Aspectos estruturais e moleculares do músculo cardíaco durante a transição entre a disfunção e a insuficiência cardiaca

Pós-graduação em Biologia Geral e Aplicada - IBB

On the nu SiO infrared absorption of polysiloxane films

The infrared absorption of polysiloxanes involves a strong band at around 1050 cm(-1), attributed to the antisymmetric vibration of siloxane bridges. The splitting of this band into two components is generally attributed to coupling between next-neighbor siloxane groups along the polysiloxane chain. From a quantitative analysis of the spectra of these materials, we find that this splitting is larger when the material is in thin-film form, and that the relative intensity of the two components is polarization dependent. We show that these effects are fully understandable in the theoretical framework of infrared absorption by thin films, and are related to long-range dipolar interactions responsible for the longitudinal-transverse splitting effect in crystalline materials. As a consequence, the polarization dependence of the infrared absorption observed for thin films does not appear to be associated with an orientational ordering in the film. (c) 2012 Elsevier B.V. All rights reserved.

SnO2 nanocrystals synthesized by microwave-assisted hydrothermal method: towards a relationship between structural and optical properties

The exploration of novel synthetic methodologies that control both size and shape of functional nanostructure opens new avenues for the functional application of nanomaterials. Here, we report a new and versatile approach to synthesize SnO2 nanocrystals (rutile-type structure) using microwave-assisted hydrothermal method. Broad peaks in the X-ray diffraction spectra indicate the nanosized nature of the samples which were indexed as a pure cassiterite tetragonal phase. Chemically and physically adsorbed water was estimated by TGA data and FT-Raman spectra to account for a new broad peak around 560 cm(-1) which is related to defective surface modes. In addition, the spherical-like morphology and low dispersed distribution size around 3-5 nm were investigated by HR-TEM and FE-SEM microscopies. Room temperature PL emission presents two broad bands at 438 and 764 nm, indicating the existence of different recombination centers. When the size of the nanospheres decreases, the relative intensity of 513 nm emission increases and the 393 nm one decreases. UV-Visible spectra show substantial changes in the optical absorbance of crystalline SnO2 nanoparticles while the existence of a small tail points out the presence of localized levels inside the forbidden band gap and supplies the necessary condition for the PL emission.

Spectroscopic, morphological and electrochromic characterization of layer-by-layer hybrid films of polyaniline and hexaniobate nanoscrolls

The combination of semiconducting oxides and polyaniline in the nanoscale range may result in hybrid materials having enhanced properties, such as electrochromism and charge capacity. This paper reports the spectroscopic, morphological and electrochromic characterization of hybrid films made up of hexaniobate one-dimensional (1D) nanoscrolls and polyaniline prepared by the layer-by-layer assembly technique (LbL). Secondary electron imaging and backscattered electron imaging techniques performed using a scanning electron microscope showed that polyaniline is adsorbed on the hexaniobate nanoscrolls, which confirms the combination of the components in the nanoscale domain. UV-VIS-NIR electronic spectra of the LbL hybrid films showed the absorption tail in the NIR region, assigned to delocalized polarons of the polyaniline. Resonance Raman spectra in the 1000-1700 cm(-1) range indicated that hybrid films present a higher relative intensity of polaron bands at 1337 and 1508 cm(-1) than pristine polyaniline in the emeraldine salt form. These results suggest that hexaniobate nanoscrolls induce a secondary doping of polyaniline. The cyclic voltammetry (CV) data for the hybrid film showed a specific capacity of 870 C cm(-3). According to CV results, the synergistic effect on charge storage properties of the hybrid material is attributed to the enhanced electroactivity of the hexaniobate component in the LbL film. Spectroelectrochemical experiments showed that the electrochromic efficiencies at 420 nm are ca. -41 and 24 cm(2) C-1 as the potential changes from 0.8 to -0.9 V and from -0.9 to -1.8 V, respectively, whereas at 800 nm the efficiencies are ca. -55 and 8 cm(2) C-1 for the same potential ranges. The electrochromic efficiencies and multi-colour character of the LbL film of hexaniobate nanoscrolls and polyaniline indicate that this novel hybrid material is an interesting modified electrode for electrochromic devices.

Non-Linear Pricing in Imperfectly Competitive Markets

This thesis is dedicated to the analysis of non-linear pricing in oligopoly. Non-linear pricing is a fairly predominant practice in most real markets, mostly characterized by some amount of competition. The sophistication of pricing practices has increased in the latest decades due to the technological advances that have allowed companies to gather more and more data on consumers preferences. The first essay of the thesis highlights the main characteristics of oligopolistic non-linear pricing. Non-linear pricing is a special case of price discrimination. The theory of price discrimination has to be modified in presence of oligopoly: in particular, a crucial role is played by the competitive externality that implies that product differentiation is closely related to the possibility of discriminating. The essay reviews the theory of competitive non-linear pricing by starting from its foundations, mechanism design under common agency. The different approaches to model non-linear pricing are then reviewed. In particular, the difference between price and quantity competition is highlighted. Finally, the close link between non-linear pricing and the recent developments in the theory of vertical differentiation is explored. The second essay shows how the effects of non-linear pricing are determined by the relationship between the demand and the technological structure of the market. The chapter focuses on a model in which firms supply a homogeneous product in two different sizes. Information about consumers' reservation prices is incomplete and the production technology is characterized by size economies. The model provides insights on the size of the products that one finds in the market. Four equilibrium regions are identified depending on the relative intensity of size economies with respect to consumers' evaluation of the good. Regions for which the product is supplied in a single unit or in several different sizes or in only a very large one. Both the private and social desirability of non-linear pricing varies across different equilibrium regions. The third essay considers the broadband internet market. Non discriminatory issues seem the core of the recent debate on the opportunity or not of regulating the internet. One of the main questions posed is whether the telecom companies, owning the networks constituting the internet, should be allowed to offer quality-contingent contracts to content providers. The aim of this essay is to analyze the issue through a stylized two-sided market model of the web that highlights the effects of such a discrimination over quality, prices and participation to the internet of providers and final users. An overall welfare comparison is proposed, concluding that the final effects of regulation crucially depend on both the technology and preferences of agents.

Species specific nitrogen isotope analysis by NanoSIMS

Der atmosphärische Kreislauf reaktiver Stickstoffverbindungen beschäftigt sowohl die Naturwissenschaftler als auch die Politik. Dies ist insbesondere darauf zurückzuführen, dass reaktive Stickoxide die Bildung von bodennahem Ozon kontrollieren. Reaktive Stickstoffverbindungen spielen darüber hinaus als gasförmige Vorläufer von Feinstaubpartikeln eine wichtige Rolle und der Transport von reaktivem Stickstoff über lange Distanzen verändert den biogeochemischen Kohlenstoffkreislauf des Planeten, indem er entlegene Ökosysteme mit Stickstoff düngt. Die Messungen von stabilen Stickstoffisotopenverhältnissen (15N/14N) bietet ein Hilfsmittel, welches es erlaubt, die Quellen von reaktiven Stickstoffverbindungen zu identifizieren und die am Stickstoffkeislauf beteiligten Reaktionen mithilfe ihrer reaktionsspezifischen Isotopenfraktionierung genauer zu untersuchen. rnIn dieser Doktorarbeit demonstriere ich, dass es möglich ist, mit Hilfe von Nano-Sekundärionenmassenspektrometrie (NanoSIMS) verschiedene stickstoffhaltige Verbindungen, die üblicherweise in atmosphärischen Feinstaubpartikeln vorkommen, mit einer räumlichen Auflösung von weniger als einem Mikrometer zu analysieren und zu identifizieren. Die Unterscheidung verschiedener stickstoffhaltiger Verbindungen erfolgt anhand der relativen Signalintensitäten der positiven und negativen Sekundärionensignale, die beobachtet werden, wenn die Feinstaubproben mit einem Cs+ oder O- Primärionenstrahl beschossen werden. Die Feinstaubproben können direkt auf dem Probenahmesubstrat in das Massenspektrometer eingeführt werden, ohne chemisch oder physikalisch aufbereited zu werden. Die Methode wurde Mithilfe von Nitrat, Nitrit, Ammoniumsulfat, Harnstoff, Aminosären, biologischen Feinstaubproben (Pilzsporen) und Imidazol getestet. Ich habe gezeigt, dass NO2 Sekundärionen nur beim Beschuss von Nitrat und Nitrit (Salzen) mit positiven Primärionen entstehen, während NH4+ Sekundärionen nur beim Beschuss von Aminosäuren, Harnstoff und Ammoniumsalzen mit positiven Primärionen freigesetzt werden, nicht aber beim Beschuss biologischer Proben wie z.B. Pilzsporen. CN- Sekundärionen werden beim Beschuss aller stickstoffhaltigen Verbindungen mit positiven Primärionen beobachtet, da fast alle Proben oberflächennah mit Kohlenstoffspuren kontaminiert sind. Die relative Signalintensität der CN- Sekundärionen ist bei kohlenstoffhaltigen organischen Stickstoffverbindungen am höchsten.rnDarüber hinaus habe ich gezeigt, dass an reinen Nitratsalzproben (NaNO3 und KNO3), welche auf Goldfolien aufgebracht wurden speziesspezifische stabile Stickstoffisotopenverhältnisse mithilfe des 15N16O2- / 14N16O2- - Sekundärionenverhältnisses genau und richtig gemessen werden können. Die Messgenauigkeit auf Feldern mit einer Rastergröße von 5×5 µm2 wurde anhand von Langzeitmessungen an einem hausinternen NaNO3 Standard als ± 0.6 ‰ bestimmt. Die Differenz der matrixspezifischen instrumentellen Massenfraktionierung zwischen NaNO3 und KNO3 betrug 7.1 ± 0.9 ‰. 23Na12C2- Sekundärionen können eine ernst zu nehmende Interferenz darstellen wenn 15N16O2- Sekundärionen zur Messung des nitratspezifischen schweren Stickstoffs eingesetzt werden sollen und Natrium und Kohlenstoff im selben Feinstaubpartikel als interne Mischung vorliegt oder die natriumhaltige Probe auf einem kohlenstoffhaltigen Substrat abgelegt wurde. Selbst wenn, wie im Fall von KNO3, keine derartige Interferenz vorliegt, führt eine interne Mischung mit Kohlenstoff im selben Feinstaubpartikel zu einer matrixspezifischen instrumentellen Massenfraktionierung die mit der folgenden Gleichung beschrieben werden kann: 15Nbias = (101 ± 4) ∙ f − (101 ± 3) ‰, mit f = 14N16O2- / (14N16O2- + 12C14N-). rnWird das 12C15N- / 12C14N- Sekundärionenverhältnis zur Messung der stabilen Stickstoffisotopenzusammensetzung verwendet, beeinflusst die Probematrix die Messungsergebnisse nicht, auch wenn Stickstoff und Kohlenstoff in den Feinstaubpartikeln in variablen N/C–Verhältnissen vorliegen. Auch Interferenzen spielen keine Rolle. Um sicherzustellen, dass die Messung weiterhin spezifisch auf Nitratspezies eingeschränkt bleibt, kann eine 14N16O2- Maske bei der Datenauswertung verwendet werden. Werden die Proben auf einem kohlenstoffhaltigen, stickstofffreien Probennahmesubstrat gesammelt, erhöht dies die Signalintensität für reine Nitrat-Feinstaubpartikel.

Photon-beam subsource sensitivity to the initial electron-beam parameters

One limitation to the widespread implementation of Monte Carlo (MC) patient dose-calculation algorithms for radiotherapy is the lack of a general and accurate source model of the accelerator radiation source. Our aim in this work is to investigate the sensitivity of the photon-beam subsource distributions in a MC source model (with target, primary collimator, and flattening filter photon subsources and an electron subsource) for 6- and 18-MV photon beams when the energy and radial distributions of initial electrons striking a linac target change. For this purpose, phase-space data (PSD) was calculated for various mean electron energies striking the target, various normally distributed electron energy spread, and various normally distributed electron radial intensity distributions. All PSD was analyzed in terms of energy, fluence, and energy fluence distributions, which were compared between the different parameter sets. The energy spread was found to have a negligible influence on the subsource distributions. The mean energy and radial intensity significantly changed the target subsource distribution shapes and intensities. For the primary collimator and flattening filter subsources, the distribution shapes of the fluence and energy fluence changed little for different mean electron energies striking the target, however, their relative intensity compared with the target subsource change, which can be accounted for by a scaling factor. This study indicates that adjustments to MC source models can likely be limited to adjusting the target subsource in conjunction with scaling the relative intensity and energy spectrum of the primary collimator, flattening filter, and electron subsources when the energy and radial distributions of the initial electron-beam change.

Terrigenous sedimentation of sediment core GeoB6007-2

Variations in deposition of terrigenous fine sediments and their grain-size distributions from a high-resolution marine sediment record offshore northwest Africa (30°51.0'N; 10°16.1'W) document climate changes on the African continent during the Holocene. End-member grain-size distributions of the terrigenous silt fraction, which are related to fluvial and aeolian dust transport, indicate millennial-scale variability in the dominant transport processes at the investigation site off northwest Africa as well as recurring periods of dry conditions in northwest Africa during the Holocene. The terrigenous record from the subtropical North Atlantic reflects generally humid conditions before the Younger Dryas, during the early to mid-Holocene, as well as after 1.3 kyr BP. By contrast, continental runoff was reduced and arid conditions were prevalent at the beginning of the Younger Dryas and during the mid- and late Holocene. A comparison with high- and low-latitude Holocene climate records reveals a strong link between northwest African climate and Northern Hemisphere atmospheric circulation throughout the Holocene. Due to its proximal position, close to an ephemeral river system draining the Atlas Mountains as well as the adjacent Saharan desert, this detailed marine sediment record, which has a temporal resolution between 15 and 120 years, is ideally suited to enhance our understanding of ocean-continent-atmosphere interactions in African climates and the hydrological cycle of northern Africa after the last deglaciation.

Biomarker and x-ray diffraction data from Site U1313 (MIS 16 - 9)

A reconstruction of Milankovitch to millennial-scale variability of sea-surface temperature (SST) and sea-surface productivity in the Pleistocene mid-latitude North Atlantic Ocean (MIS 16-9) and its relationship to ice sheet instability was carried out on sediments from IODP Site U1313. This reconstruction is based on alkenone and n-alkane concentrations, Uk37' index, total organic carbon (TOC) and carbonate contents, X-Ray diffraction (XRD) data, magnetic susceptibility, and accumulation rates. Increased input of ice-rafted debris (IRD) occurred during MIS 16, 12, and 10, characterized by high concentrations of dolomite, quartz, and feldspars and elevated accumulation rates of terrigenous matter. Minimum input values of terrigenous matter, on the other hand, were determined for MIS 13 and 11. Peak values of dolomite, coinciding with quartz, plagioclase, and kalifeldspar peaks and maxima in long-chain n-alkanes indicative for land plants, are interpreted as Heinrich-like Events related to sudden instability of the Laurentide Ice Sheet during early and late (deglacial) phases of the glacials. The coincidence of increased TOC values with elevated absolute concentrations of alkenones suggest increased glacial productivity, probably due to a more southern position of the Polar Front. Alkenone-based SST reached absolute maxima of about 19°C during MIS 11.3 and absolute minima of <10°C during MIS 12 and 10. Within MIS 11, prominent cooling events (MIS 11.22 and 11.24) occurred. The absolute SST minima recorded directly before and after the glacial maxima MIS 10.2 and 12.2, are related to Heinrich-like Event meltwater pulses, as supported by the coincidence of SST minima and maxima in C37:4 alkenones and dolomite. These sudden meltwater pulses - especially during Terminations IV and V - probably caused a collapse of phytoplankton productivity as indicated by the distinct drop in alkenone concentrations. Ice-sheet disintegration and subsequent surges and outbursts of icebergs and meltwater discharge may have been triggered by increased insolation in the Northern High Latitudes.

O 1s excitation and ionization processes in the CO2 molecule studied via detection of low-energy fluorescence emission

Oxygen 1s excitation and ionization processes in the CO2 molecule have been studied with dispersed and non-dispersed fluorescence spectroscopy as well as with the vacuum ultraviolet (VUV) photon?photoion coincidence technique. The intensity of the neutral O emission line at 845 nm shows particular sensitivity to core-to-Rydberg excitations and core?valence double excitations, while shape resonances are suppressed. In contrast, the partial fluorescence yield in the wavelength window 300?650 nm and the excitation functions of selected O+ and C+ emission lines in the wavelength range 400?500 nm display all of the absorption features. The relative intensity of ionic emission in the visible range increases towards higher photon energies, which is attributed to O 1s shake-off photoionization. VUV photon?photoion coincidence spectra reveal major contributions from the C+ and O+ ions and a minor contribution from C2+. No conclusive changes in the intensity ratios among the different ions are observed above the O 1s threshold. The line shape of the VUV?O+ coincidence peak in the mass spectrum carries some information on the initial core excitation

Considering cycling for commuting : the role of mode familiarity : an exploration on the (circular) relation between cycling behaviours and attitudes toward cycling in Vitoria-Gasteiz, Spain

¿La gente utiliza la bicicleta porque les gusta? ¿O es el propio hecho de usarla la razón por la que les gusta hacerlo? ¿O es una combinación de las dos? Este tipo de preguntas reflejan un problema que se puede llamar ‘el círculo de la consideración de la bicicleta’: para poder considerar el uso de la bicicleta en el conjunto de posibles opciones a escoger, un individuo tiene que tener creencias positivas sobre ella, sobre todo en el caso de ‘contextos de bajo uso’. Pero parece poco probable que se formen creencias positivas cuando hay bajos niveles de familiaridad al modo, es decir, con un bajo conocimiento de sus características, su funcionamiento y del imaginario asociado; al mismo tiempo, la familiaridad irá alcanzando niveles más altos conforme aumente el tiempo y la intensidad con la que se utilice la bicicleta a lo largo de la vida de los individuos. El problema parece un circulo recursivo huevo-gallina, ya que es difícil que alguien considere el usar la bicicleta en lugares donde su uso es una práctica poco extendida. En estos lugares, y dentro del conglomerado actual de tecnologías, infraestructuras, reglas, prácticas de los usuarios y preferencias culturales que se han desarrollado alrededor del automóvil (el actual "sistema socio-técnico de la movilidad urbana", Urry 2004; Geels 2005, 2012) usar la bicicleta es considerado por la mayoría como algo difícil, inseguro, y anormal. Como consecuencia, los procesos de aumento de familiaridad con la bicicleta permanecen inactivos. La tesis asume la familiaridad como una fuente de información e influencia sobre las creencias positivas sobre la bicicleta. En ‘contextos de bajo uso’, sin familiaridad al uso de la bicicleta, estas creencias sólo pueden surgir de ciertos rasgos personales (afecto, valores, identidades, voluntad, etc.). Tal como han evidenciado investigaciones recientes, en estos contextos la posibilidad de considerar el uso de la bicicleta (y su eventual adopción), se circunscribe principalmente a los ‘entusiastas’, a los que están dispuestos a “ir contra corriente” (Horton & Parkin 2012), limitando el alcance de las políticas de promoción. La investigación llevada a cabo en esta tesis ofrece un nuevo enfoque al problema del ‘círculo de la consideración de la bicicleta’. Para ello, plantea un modelo en el que se introduce a la familiaridad como un constructo que media entre el comportamiento final –qué modo de transporte elige el individuo– y el conjunto de constructos psicosociales que preceden la elección modal (creencias y actitudes). La familiaridad al uso de la bicicleta se concibe como una medida de la intensidad relativa del uso de una bicicleta, real y percibida (basándose en Diana & Mokhtarian 2009) que puede formarse de manera distinta según sus fines (utilitarios o no utilitarios). El constructo familiaridad con el modo bicicleta está relacionado con la cantidad de tiempo, la intensidad y la regularidad con la que un individuo ha hecho uso de la bicicleta a lo largo de su vida. La familiaridad se concibe así como una condición que permite definir adecuadamente el contexto en el que se toman las decisiones modales de los individuos, en línea con investigaciones que postulan patrones de causalidad alternativos entre los procesos cognitivos de elección y los comportamientos modales (Tardif 1977; Dobson et al. 1978; Golob et al. 1979; Golob 2001; Schwanen et al. 2012; Diana et al. 2009; Vij & Walker 2014). De este modo se plantea que el esquema unidireccional actitudesconductas podría no ser completamente valido en el caso de la consideración de la bicicleta, explorando la hipótesis que sean las propias conductas a influenciar la formación de las actitudes. En esta tesis, el constructo de familiaridad se articula teórica y metodológicamente, y se emplea un instrumento de diseño transversal para contrastarlo. Los resultados de una encuesta telefónica a una muestra representativa de 736 personas en la ciudad española de Vitoria-Gasteiz proveen evidencias que sugieren –aunque de forma preliminar– que la familiaridad juega un papel de mediadora en la relación entre la utilización de la bicicleta y la formación de las creencias y actitudes hacia el su uso. La tesis emplea mediciones para cada individuo con respecto tanto a su consideración como a su familiaridad al uso de la bicicleta. Éstas mediciones se definen haciendo uso del análisis factorial exploratorio (AFE). Por un lado, el AFE arroja una estructura del constructo ‘consideración’ formada por cuatro factores, tres de ellos asociados con elementos positivos y uno con elementos negativos: (1) de cómo el uso de la bicicleta se considera verde e inteligente (G&S); (2) sobre su carácter agradable y adecuado (P&S); (3) sobre su eficacia como modo de transporte para ir al trabajo (E); y (4) sobre los principales inconvenientes de su uso, es decir, las dificultades implícitas (sudoración y estar expuestos a las inclemencias del tiempo) y la sensación de inseguridad que genera (sentirse en riesgo de accidentes y estresarse por el tráfico) (D&T). Por otro lado, la familiaridad al uso de la bicicleta se mide en dos distintas variables ordinales (según se base en el uso utilitario o no utilitario). Como resultado, se puede hablar de que cada individuo se encuentra en una de las siguientes cuatro etapas en orden creciente hacia una familiaridad completa al modo: no familiarizados; apenas familiarizados; moderadamente familiarizados; totalmente familiarizados. El análisis de los datos de los cuatro grupos de sujetos de la muestra, –definidos de acuerdo con cada una de las cuatro etapas de familiaridad definidas– ha evidenciado la existencia de diferencias intergrupo estadísticamente significativas, especialmente para la medida relacionada con el uso utilitario. Asimismo, las personas en los niveles inferiores de familiaridad tienen una consideración menor de los aspectos positivos de la bicicleta y por el contrario presentan preocupaciones mayores hacia las características negativas respecto a aquellas personas que están más familiarizados en el uso utilitario. El uso, aunque esporádico, de una bicicleta para fines utilitarios (ir de compras, hacer recados, etc.), a diferencia de no usarla en absoluto, aparece asociado a unas puntuaciones significativamente más altas en los tres factores positivos (G&S, E, P&S), mientras que parece estar asociado a puntuaciones significativamente más bajas en el factor relacionado con las características negativas (D&U). Aparecen resultados similares cuando se compara un uso moderado, con uno esporádico, sobre todo con respecto a la consideración de las características negativas. Los resultados de esta tesis están en línea con la literatura anterior que se ha basado en variables similares (por ejemplo, de Geus et al. 2008; Stinson & Bhat 2003, 2004; Hunt & Abraham 2006; y van Bekkum et al. 2011a, entre otros), pero en este estudio las diferencias se observan en un contexto de bajo uso y se derivan de un análisis de toda la población de personas que se desplazan a su lugar de trabajo o estudio, lo cual eleva la fiabilidad de los resultados. La posibilidad de que unos niveles más altos de uso de la bicicleta para fines utilitarios puedan llevar a niveles más positivos de su consideración abre el camino a implicaciones teóricas y de políticas que se discuten en la tesis. Con estos resultados se argumenta que el enfoque convencional basado en el cambio de actitudes puede no ser el único y prioritario para lograr cambios a la hora de fomentar el uso de la bicicleta. Los resultados apuntan al potencial de otros esquemas de causalidad, basados en patrones de influencia más descentrados y distribuidos, y que adopten una mirada más positiva hacia los hábitos de transporte, conceptualizándolos como “inteligencia encarnada y pre-reflexiva” (Schwanen et al. 2012). Tales esquemas conducen a un enfoque más práctico para la promoción del uso de la bicicleta, con estrategias que podrían basarse en acciones de ‘degustación’ de su uso o de mayor ‘exposición’ a su uso. Is the fact that people like cycling the reason for them to cycle? Or is the fact that they do cycle the reason for them to like cycling? Or is a combination of the two? This kind of questions reflect a problem that can be called ‘the cycle of cycling consideration’: in order to consider cycling in the set of possible options to be chosen, an individual needs to have positive beliefs about it, especially in the case of ‘low-cycling contexts’. However, positive beliefs seem unlikely to be formed with low levels of mode familiarity, say, with a low acquaintance with mode features, functioning and images; at the same time, higher levels of familiarity are likely to be reached if cycling is practised over relative threshold levels of intensities and extensively across individual life courses. The problem looks like a chicken-egg recursive cycle, since the latter condition is hardly met in places where cycling is little practised. In fact, inside the current conglomerate of technologies, infrastructures, regulations, user practices, cultural preferences that have grown around the automobile (the current “socio-technical system of urban mobility”, Urry 2004; Geels 2005, 2012) cycling is commonly considered as difficult, unsafe, and abnormal. Consequently, the processes of familiarity forming remain disabled, and, as a result, beliefs cannot rely on mode familiarity as a source of information and influence. Without cycling familiarity, origins of positive beliefs are supposed to rely only on personal traits (affect, values, identities, willingness, etc.), which, in low-cycling contexts, confine the possibility of cycling consideration (and eventual adoption) mainly to ‘cycling enthusiasts’ who are willing to “go against the grain” (Horton & Parkin 2012), as it results from previous research. New research conducted by author provides theoretical insights for a different approach of the cycling consideration problem in which the presence of the new construct of cycling familiarity is hypothesised in the relationship between mode choice behaviour and the set of psychosocial constructs that are supposed to precede it (beliefs and attitudes). Cycling familiarity is conceived as a measure of the real and the perceived relative intensity of use of a bicycle (building upon Diana & Mokhtarian 2009) which may be differently formed for utilitarian or non-utilitarian purposes. The construct is assumed to be related to the amount of time, the intensity and the regularity an individual spends in using a bicycle for the two distinct categories of purposes, gaining in this way a certain level of acquaintance with the mode. Familiarity with a mode of transport is conceived as an enabling condition to properly define the decision-making context in which individual travel mode choices are taken, in line with rather disperse research efforts postulating inverse relationships between mode behaviours and mode choices (Tardiff 1977; Dobson et al. 1978; Golob et al. 1979; Golob 2001; Schwanen et al. 2012; Diana et al. 2009; Vij & Walker 2014). The new construct is built theoretically and methodologically, and a cross-sectional design instrument is employed. Results from a telephone survey in a representative sample of 736 commuters in the Spanish city of Vitoria-Gasteiz, provide suggestive –although preliminary– evidence on the role of mode familiarity as a mediator in the relationship between cycling use and the formation of beliefs and attitudes toward cycling. Measures of both cycling consideration and cycling familiarity are defined making use of exploratory factor analysis. On the one hand, four distinct cycling consideration measures are created, based on attitude expressions on four underlying factors relating to the cycling commuting behaviour: on how cycling commuting is considered green and smart (G&S); on its pleasant and suited character (P&S); on its efficiency as a mode of transport for commuting (E); and on the main drawbacks of its use, namely the difficulties implied (sweating and being exposed to adverse weather conditions) and the sense of unsafety it generates (feeling at risk of accidents and getting stressed by traffic) (D&U). On the other hand, dimensions of cycling familiarity are measured on two distinct ordinal variables (whether based on the utilitarian or non-utilitarian use) comprising four stages to a complete mode familiarity: not familiar; barely familiar; moderately familiar; fully familiar. For each of the four stages of cycling familiarity defined, statistical significant differences are found, especially for the measure related to the utilitarian use. Consistently, people at the lower levels of cycling familiarity have a lower consideration of the positive aspects of cycling and conversely they exhibit higher concerns towards the negative characteristics than those individuals that are more familiar in utilitarian cycling. Using a bicycle occasionally for practical purposes, as opposed to not using it at all, seems associated to significant higher scores in the three positive factors (G&S, E, P&S) while it appears to be associated to significant lower scores in the factor relating with the negative characteristics of cycling commuting (D&U). A same pattern also occurs with a moderate use, as opposed to an occasional one, especially for the consideration of the negative characteristics. The results are in line with previous literature based on similar variables (e.g. de Geus et al. 2008; Stinson & Bhat 2003, 2004; Hunt & Abraham 2006; and van Bekkum et al. 2011a, among others), but in this study the differences are observed in a low-cycling context and derive from an analysis of the entire population of commuters, which rises the reliability of results.

Análise Conformacional e estudo das interações eletrônicas de algumas α-fenilseleno-α-dietóxifosforilacetofenonas para-substituídas

A presente Dissertação relata a síntese e o estudo conformacional das α-fenilseleno-α-dietóxifosforilacetofenonas para-substituídas p-X-Φ-C(O)CH[SeΦ][P(O)(OEt2] (X=OMe 1, Me 2, H 3, F 4, Cl 5, Br 6 e NO2 7) através da banda de estiramento da carbonila no infravermelho, em solventes de polaridade crescente apoiado por cálculos ab initio HF/6-3IG**. A comparação entre a freqüência e a intensidade relativa dos componentes do dubleto, para os derivados 6 e 7, e do singleto para os derivados 1-5, no solvente apolar tetracloreto de carbono, e dos componentes do dubleto, nos solventes de polaridade crescente (clorofórmio, diclorometano e acetonitrila), para os derivados 1-7, com os dados do cálculo ab initio de 3 (composto de referência), indicou que ambas as conformações estáveis (g1 e g2) apresentam a ligação C-Se na geometria anti-clinal (gauche) em relação à carbonila (C=O), enquanto que a ligação C-P assume uma geometria sin-periplanar (cis) em relação à carbonila. A análise dos contatos interatômicos de átomos relevante em comparação com a soma de seus raios de van der Waals, indicou que ambas as conformações g1 e g2 são fortemente estabilizadas pelo sinergismo das interações orbitalares e eletrostáticas π*(CO) / nSe e Oδ-[CO].....Pδ+[PO]. Analogamente, as interações mais fracas Oδ-[OR]..... Cδ+[CO], 0-Hδ+[SeΦ]....Oδ-[PO] e 0-Hδ+[ΦC(O)]....Oδ-[CO] estabilizam as conformações g1 e g2, aproximadamente na mesma extensão. No entanto, somente a conformação g1 é estabilizada pela interação eletrostática (ligação de hidrogênio) Hδ+[α-CH].....Oδ-[OR], enquanto que sómente a conformação g2 é desestabilizada pelo Efeito de Campo Repulsivo entre os dipolos Cδ+=.Oδ- e Pδ+-ORδ- Assim sendo, pode-se concluir que no dubleto de VCO no IV, o componente de maior freqüência e de menor intensidade corresponde à conformação menos estável g2 (do cálculo) enquanto que o componente de menor freqüência e mais intenso corresponde à conformação mais estável g1 (do cálculo). Estes dados estão de pleno acordo com os deslocamentos de freqüência mais negativos da carbonila (ΔVCO) do confôrmero mais estável g1 em relação ao menos estável g2.