Spettroscopia di assorbimento di raggi X: apparato per misure in condizioni di illuminazione ottica differenziale come primo passo verso una misura risolta in tempo della struttura locale di molecole metallo-organiche

Il continuo sviluppo negli ultimi anni di diverse declinazioni della spettroscopia d'assorbimento a raggi X (XAS) con radiazione di sincrotrone ha permesso la determinazione della struttura locale di campioni di ogni tipo, dagli elementi puri, ai più moderni materiali, indagando e approfondendo la conoscenza di quei meccanismi che conferiscono a questi ultimi delle proprietà innovative e, a volte, rivoluzionarie. Il vantaggio di questa tecnica è quello di poter ottenere informazioni sulla struttura del campione soprattutto a livello locale, rendendo relativamente agevole l'analisi di sistemi senza ordine a lungo raggio, quali per esempio i film molecolari. Nell'elaborato verrà preliminarmente illustrata la fenomenologia della XAS e l’interpretazione teorica dell'origine della struttura fine. Saranno successivamente descritte le innovative tecniche di misura che permettono di studiare i cambiamenti della struttura locale indotti dall'illuminazione con luce visibile, inclusi gli esperimenti di tipo pump probe. Un capitolo della tesi è interamente dedicato alla descrizione dei campioni studiati, di cui sono stati analizzati alcuni dati acquisiti in condizioni statiche. Quest'analisi è stata compiuta sfruttando anche dei cammini di multiplo scattering dedicando particolare attenzione alla trattazione del fattore di Debye Waller. Nella parte principale della tesi verranno descritti la progettazione ed il test di un apparato sperimentale per l'acquisizione di spettri differenziali da utilizzare alla beamline BM08 dell'European Synchrotron Radiation Facility di Grenoble. Saranno presentate principalmente le modifiche apportate al software d'acquisizione della linea e la progettazione di un sistema ottico d'eccitazione da montare nella camera sperimentale. Nella fase di studio dell'ottica è stato creato in LabView un simulatore basato sul metodo Monte Carlo, capace di prevedere il comportamento del sistema di lenti.

The effects of hypocalcemia on spatial alternans and ventricular fibrillation studied with the optical mapping technique

The heart is a wonderful but complex organ: it uses electrochemical mechanisms in order to produce mechanical energy to pump the blood throughout the body and allow the life of humans and animals. This organ can be subject to several diseases and sudden cardiac death (SCD) is the most catastrophic manifestation of these diseases, responsible for the death of a large number of people throughout the world. It is estimated that 325000 Americans annually die for SCD. SCD most commonly occurs as a result of reentrant tachyarrhythmias (ventricular tachycardia (VT) and ventricular fibrillation (VF)) and the identification of those patients at higher risk for the development of SCD has been a difficult clinical challenge. Nowadays, a particular electrocardiogram (ECG) abnormality, “T-wave alternans” (TWA), is considered a precursor of lethal cardiac arrhythmias and sudden death, a sensitive indicator of risk for SCD. TWA is defined as a beat-to-beat alternation in the shape, amplitude, or timing of the T-wave on the ECG, indicative of the underlying repolarization of cardiac cells [5]. In other words TWA is the macroscopic effect of subcellular and celluar mechanisms involving ionic kinetics and the consequent depolarization and repolarization of the myocytes. Experimental activities have shown that TWA on the ECG is a manifestation of an underlying alternation of long and short action potential durations (APDs), the so called APD-alternans, of cardiac myocytes in the myocardium. Understanding the mechanism of APDs-alternans is the first step for preventing them to occur. In order to investigate these mechanisms it’s very important to understand that the biological systems are complex systems and their macroscopic properties arise from the nonlinear interactions among the parts. The whole is greater than the sum of the parts, and it cannot be understood only by studying the single parts. In this sense the heart is a complex nonlinear system and its way of working follows nonlinear dynamics; alternans also, they are a manifestation of a phenomenon typical in nonlinear dynamical systems, called “period-dubling bifurcation”. Over the past decade, it has been demonstrated that electrical alternans in cardiac tissue is an important marker for the development of ventricular fibrillation and a significant predictor for mortality. It has been observed that acute exposure to low concentration of calcium does not decrease the magnitude of alternans and sustained ventricular Fibrillation (VF) is still easily induced under these condition. However with prolonged exposure to low concentration of calcium, alternans disappears, but VF is still inducible. This work is based on this observation and tries to make it clearer. The aim of this thesis is investigate the effect of hypocalcemia spatial alternans and VF doing experiments with canine hearts and perfusing them with a solution with physiological ionic concentration and with a solution with low calcium concentration (hypocalcemia); in order to investigate the so called memory effect, the experimental activity was modified during the way. The experiments were performed with the optical mapping technique, using voltage-sensitive dye, and a custom made Java code was used in post-processing. Finding the Nolasco and Dahlen’s criterion [8] inadequate for the prediction of alternans, and takin into account the experimental results, another criterion, which consider the memory effect, has been implemented. The implementation of this criterion could be the first step in the creation of a method, AP-based, discriminating who is at risk if developing VF. This work is divided into four chapters: the first is a brief presentation of the physiology of the heart; the second is a review of the major theories and discovers in the study of cardiac dynamics; the third chapter presents an overview on the experimental activity and the optical mapping technique; the forth chapter contains the presentation of the results and the conclusions.

In-situ detection of defect formation in organic flexible electronics by Kelvin Probe Force Microscopy

Organic semiconductor technology has attracted considerable research interest in view of its great promise for large area, lightweight, and flexible electronics applications. Owing to their advantages in processing and unique physical properties, organic semiconductors can bring exciting new opportunities for broad-impact applications requiring large area coverage, mechanical flexibility, low-temperature processing, and low cost. In order to achieve highly flexible device architecture it is crucial to understand on a microscopic scale how mechanical deformation affects the electrical performance of organic thin film devices. Towards this aim, I established in this thesis the experimental technique of Kelvin Probe Force Microscopy (KPFM) as a tool to investigate the morphology and the surface potential of organic semiconducting thin films under mechanical strain. KPFM has been employed to investigate the strain response of two different Organic Thin Film Transistor with active layer made by 6,13-bis(triisopropylsilylethynyl)-pentacene (TIPS-Pentacene), and Poly(3-hexylthiophene-2,5-diyl) (P3HT). The results show that this technique allows to investigate on a microscopic scale failure of flexible TFT with this kind of materials during bending. I find that the abrupt reduction of TIPS-pentacene device performance at critical bending radii is related to the formation of nano-cracks in the microcrystal morphology, easily identified due to the abrupt variation in surface potential caused by local increase in resistance. Numerical simulation of the bending mechanics of the transistor structure further identifies the mechanical strain exerted on the TIPS-pentacene micro-crystals as the fundamental origin of fracture. Instead for P3HT based transistors no significant reduction in electrical performance is observed during bending. This finding is attributed to the amorphous nature of the polymer giving rise to an elastic response without the occurrence of crack formation.