipeptide and their derivatives were synthesized and analyzed by LCQ-Deca mass spectroscopy to get the fragmentation mechanism. To confirm that fragmentation path, we also synthesized dikitopeparazines and oxazolines from all combinations of the dipeptides. All these analyses were confirmed by isotopic labeling experiments and determination and optimization of structures were carried out using theoretical calculation. We have found that the fragmentation of Phe*Pro and ProPhe* dipeptides form sequence specific b₂ ions. In addition, not only is the ‘mobile proton’ involved in the dissociation process, but also is the ‘backbone hydrogen’ is involved in forming b₂ ions. </p> <p> </p>

Background: Gait initiation is a major issue in Parkinson’s disease (PD). Moreover, the effect of current treatment on motor deficits vary alongside individual differences and disease severity. In some cases, postural instability has been documented as a major side-effect and refractory symptom to dopaminergic medication. Despite these shortcomings, research involving other forms of therapy including deep brain stimulation (DBS) and transcranial magnetic stimulation (TMS), has evidenced the improvement of postural deficits in PD. In this regard, there is a strong rational for the modulation of subcortical brain activity via the application of non-invasive transcranial direct current stimulation (tDCS) to interconnected cortical brain structures. Purpose: Therefore, we sought to determine the effect of tDCS applied to the supplementary motor area (SMA), on gait initiation preparation and performance in PD. Methods: A within subjects repeated measures quasi-experimental design was used to investigate the effects of a 10-minute sham-controlled tDCS intervention. Clinically diagnosed participants (n=12) with idiopathic PD were tested on medication during two sessions that bookended one week. Those who had previously undergone other forms of brain stimulation, had diabetes, severe freezing of gait, or any other neurological or functional limitations that could interfere with gait initiation were excluded from the study. Statistical Analyses/Results: Two-way repeated measures ANOVAs with Bonferroni corrections and a post-hoc analyses when appropriate, revealed a significant reduction in the magnitude of center of pressure (CoP) displacement and velocity in the mediolateral (ML) direction following tDCS. Conclusions: Findings from this study provide insights that may guide scientific research regarding the effects of tDCS on gait initiation among those with PD. Additionally, our work may highlight the importance of ML postural stability for individuals with comorbid and/or pharmacologically induced postural instabilities.

The work at hand presents a novel approach to transport in closed quantum systems. To this end a method is introduced which is essentially based on projection operator techniques, in particular on the time-convolutionless (TCL) technique. The projection onto local densities of quantities such as energy, magnetization, particles, etc. yields the reduced dynamics of the respective quantities in terms of a systematic perturbation expansion. Especially, the lowest order contribution of this expansion is used as a strategy for the analysis of transport in "modular" quantum systems. The term modular basically corresponds to (quasi-) one-dimensional structures consisting of identical or at least similar many-level subunits. Modular quantum systems are demonstrated to represent many physical situations and several examples are given. In the context of these quantum systems lowest order TCL is shown as an efficient tool which also allows to investigate the dependence of transport on the considered length scale. In addition an estimation for the validity range of lowest order TCL is derived. As a first application a "design" model is considered for which a complete characterization of all available transport types as well as the transitions to each other is possible. For this model the relationship to quantum chaos and the validity of the Kubo formula is further discussed. As an example for a "real" system the Anderson model is finally analyzed. The results are partially verified by the numerical solution of the full time-dependent Schroedinger equation which is obtained by exact diagonalization or approximative integrators.

No description available.

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The following thesis is a study of how communities of Washington County, Utah developed within one of the most inhospitable deserts of the American West. A trend of reliance on public works programs during economic depressions, not only put people to work, but also provided an influx of outside aid to develop an infrastructure for future economic stability and growth. Each of these public works was carefully planned by leaders who not only saw the immediate impact these projects would have, but also future benefits they would confer. These communities also became dependent on acquiring outside investment capital from the Mormon Church, private companies and government agencies. This dependency required residents to cooperate not only with each other, but with these outside interests who now had a stake in the county's development. The construction of the Mormon Tabernacle and Temple in St. George during the 1870s made that community an important religious and cultural hub for the entire region. Large-scale irrigation and reclamation projects in the 1890s opened up new areas for agriculture and settlement. And in the 1920s and 1930s the development of Zion National Park and the construction of roads provided the infrastructure for one of the county's most important industries, tourism. Long after these projects' completion they still provided economic and cultural value to the communities they served. Some of these projects provided the infrastructural foundation that allowed Washington County communities to have greater security and control over their economic future. Over time the communities of southern Utah created dramatic reenactments and erected monuments of these very projects to celebrate and preserve the story of their construction. During the first decade of the twenty-first century Washington County has become one of the fastest growing areas in the country, and as a result public works programs continue to be important to support this growth.