Solid-state NMR investigation of phosphonic acid based proton conducting materials

In this work, new promising proton conducting fuel cell membrane materials were characterized in terms of their structure and dynamic properties using solid-state nuclear magnetic resonance (NMR) spectroscopy and X-ray diffraction. Structurally different, phosphonic acid (PA) containing materials were systematically evaluated for possible high-temperature operation (e.g. at T>100°C). Notably, 1H, 2H and 31P magic angle spinning (MAS) NMR provided insight into local connectivities and dynamics of the hydrogen bonded network, while packing arrangements were identified by means of heteronuclear dipolar recoupling techniques.rnThe first part of this work introduced rather crystalline, low molecular weight ionomers for proton conducting membranes, where six different geometries such as line, triangle, screw, tetrahedron, square and hexagon, were investigated. The hexagon was identified as the most promising geometry with high-temperature bulk proton conductivities in the range of 10-3 Scm-1 at a relative humidity of 50%. However, 2H NMR and TGA-MS data suggest that the bulk proton transport is mainly due to the presence of crystal water. Single crystal X-ray data revealed that in the tetrahedron phosphonic acids form tetrameric clusters isolating the mobile protons while the phosphonic acids in the hexagon form zigzag-type pathways through the sample.rnThe second part of this work demonstrates how acid-base pairing and the choice of appropriate spacers may influence proton conduction. Different ratios of statistical copolymers of poly (vinylphosphonic acid) and poly (4-vinylpyridine) were measured to derive information about the local structure and chemical changes. Though anhydrous proton conductivities of all statistical copolymers are rather poor, the conductivity increases to 10-2 S cm-1 when exposing the sample to relative humidity of 80%. In contrast to PVPA, anhydride formation of phosphonic acids in the copolymer is not reversible even when exposing the sample to a relative humidity of 100%.rnIn addition, the influence of both spacers and degree of backbone crystallinity on bulk proton conductivity was investigated. Unlike in systems such as poly benzimidazole (PBI), spacers were inserted between the protogenic groups along the backbone. It was found that dilution of the protogenic groups decreases the conductivity, but compared to PVPA, similar apparent activation energies for local motions were obtained from both variable temperature 1H NMR and impedance spectroscopy data. These observations suggest the formation of phosphonic acid clusters with high degrees of local proton motion, where only a fraction of motions contribute to the observable bulk proton conductivity. Additionally, it was shown that gradual changes of the spacer length lead to different morphologies.rnIn summary, applying advanced solid-state NMR and X-ray analysis, structural and dynamic phenomena in proton conducting materials were identified on a molecular level. The results were discussed with respect to different proton conduction mechanisms and may contribute to a more rational design or improvement of proton conducting membranes.rn

Representaciones Sociales de la Medicina Popular en el paciente oncológico adulto, la familia del paciente y los miembros del equipo de salud

Esta investigación tuvo como objetivo general develar las representaciones sociales sobre la Medicina Popular en tres grupos poblacionales, pacientes oncológicos (n=100), familiares de los pacientes (n=25) y miembros del equipo de salud (n=26). Para ello, se realizaron tres estudios cualitativos con cada grupo poblacional y un cuarto en el que se describen las similitudes y las diferencias entre ellos en relación con el objeto de representación. En general, se utilizaron entrevistas en profundidad, ejercicios de asociaciones libres y grupos focales (7 con 62 pacientes). Resultados: paciente oncológico: Medicina Popular representada como una salida optimista a la angustiante situación que está viviendo frente al cáncer; una apuesta a la vida. Para la familia: una contra capaz de mantener con vida y fortaleza al paciente y para el equipo de salud, una realidad incombatible de los pacientes y de la familia, que tiene efecto placebo sobre ellos y que está relacionada con el pensamiento mágico religioso, la fé y la ignorancia de quienes la realizan. En cuanto a las diferencias, el paciente y la familia consideran que la Medicina Popular es una alternativa en la que depositan su fé y confianza; el personal de salud no cree en sus efectos sobre el cáncer y la considera como estafa y engaño para el paciente. En las similitudes, todos coinciden en que es una alternativa, generadora de esperanza, basada en compuestos naturales que le permiten al paciente contribuir a la curación del cáncer y a sobrellevar el malestar provocado por la quimioterapia. Finalmente, se presentan conclusiones generales, se discuten algunos de los hallazgos y la importancia de las RS de la Medicina Popular y su impacto sobre la atención y la calidad de vida del paciente y se plantean algunos interrogantes que podrían favorecer el desarrollo de una línea de investigación en el tema.

Sistemi per il monitoraggio ecg domiciliare

È nata la necessità di trasferire nell’abitazione del paziente il percorso terapeutico, realizzando forme di assistenza a domicilio, che evitino da un lato il disagio dell’accesso alle strutture specialistiche, dall’altro che consentano di ridurre il carico di pazienti gestiti direttamente dalle strutture ospedaliere. Questi servizi sono in grado di favorire una delocalizzazione delle cure, decongestionando ospedali ed ambulatori. Questi sistemi di monitoraggio potranno così aiutare a risolvere una delle principali criticità del nostro servizio sanitario, ovvero la lunghezza delle liste d'attesa per le visite ambulatoriali,e contribuire a ridurre le spese per la loro erogazione. Nel mio elaborato discuto e analizzo due dispositivi in particolare il sensore BioHarness BH3 ed un prodotto innovativo studiato in Italia la MagIc.

1967-1987: l'altra civiltà del testo. Impulsi storici e scrittura nel teatro d'innovazione francese

Lo studio analizza le svolte nel teatro di innovazione francese prodotte dalla rivolta sociale e dalla sua rivoluzione culturale del 1968. La ricerca si è concentrata su tre livelli di analisi: un'analisi – storica, politica, sociale, culturale – dell'anno-tournant; un'analisi delle reazioni nel mondo del teatro contemporanee alla rivolta; un'analisi delle prassi spettacolari di lunga durata originate dall'evento. Sono stati, quindi, esaminati criticamente i testi cardine degli intellettuali ispiratori, protagonisti e interpreti della breccia culturale, per poi rintracciare i valori emersi all'interno del mondo dello spettacolo. La contestazione sociale ha agito sul mondo del teatro producendo delle ripercussioni immediate – l'occupazione dell'Odéon, la contestazione al XXII Festival d'Avignon, la produzione della Déclaration de Villeurbanne – e delle prassi di lunga durata che hanno agito sui processi formativi e creativi delle compagnie francesi che, dalla fine degli anni Sessanta, hanno prodotto creazioni collettive (in particolare il Théâtre du Soleil e il Théâtre de l'Aquarium, ma anche la Nouvelle Compagnie d'Avignon, il Grand Magic Circus e il Théâtre Populaire di Lorraine) e sul corpus drammaturgico e teorico di Michel Vinaver. Sono state, quindi, analizzate le relazioni che si sono instaurate tra i protagonisti appena nominati e i differenziati contesti, sociali e teatrali, facendo emergere nuove istanze creative. Tali istanze hanno saputo rispondere alle spinte etiche ed estetiche del momento storico, le hanno declinate sul piano delle prassi teatrali e rilanciate verso modalità nuove che hanno favorito l'emersione di una nuova civiltà del testuale.

Laser systems for collinear spectroscopy and the charge radius of 12 Be

Die kollineare Laserspektroskopie hat sich in den vergangenen drei Jahrzehnten zur Bestimmung der Kernladungsradien mittelschwerer und schwerer kurzlebiger Atomkerne in ausgezeichneter Weise bewährt. Auf die Isotope sehr leichter Elemente konnte sie allerdings erst kürzlich erweitert werden. Dieser Bereich der Nuklidkarte ist von besonderem Interesse, denn die ersten ab-initio Modelle der Kernphysik, die den Aufbau eines Atomkerns basierend auf individuellen Nukleonen und realistischenWechselwirkungspotentialen beschreiben, sind gegenwärtig nur für die leichtesten Elemente anwendbar. Außerdem existiertrnin dieser Region eine besonders exotische Form von Atomkernen, die sogenanntenrnHalokerne. Die Isotopenkette der Berylliumisotope zeichnet sich durch das Auftreten des Ein-Neutronen Halokerns 11Be und des Zwei- oder Vier-Neutronen-Halos 14Be aus. Dem Isotop 12Be kommt durch seine Position zwischen diesen beiden Exoten und den im Schalenmodell erwarteten magischen Schalenabschluss N = 8 eine besondere Bedeutung zu.rnIm Rahmen dieser Arbeit wurden mehrere frequenzstabilisierte Lasersysteme für die kollineare Laserspektroskopie aufgebaut. An TRIGA-SPEC stehen nun unter anderem ein frequenzverdoppeltes Diodenlasersystem mit Trapezverstärker und frequenzkammstabilisierter Titan-Saphirlaser mit Frequenzverdopplungsstufe für die Spektroskopie an refraktären Elementen oberhalb von Molybdän zur Verfügung, die für erste Testexperimente eingesetzt wurden. Außerdem wurde die effiziente Frequenzvervierfachung eines Titan-Saphirlasers demonstriert. An ISOLDE/CERN wurde ein frequenzkammstabilisierter und ein jodstabilisierter Farbstofflaser installiert und für die Laserspektroskopie an 9,10,11,12Be eingesetzt. Durch das verbesserte Lasersystem und den Einsatz eines verzögerten Koinzidenznachweises für Photonen und Ionen gelang es die Empfindlichkeitrnder Berylliumspektroskopie um mehr als zwei Größenordnungen zu steigern und damit die früheren Messungen an 7−11Be erstmals auf das Isotop 12Be auszuweiten. Außerdem wurde die Genauigkeit der absoluten Übergangsfrequenzen und der Isotopieverschiebungen der Isotope 9,10,11Be signifikant verbessert.rnDurch den Vergleich mit Ergebnissen des Fermionic Molecular Dynamics Modells kann der Trend der Ladungsradien der leichteren Isotope durch die ausgeprägte Clusterstruktur der Berylliumkerne erklärt werden. Für 12Be wird ersichtlich, dass der Grundzustand durch eine (sd)2 Konfiguration statt der vom Schalenmodell erwarteten p2 Konfiguration dominiert wird. Dies ist ein klares Indiz für das bereits zuvor beobachtete Verschwinden des N = 8 Schalenabschlusses bei 12Be.

Kollineare Laserspektroskopie an radioaktiven Praseodymionen und Cadmiumatomen

Die Analyse optischer Spektren liefert einen kernmodellunabhängigen Zugang zur Bestimmung der Kernspins, Ladungsradien und elektromagnetischen Momente von Atomkernen im Grundzustand und von langlebigen Isomeren. Eine der vielseitigsten Methoden zur optischen Spektroskopie an kurzlebigen Isotopen ist die kollineare Laserspektroskopie. Im Rahmen dieser Arbeit wurde zum einen die TRIGA-LASER Strahlstrecke am Institut für Kernchemie der Universität Mainz durch die Implementierung einer neuen offline Oberflächenionenquelle für hohe Verdampfungstemperaturen und eines Strahlanalysesystems weiterentwickelt. Zum anderen wurde kollineare Laserspektroskopie an kurzlebigen Praseodym- und Cadmiumisotopen an ISOLDE/CERN durchgeführt. Die neue Ionenquelle ermöglichte dabei den Test der kollinearen Laserspektroskopie an Praseodymionen am TRIGA-LASER Experiment. Die Spektroskopie der Prasdeodymionen motivierte sich aus der Beobachtung einer zeitlichen Modulation der EC-Zerfallsrate von wasserstoffähnlichem 140Pr58+. Für die Erklärung dieser sogenannten GSI Oszillationen wird unter anderem das magnetische Moment des Kerns benötigt, welches bislang noch nicht experimentell bestimmt wurde. Zudem wurde für wasserstoffähnliches 140Pr58+ überraschenderweise eine kleinere EC-Zerfallskonstante gemessen als für heliumähnliches 140Pr57+. Die Erklärung dieses Phänomens setzt ein positives magnetisches Moment voraus. Bei der Spektroskopie am COLLAPS Experiment wurden erstmals die magnetischen Momente von 135Pr, 136Pr und 137Pr vermessen. Aufgrund zu geringer Produktionsraten war die Spektroskopie des gewünschten Isotops 140Pr jedoch nicht erfolgreich. Die Untersuchung der Cadmiumisotope ist kernphysikalisch motiviert. In der Zinnregion erstrecken sich die Isotope über die beiden magischen Zahlen N=50 und N=82 bei gleichzeitiger Nähe des Z=50 Schalenabschlusses. Hier können verschiedene Kernmodelle getestet werden, die sich beispielsweise hinsichtlich der Stärke des N=82 Schalenabschlusses widersprechen. Diese Arbeit berichtet über erste Ergebnisse der Spektroskopie an Cadmiumatomen, die sich über die Isotope 106−124,126Cd sowie die zugehörigen langlebigen I=11/2− Isomere erstreckt. Die zuvor experimentell bekannten oder aus dem erweiterten Schalenmodell abgeleiteten Kernspins konnten für alle Isotope bis auf 119Cd bestätigt werden. Der Kernspin von 119Cd wurde eindeutig zu I=1/2 bestimmt. Die elektrischen Quadrupolmomente der Isomere zeigen ein bemerkenswert lineares Verhalten in Abhängigkeit von der Neutronenzahl und dies über die eigentliche Kapazität der 1h11/2 Unterschale hinaus. Die Änderungen der mittleren quadratischen Ladungsradien zeigen den auch an Indium- und Zinnisotopen beobachteten stetigen Verlauf. Der lineare Anteil passt sehr gut zu den Berechnung des Tröpfchenmodells in der Parametrisierung nach Berchidevsky und Tondeur. Die Differenzen der mittleren quadratischen Ladungsradien zwischen Grund- und isomeren Zustand der ungeraden Cadmiumisotope zeigen einen interessanten parabolischen Verlauf mit einem Minimum zwischen A=117 und A=119.

Spins, moments and radii of cd isotopes

The complex nature of the nucleon-nucleon interaction and the wide range of systems covered by the roughly 3000 known nuclides leads to a multitude of effects observed in nuclear structure. Among the most prominent ones is the occurence of shell closures at so-called ”magic numbers”, which are explained by the nuclear shell model. Although the shell model already is on duty for several decades, it is still constantly extended and improved. For this process of extension, fine adjustment and verification, it is important to have experimental data of nuclear properties, especially at crucial points like in the vicinity of shell closures. This is the motivation for the work performed in this thesis: the measurement and analysis of nuclear ground state properties of the isotopic chain of 100−130Cd by collinear laser spectroscopy.rnrnThe experiment was conducted at ISOLDE/CERN using the collinear laser spectroscopy apparatus COLLAPS. This experiment is the continuation of a run on neutral atomic cadmium from A = 106 to A = 126 and extends the measured isotopes to even more exotic species. The required gain in sensitivity is mainly achieved by using a radiofrequency cooler and buncher for background reduction and by using the strong 5s 2S1/2 → 5p 2P3/2 transition in singly ionized Cd. The latter requires a continuous wave laser system with a wavelength of 214.6 nm, which has been developed during this thesis. Fourth harmonic generation of an infrared titanium sapphire laser is achieved by two subsequent cavity-enhanced second harmonic generations, leading to the production of deep-UV laser light up to about 100 mW.rnrnThe acquired data of the Z = 48 Cd isotopes, having one proton pair less than the Z = 50 shell closure at tin, covers the isotopes from N = 52 up to N = 82 and therefore almost the complete region between the neutron shell closures N = 50 and N = 82. The isotope shifts and the hyperfine structures of these isotopes have been recorded and the magnetic dipole moments, the electric quadrupole moments, spins and changes in mean square charge radii are extracted. The obtained data reveal among other features an extremely linear behaviour of the quadrupole moments of the I = 11/2− isomeric states and a parabolic development in differences in mean square nuclear charge radii between ground and isomeric state. The development of charge radii between the shell closures is smooth, exposes a regular odd-even staggering and can be described and interpreted in the model of Zamick and Thalmi.

Spatial computing per smart devices

Magic Carpet, nato come un middleware orientato a una dimostrazione sullo spatial computing, che inizialmente coinvolgeva solo smart devices ed un tappeto di tag NFC, è il punto di partenza per uno studio sulle tecnologie abilitanti in tale campo. Il prodotto finale è una toolchain per lo sviluppo e la distribuzione, su dispositivi connessi, di applicazioni di spatial computing. Essa comprende un interprete per un DSL basato su un core calculus formalizzato, Field Calculus, e un middleware che supporta l'astrazione curando, a basso livello, le comunicazioni con il vicinato e le percezioni ambientali.

"Who Fears Death" di Nnedi Okorafor, una proposta di traduzione

This dissertaton deals with the translation of selected chapters from Nnedi Okorafor’s novel Who Fears Death. The novel, set in a post-apocalyptic Africa ravaged by inter-ethnic violence, narrates the tale of Onyesonwu, an Ewu, a half-breed born of rape, facing the rejection of her community. Growing up Onyesonwu realizes that the color of her skin is not the only thing that sets her apart from the other inhabitants of Jwahir, as she starts to manifest magical powers, and during an unintentional visit to the spirit realms she finds out that her biological father, a very powerful sorcerer, wants to kill her. At this point the only option left to her is to learn the secret arts of magic under the guidance of Aro, the sorcerer, and then embark on a journey to put and end to the menace posed by her biological father, stop the massacres between the Okeke and Nuru people, and rewrite history. This work is structured in five chapters. The first presents a brief retelling of the author’s life and works. The second chapter constitutes the theoretical frame according to which the novel will be described, and illustrates an analysis on the function of sci-fi literature. The third chapter introduces the novel itself, dealing with its setting and cultural peculiarities, the literary genre to which it belongs, and analysing the themes deemed most relevant, among which the racial and gender issues. The fourth chapter consists of the translation of some chapters from the novel Who Fears Death, and the fifth of a comment on the translation, presenting both a textual analysis, and notes on the choices deemed most interesting or challenging in a translation process perspective.

Spatial computing per dispositivi mobile ed embedded

Questa tesi si focalizza sulle possibili tecnologie per realizzare comunicazioni opportunistiche fra dispositivi mobile ed embedded, con l'obiettivo di integrarle nel contesto di sistemi a larga scala situati, e con particolare riferimento al prototipo denominato "Magic Carpet". Vengono considerate in particolare le tecnologie WiFi ad-hoc e Bluetooth Low Energy su Android e Raspberry Pi.

Biunal Lantern

A biunial magic lantern is a wooden box with two lenses, one on top of the other. The lenses have shutters and slots to insert glass slides. The light source is placed inside the box and the images are projected through either of the two lenses. It works in the same way as traditional magic lanterns, but allows for dissolving images and special effects.

Dads, Daughters, And Disney: The Historical Trajectory Of Fairy Tale Fathers And Daughters

In my thesis I use a historical approach to close readings of fairy tale texts and movies to study the evolution of fathers, daughters, and marriage within three landmark tales: ¿Cinderella,¿ ¿Sleeping Beauty,¿ and ¿Snow White.¿ Using the works of Giambattista Basile, Charles Perrault, Jacob and Wilhelm Grimm, and Walt Disney and his cohort of animators, I trace the historical trajectory of these three elements, analyzing both the ways they change and develop as history progresses as well as the ways they remain consistent. Through close and comparative readings of primary sources and films, I demonstrate the power structures and familial dynamics evident through the interactions of fathers and daughters. Specifically, I show that through the weakness and ineptitude of fairy tale fathers, fairy tale daughters are able to gain power, authority, and autonomy by using magic and marriage to navigate patriarchal systems. The work I have done is important because it explores how each tale is a product of the story before it and thus that in order for these tales to continue to survive the test of time, we must not only recognize the validity of the academic merit of the Disney stories, but also remember them and others as we forge new paths in the stories we use to teach both children and parents. Specifically, this work is important because it explores the historical trend evident in the evolving relationships between fathers and daughters. This relationship ultimately it reveals the deep underlying need for family within all of us.

Sensitivity Gains, Linearity, and Spectral Reproducibility in Nonuniformly Sampled Multidimensional MAS NMR Spectra of High Dynamic Range

Recently, we have demonstrated that considerable inherent sensitivity gains are attained in MAS NMR spectra acquired by nonuniform sampling (NUS) and introduced maximum entropy interpolation (MINT) processing that assures the linearity of transformation between the time and frequency domains. In this report, we examine the utility of the NUS/MINT approach in multidimensional datasets possessing high dynamic range, such as homonuclear C-13-C-13 correlation spectra. We demonstrate on model compounds and on 1-73-(U-C-13,N-15)/74-108-(U-N-15) E. coli thioredoxin reassembly, that with appropriately constructed 50 % NUS schedules inherent sensitivity gains of 1.7-2.1-fold are readily reached in such datasets. We show that both linearity and line width are retained under these experimental conditions throughout the entire dynamic range of the signals. Furthermore, we demonstrate that the reproducibility of the peak intensities is excellent in the NUS/MINT approach when experiments are repeated multiple times and identical experimental and processing conditions are employed. Finally, we discuss the principles for design and implementation of random exponentially biased NUS sampling schedules for homonuclear C-13-C-13 MAS correlation experiments that yield high-quality artifact-free datasets.

Eluding oblivion with smart stochastic selection of synaptic updates

The variables involved in the equations that describe realistic synaptic dynamics always vary in a limited range. Their boundedness makes the synapses forgetful, not for the mere passage of time, but because new experiences overwrite old memories. The forgetting rate depends on how many synapses are modified by each new experience: many changes means fast learning and fast forgetting, whereas few changes means slow learning and long memory retention. Reducing the average number of modified synapses can extend the memory span at the price of a reduced amount of information stored when a new experience is memorized. Every trick which allows to slow down the learning process in a smart way can improve the memory performance. We review some of the tricks that allow to elude fast forgetting (oblivion). They are based on the stochastic selection of the synapses whose modifications are actually consolidated following each new experience. In practice only a randomly selected, small fraction of the synapses eligible for an update are actually modified. This allows to acquire the amount of information necessary to retrieve the memory without compromising the retention of old experiences. The fraction of modified synapses can be further reduced in a smart way by changing synapses only when it is really necessary, i.e. when the post-synaptic neuron does not respond as desired. Finally we show that such a stochastic selection emerges naturally from spike driven synaptic dynamics which read noisy pre and post-synaptic neural activities. These activities can actually be generated by a chaotic system.