Synthese und Charakterisierung von Modellen für Photoschalter und elektronische Ventile

Gegenstand der vorliegenden Arbeit war die Synthese von organischen Photoschalter-Modellen auf der Basis von mesoionischen Pyrimidinium-olaten und Bis(thienylperfluorocyclopentenen), sowie die Darstellung substituierter Biphenyl-Biradikale als Modelle für Ventil-Systeme im Sinne eines neuen Schalter-Ventil-Konzeptes.Aufbauend auf meiner Arbeit über mesoionische Pyrimidinium-olate wurde ein henkelverbrücktes Ansa-Mesoion mit einem 16-gliedrigen Makrocyclus, sowie drei mehrcyclische mesoionische Systeme synthetisiert und auf ihr Schaltverhalten hin untersucht. Das Ansa-Mesoion stellt ein erstes einfaches Modell für Schalter-Ventil-Konjugate dar. Zur Darstellung der photochromen Bis(thienylethene) wurden die aus der Literatur bekannten Syntheserouten nach Irie als auch nach Feringa auf neue Strukturen angewandt und die Schalteigenschaften der Bis(thienylethene) optisch nachgewiesen. Die Anordnung der reaktiven Endgruppen in den synthetisierten Verbindungen schafft ideale Voraussetzungen für eine große konformelle Änderung, welche im Schalter-Ventil-Konjugat erwünscht ist. Durch vielfaches Durchlaufen des Schaltprozesses (> 100 Cyclen) konnte die hohe Reversibilität des Schaltvorganges belegt werden.Als Ventilmodelle wurden mit stabilen Nitroxidradikalen substituierte Biphenyle verwendet, deren primärer konformativer Freiheitsgrad durch die Drehung um die Phenyl-Phenyl-Einfachbindung gegeben ist. Experimentelle ESR-Daten und deren Vergleich mit Spektrensimulationen bestätigten die Abhängigkeit der Austauschwechselwirkung J zwischen den Radikalen vom Biphenyldiederwinkel.

Polyphenylene dendrimers

The main goals of this work were the design, synthesis, and characterization of new functional polyphenylene dendrimers. Polyphenylene dendrimers are highly branched, monodisperse macromolecules consisting exclusively of benzene rings. They can be obtained in high yield by a repetitive Diels-Alder cycloaddition - deprotection protocol. Their shape-persistent dendritic scaffold allows to obtain nanoparticles with functional groups in defined relative orientation. In the first chapter polyphenylene dendrimers with a pyrene core are presented. The focus of the investigations was upon the shielding efficiency of dendritic shells of different generations upon the pyrene-functionality in the core. The herein presented materials combine high quantum efficiency, good solubility and improved film forming properties making them possible candidates for several applications in electronic devices. The defined functionalization of polyphenylene dendrimers often requires a great synthetic effort, since for every desired function the appropriate building block has to be synthesized. To overcome these disadvantages, a new functionalization concept based upon benzophenone precursors has been developed. This new concept has successfully been applied for the functionalization of the dendritic core, the dendrimer shell, and the dendrimer surface. To investigate the accessibility and reactivity of the embedded groups, many functions of different size and nature were introduced. Moreover, suitable precursors for the synthesis of dendrimer entrapped species, trityl cations, trityl radicals, and ketyl radical anions, were obtained. The combination of the synthetic protocols of core- and surface-functionalization resulted in a new type of functional molecules, highly interesting from the point of electron transfer processes. A polyphenylene dendron was used to arrange a triphenylamine donor and a perylene acceptor moiety in a defined spatial distance and orientation. The in-depth photophysical investigation of a first model compound is reported. The herein presented functionalized dendrimers are highly interesting as well from the point of view of fundamental research (looking into the optic and electronic properties of such unique shape persistent structures) as from the point of view of their potential application as tailor-made nanomaterials in the field of optoelectronics.

Nano-fabrication of complex functional structures using non- conventional lithography

In Chapter 1 I will present a brief introduction on the state of art of nanotechnologies, nanofabrication techniques and unconventional lithography as a technique to fabricate the novel electronic device as resistive switch so-called memristor is shown. In Chapter 2 a detailed description of the main fabrication and characterization techniques employed in this work is reported. Chapter 3 parallel local oxidation lithography (pLOx) describes as a main technique to obtain accurate patterning process. All the effective parameters has been studied and the optimized condition observed to highly reproducible with excellent patterned nanostructures. The effect of negative bias, calls local reduction (LR) studied. Moreover, the use of AC bias shows faster patterning process respect to DC bias. In Chapter 4 (metal/ e-SiO2/ Si nanojunction) it is shown how the electrochemical oxide nanostructures by using pLOx can be used in the fabrication of novel devices call memristor. We demonstrate a new concept, based on conventional materials, where the lifetime problem is resolved by introducing a “regeneration” step, which restores the nano-memristor to its pristine condition by applying an appropriate voltage cycle. In Chapter 5 (Graphene/ e-SiO2/ Si), Graphene as a building block material is used as an electrode to selectively oxidize the silicon substrate by pLOx set up for the fabrication of novel resistive switch device. In Chapter 6 (surface architecture) I will show another application of pLOx in biotechnology is shown. So the surface functionalization combine with nano-patterning by pLOx used to design a new surface to accurately bind biomolecules with the possibility of studying those properties and more application in nano-bio device fabrication. So, in order to obtain biochips, electronic and optical/photonics devices Nano patterning of DNA used as scaffolds to fabricate small functional nano-components.

A lung-on-chip array with an integrated bio-inspired respiration mechanism

We report about a lung-on-chip array that mimics the pulmonary parenchymal environment, including the thin, alveolar barrier and the three-dimensional cyclic strain induced by the breathing movements. A micro-diaphragm used to stretch the alveolar barrier is inspired by the in-vivo diaphragm, the main muscle responsible for inspiration. The design of this device aims not only at best reproducing the in-vivo conditions found in the lung parenchyma, but also at making its handling easy and robust. An innovative concept, based on the reversible bonding of the device, is presented that enables to accurately control the concentration of cells cultured on the membrane by easily accessing both sides of the membranes. The functionality of the alveolar barrier could be restored by co-culturing epithelial and endothelial cells that formed tight monolayers on each side of a thin, porous and stretchable membrane. We showed that cyclic stretch significantly affects the permeability properties of epithelial cell layers. Furthermore, we could also demonstrate that the strain influences the metabolic activity and the cytokine secretion of primary human pulmonary alveolar epithelial cells obtained from patients. These results demonstrate the potential of this device and confirm the importance of the mechanical strain induced by the breathing in pulmonary research.

Motive-Oriented Psychotherapeutic Relationship Facing a Patient Presenting with Narcissistic Personality Disorder: A Case Study

Motive-oriented therapeutic relationship (MOTHER), a prescriptive concept based on an integrative form of case formulation, the Plan Analysis (PA) method (Caspar, in: Eells (ed.), Handbook of psychotherapy case formulations, 2007), has shown to be of particular relevance for the treatment of patients presenting with personality disorders, in particular contributing to better therapeutic outcome and to a more constructive development of the therapeutic alliance over time (Kramer et al., J Nerv Ment Dis 199:244–250, 2011). Several therapy models refer to MOTHER as intervention principle with regard to borderline and Narcissistic Personality Disorder (NPD) (Sachse et al., Clarification-oriented psychotherapy of narcissistic personality disorder, 2011; Caspar and Berger, in: Dulz et al. (eds.), Handbuch der Borderline-Störungen, 2011). The present case study discusses the case of Mark, a 40-year-old patient presenting with NPD, along with anxious, depressive and anger problems. This patient underwent a seven-session long pre-therapy process, based on psychiatric and psychotherapeutic principles complemented with PA and MOTHER, in preparation for further treatment. MOTHER will be illustrated with patient–therapist verbatim from session 4 and the links between MOTHER and confrontation techniques will be discussed in the context of process-outcome hypotheses, in particular the effect of MOTHER on symptom reduction.

Investigación experimental del flujo aerodinámico sobre helipuertos embarcados

La investigación del flujo aerodinámico sobre helipuertos embarcados se encuentra estrechamente relacionada con la operación segura de las aeronaves, pues las condiciones del flujo que tiene lugar en ese entorno pueden exceder los límites para los que están certificadas dichas aeronaves. El ambiente aerodinámico en las inmediaciones de un barco es altamente complejo y se encuentra influenciado por gran número de factores (chimeneas, antenas, mástiles, etc.) relacionados con la configuración específica del propio barco. El flujo objeto de investigación corresponde a la estela que se desarrolla sobre la cubierta de vuelo de una fragata, el cual está fuertemente influenciado por la superestructura de la misma, y que cualitativamente es similar al flujo que tiene lugar entre edificios altos o helipuertos situados en áreas urbanas, pues comprende estructuras tipo caja, con bordes afilados, que generan flujos tridimensionales altamente turbulentos. En esta Tesis se aborda el estudio del problema desde el punto de vista experimental, mediante simulación en túnel aerodinámico y medida de las variables del campo fluido sobre maquetas de fragatas a escala reducida. Las herramientas empleadas para tal cometido, han sido técnicas experimentales, tales como la visualización del flujo, la velocimetría láser por imágenes de partículas, la anemometría láser Doppler y los scanners electrónicos de presión, que han permitido investigar el flujo problema con objeto de obtener información, y adquirir así, un conocimiento más profundo de dicho flujo. La explotación de este conocimiento, ha dado lugar al diseño de una nueva solución, basada en la modificación de geometría básica de la fragata, por medio del cambio de la curvatura del techo del hangar, permitiendo suavizar el escalón descendente que se produce aguas abajo del mismo. Las geometrías modificadas han sido ensayada en túnel mediante la misma metodología empleada para la fragata original, de modo que, ha podido establecerse un análisis comparativo, para valorar la efectividad de la solución propuesta, el cual ha mostrado resultados satisfactorios, retirando el flujo adverso de la zona de operación de helicópteros y desplazándolo hacia el hangar, donde resulta menos peligroso, de modo que se reduce la carga del piloto y los riesgos de accidente durante las operaciones a bordo de embarcaciones. ABSTRACT The investigation of aerodynamic flow above the ship’s heliports is directly related to the aircraft safe operation, because the environment flow conditions may exceed the aircraft certification limits. Aerodynamic ship’s environment is highly complex and it is influenced by a large number of factors (stacks, antennae, masts, …) related to each specific ship configuration. The flow under investigation occurs into the wake produced above the flight deck of a frigate, that is strongly influenced by the superstructure. This flow is similar to one produced around tall buildings or heliports located in urban areas, thus in both of them, the air is flowing around sharp-edges box-like structures, producing three-dimensional and highly turbulent flows. This Thesis studies the problem from an experimental point of view, by means of wind tunnel simulations and measurements of the flow field around reduced scale frigates models. Tools used in this work are the experimental techniques, as flow visualization, particle image velocimetry, laser Doppler anemometry and pressure electronic scanners. These techniques provide information about the flow in order to obtain a more complete insight of this kind of flows. The exploitation of this insight is used for the design of a new flow control concept, based on the modification of the basic frigate geometry. This new design consists in the hangar roof curvature modification that produces a smoothing of the descendent step located downstream the hangar. Modified geometries are tested in wind tunnel by means of the same methodology as the original frigate, thus a comparative analysis is established in order to perform an assessment of effectiveness. This analysis has shown good results in displacing the adverse flow from the helicopter operation path to the nearest hangar region, reducing the pilot load and the accident risks during on board operations.

La casa de Norman Foster en Hampstead: tecnología y domesticidad

Entre 1978 y 1979, Norman y Wendy Foster proyectan su propia vivienda en el barrio londinense de Hampstead. El proyecto más personal de los Foster permite —como en tantos otros casos— rastrear los referentes, obsesiones, sueños y frustraciones de sus autores. Este proyecto representa el primer y único intento de aplicación en el campo de la arquitectura doméstica de un modelo, denominado por Reyner Banham “la nave bien servida”, que utiliza la integración de sistemas como principal estrategia proyectual. Los 18 meses de intenso trabajo reflejan, a través de las múltiples opciones desarrolladas, la evolución de la obra de la pareja de arquitectos, que avanza desde el funcionalismo fabril de la “nave bien servida”, hacia el expresionismo tecnológico del denominado High-Tech. En los motivos del fracaso del proyecto, que no llegaría a construirse, subyacen los debates y conflictos —entre arquitectura e ingeniería, prefabricación y artesanía, expresionismo y funcionalismo— en los que el estudio se encuentra inmerso a finales de los años 70, y que precipitarán una nueva forma de entender la relación entre arquitectura y tecnología. | Between 1978 and 1979 Norman and Wendy Foster design their own home in the London neighbourhood of Hampstead. The most personal project of the Fosters allows us —as in many other cases— to trace the references, obsessions, dreams and frustrations of its creators. This project represents a unique attempt to apply the “well-serviced shed” concept —as described by Reyner Banham— to the domestic realm. A concept based in the use of systems integration as the main project strategy. The 18 months of intense work show, through the various options developed, the evolution of the production of the couple of architects, from the industrial functionalism of the “well-serviced shed”, towards the technological expressionism of the so-called High-Tech movement. In the reasons behind the failure of this unbuilt project, one can read the debates and conflicts —between architecture and engineering, prefabrication and craftsmanship, expressionism and functionalism— in which the practice is immerse by the end of the 1970s. A series of events that will precipitate a new way of understanding the relationship between architecture and technology.

Exploring Multi-Component Superconducting Compounds by a High-Pressure Method and Ceramic Combinatorial Chemistry

In this short review, we provide some new insights into the material synthesis and characterization of modern multi-component superconducting oxides. Two different approaches such as the high-pressure, high-temperature method and ceramic combinatorial chemistry will be reported with application to several typical examples. First, we highlight the key role of the extreme conditions in the growth of Fe-based superconductors, where a careful control of the composition-structure relation is vital for understanding the microscopic physics. The availability of high-quality LnFeAsO (Ln = lanthanide) single crystals with substitution of O by F, Sm by Th, Fe by Co, and As by P allowed us to measure intrinsic and anisotropic superconducting properties such as Hc2, Jc. Furthermore, we demonstrate that combinatorial ceramic chemistry is an efficient way to search for new superconducting compounds. A single-sample synthesis concept based on multi-element ceramic mixtures can produce a variety of local products. Such a system needs local probe analyses and separation techniques to identify compounds of interest. We present the results obtained from random mixtures of Ca, Sr, Ba, La, Zr, Pb, Tl, Y, Bi, and Cu oxides reacted at different conditions. By adding Zr but removing Tl, Y, and Bi, the bulk state superconductivity got enhanced up to about 122 K.

Transformational leadership, innovative behavior and task performance:test of mediation and moderation processes

We use the self-concept based theory of leadership and social exchange theory to hypothesize processes linking transformational leadership to follower performance outcomes. Specifically, we hypothesize that (a) transformational leadership relates to followers' work engagement both directly and indirectly through their psychological states, (b) work engagement relates to innovative behavior, (c) innovative behavior relates to task performance, and (d) the work engagement–innovative behavior relationship is moderated by leader–member exchange. Results from a test of these relationships in a sample of employees of a large telecommunication company in China largely support our hypothesized model.

“Currículo encarnado”: cartografia simbólica e afinidades pós-coloniais

This thesis has as main objective to reflect about the defining conceptual elements of the embodied curriculum concept, ident ified curriculum conception from the analysis about the rationality employed in the doctoral work of teacher Antonio Fernando Gouvê a da Silva, entitled The construction of the curriculum in popular critical perspective: the significant words to the context ualized practices , written and defended in the Postgraduate Program in Education: Curriculum, in the Pontifícia Catholic University of São Paulo, in 2004. We looked, also, on the problematization of the affinities between postcolonial theories – analytical perspectives towards the discussion about coloniality and their effect on contemporary social weaving – and the embodied curriculum concept. We argue that the reflections present in the aforementioned work bring an articulated curriculum concept based on three conceptual symbiotic elements, namely: negativity, dialogue and praxis, which, by endorsing the possibility of a curricular ingrained practice in the life context of the individuals, have some post - colonial inclinations that lead to the problematizat ion about the neo - colonial manifestations in curricular sphere, outlining a critique of the modus operandi of the colonialism, particularly, in its cultural and epistemic dimension from which the education is inseparable. For that, we used as methodologica l procedure the symbolic cartography, knowledge building strategy systematized by Boaventura de Sousa Santos, which allowed us to construct interpretive maps that enabled the symbolization of the universe which we longed to understand, that is, the concept ual categories mentioned above, which, in our view, underlie the concept of embodied curriculum. In this direction, we anchored ourselves in a meaningful dialogue with the theoretical approach of Paulo Freire and some of his interpreters regarding the disc ussion on curriculum, especially the reflections dev eloped by Antonio Fernando Gouvê a da Silva, and authors whose theoretical developments resonate in prospects for humanization, social justice and empowerment, among which we highlight: Theodor Adorno, Hug o Zemelman, Wilfred Carr, Adolfo Sánchez Vázquez, among others. We seek, in the same manner, on the contributions of authors considered post - colonial, as Hugo Achugar, Gayatri Spivak, Boaventura de Sousa Santos and Enrique Dussel, to name a few, the reason s why we consider the embodied curriculum as a place of political - pedagogical enunciation, conducive to an educational praxis that engages in a curricular work of reality translation in order to see what overwhelms it to, then, elicit the construction of a school curriculum as an awareness project for releasing in relation to what is unjust and inhumane. We consider, finally, that the success of this curriculum embodied translation implies a larger number of speakers mobilized in the production of knowledge that yearns for social emancipation and contribute to the enrichment of human capabilities as the maintenance of the life and the dignity of people.

Transient Receptor Potential Vanilloid 4 Ion Channel Functions as a Pruriceptor in Epidermal Keratinocytes to Evoke Histaminergic Itch.

TRPV4 ion channels function in epidermal keratinocytes and in innervating sensory neurons; however, the contribution of the channel in either cell to neurosensory function remains to be elucidated. We recently reported TRPV4 as a critical component of the keratinocyte machinery that responds to ultraviolet B (UVB) and functions critically to convert the keratinocyte into a pain-generator cell after excess UVB exposure. One key mechanism in keratinocytes was increased expression and secretion of endothelin-1, which is also a known pruritogen. Here we address the question of whether TRPV4 in skin keratinocytes functions in itch, as a particular form of "forefront" signaling in non-neural cells. Our results support this novel concept based on attenuated scratching behavior in response to histaminergic (histamine, compound 48/80, endothelin-1), not non-histaminergic (chloroquine) pruritogens in Trpv4 keratinocyte-specific and inducible knock-out mice. We demonstrate that keratinocytes rely on TRPV4 for calcium influx in response to histaminergic pruritogens. TRPV4 activation in keratinocytes evokes phosphorylation of mitogen-activated protein kinase, ERK, for histaminergic pruritogens. This finding is relevant because we observed robust anti-pruritic effects with topical applications of selective inhibitors for TRPV4 and also for MEK, the kinase upstream of ERK, suggesting that calcium influx via TRPV4 in keratinocytes leads to ERK-phosphorylation, which in turn rapidly converts the keratinocyte into an organismal itch-generator cell. In support of this concept we found that scratching behavior, evoked by direct intradermal activation of TRPV4, was critically dependent on TRPV4 expression in keratinocytes. Thus, TRPV4 functions as a pruriceptor-TRP in skin keratinocytes in histaminergic itch, a novel basic concept with translational-medical relevance.

Thinking Architecture with an Indian Ocean Aquapelago

This article takes up the charge of thinking architecture with one of the Indian Ocean’s central coral atoll formations, the Maldives archipelago. It is undertaken as a critique of the concept of the archipelago as deployed in architecture since the 1970’s. Architects have used the archipelago as a metaphoric metageographical concept based on a land/sea binary, to conceive of architecture as autonomous from its environments. This permits the discipline exemption from its contexts and frames its engagement with the diverse mobilities of contemporary globalization. To counter this, the article draws from a broad body of literature familiar to readers of GeoHumanities, namely island studies, urban island studies, political ecology and thinking with water to undertake a reading of the Maldives as an oceanic aquapelago, as an alternative metageographical concept for architecture in today’s globalized world.

Interaction-free measurements by quantum Zeno stabilization of ultracold atoms

Quantum mechanics predicts that our physical reality is influenced by events that can potentially happen but factually do not occur. Interaction-free measurements (IFMs) exploit this counterintuitive influence to detect the presence of an object without requiring any interaction with it. Here we propose and realize an IFM concept based on an unstable many-particle system. In our experiments, we employ an ultracold gas in an unstable spin configuration, which can undergo a rapid decay. The object-realized by a laser beam-prevents this decay because of the indirect quantum Zeno effect and thus, its presence can be detected without interacting with a single atom. Contrary to existing proposals, our IFM does not require single-particle sources and is only weakly affected by losses and decoherence. We demonstrate confidence levels of 90%, well beyond previous optical experiments.

Catalytic dehydration of glycerol to acrolein: catalysts and processes

The valorization of glycerol has been widely studied notably due to the oversupply of the latter from biodiesel production. Among the different upgrading reactions, dehydration to acrolein is of high interest due to the importance of acrolein as an intermediate for polymer industry (via acrylic acid) and for feed additive (synthon for DL-methionine). It is known that acrolein can be obtained by glycerol catalytic dehydration over acid catalysts. Zeolites and heteropolyacid catalysts are initially highly active, but deactivate rapidly with time on stream by coking, whilst mixed metal oxides are more stable catalytic systems but less selective and in addition they require an activation period. In this talk, the strategy we followed is described. It consisted in a parallel approach in which we developed supported heteropolyacid-based catalysts with increased stability and acrolein selectivity by using a ZrO2-grafted SBA-15 playing the role of the support for silico-tungstic acid active phase, as well as a new concept based on a two zones fluidized bed reactor (TZFBR) to tackle the unavoidable deactivation issue of the HPA catalysts. This type of reactor comprises – in one single capacity – reaction and regeneration zones. In the second part of the lecture the REALCAT platform was introduced. REALCAT (French acronym standing for ‘Advanced High-Throughput Technologies Platform for Biorefineries Catalysts Design’) is an highly integrated platform devoted to the acceleration of innovation in all the fields of industrial catalysis with an emphasis on emergent biorefinery catalytic processes. In this extremely competitive field, REALCAT consists in a versatile High-Throughput Technologies (HTT) platform devoted to innovation in heterogeneous, homogeneous or biocatalysts AND their combinations under the ultra-efficient very novel concept of hybrid catalysis.

Enhancing business English terminology through concept mapping

Given the need of a growing internationalization of business, to have a good command of English is, most of the times important for the development of technical (specific) competences. It is, thus, critical that professionals use accurate terminology to set grounds for a well-succeeded communication. Furthermore, business communication is increasingly moving to ICT-mediated sets and professionals have to be able to promptly adjust to these needs, resorting to trustworthy online information sources, but also using technologies that better serve their business purposes. In this scenario, the main objective of this study is to find evidence as to the utility of concept mapping as a teaching and learning strategy for the appropriation of business English terminology, enabling students to use English more efficiently as language of communication in business context. This study was based on a case study methodology, mainly of exploratory nature. Participants were students (n= 30) enrolled in the subject English Applied to Management II at Águeda School of Technology and Management – University of Aveiro (2013/14 edition). They were asked to create and peer review two concept maps (cmaps), one individually and another in pairs. The data gathered were treated and analysed resorting qualitative (content analysis) and to quantitative (descriptive statistical analysis) techniques. Results of the data analysis unveil that the use of a collaborative concept mapping tool promotes the development of linguistic competences as to the use of business terminology, but also of communication and collaboration competences. Besides, it was also a very important motivation element in the students’ engagement with the subject content.