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The photocatalytic degradation of the wastewater dye pollutant methylene blue (MB) at ZnO nanostructured porous thin films, deposited by direct current reactive magnetron sputtering on Si substrates, was studied. It was observed that over 4 photocatalytic cycles (0.3 mg · l−1 MB solution, 540 minUV irradiation), the rate constant k of MB degradation decreased by ∼50%, varying in the range (1.54 ÷ 0.78) · 10–9 (mol·l−1·min−1). For a deeper analysis of the photodegradation mechanism, detailed information on the nanostructured ZnO surface morphology and local surface and subsurface chemistry (nonstoichiometry) were obtained by using scanning electron microscopy (SEM) and x-ray photoelectron spectroscopy (XPS) as complementary analytical methods. The SEM studies revealed that at the surface of the nanostructured ZnO thin films a coral reef structure containing polycrystalline coral dendrites is present, and that, after the photocatalytic experiments, the sizes of individual crystallites increased, varying in the range 43 ÷ 76 nm for the longer axis, and in the range 28 ÷ 58 nm for the shorter axis. In turn, the XPS studies showed a slight non-stoichiometry, mainly defined by the relative [O]/[Zn] concentration of ca. 1.4, whereas [C]/[Zn] was ca. 1.2, both before and after the photocatalytic experiments. This phenomenon was directly related to the presence of superficial ZnO lattice oxygen atoms that can participate in the oxidation of the adsorbed MB molecules, as well as to the presence of surface hydroxyl groups acting as hole-acceptors to produce OH· radicals, which can be responsible for the generation of superoxide ions. In addition, after experiments, the XPS measurements revealed the presence of carboxyl and carbonyl functional groups, ascribable to the oxidation by-products formed during the photodegradation of MB.

Adsorption and advanced oxidation processes, especially photocatalysis, are amongst the most common water treatment methodologies. Unfortunately, using each of these techniques independently does not fully eliminate the pollutants of diverse nature, which are present in wastewater. Here, an avenue for multifunctional materials for water treatment is opened by reporting for the first time the preparation, characterization, and study of the properties of a novel multifunctional nanocomposite with both adsorption and visible-light-driven photocatalysis abilities. These multifunctional nanocomposites, namely iron (II, III) oxide/poly(N-isopropylacrylamide-co-methacrylic acid)/silver-titanium dioxide (Fe3O4/P(NIPAM-co-MAA)/Ag-TiO2), are prepared by combining magnetic polymeric microspheres (Fe3O4/P(NIPAM-co-MAA)) with silver-decorated titanium dioxide nanoparticles (Ag-TiO2 NPs). Cationic dyes, such as basic fuchsin (BF), can be adsorbed by the nanocomposites thanks to the carboxylic groups of Fe3O4/P(NIPAM-co-MAA) microspheres. Concomitantly, the presence of Ag-TiO2 NPs endows the system with the visible-light-driven photocatalytic degradation ability toward antibiotics such as ciprofloxacin (CIP) and norfloxacin (NFX). Furthermore, the proposed nanocomposites show antibacterial activity toward Escherichia coli (E. coli), thanks to the presence of silver nanoparticles (Ag NPs). Due to the superparamagnetic properties of iron (II, III) oxide nanoparticles (Fe3O4 NPs), the nanocomposites can be also recycled and reused, after the cleaning process, by using an external magnetic field.

Coronary artery disease (CAD) affects every fifth person in the world. The gold-standard treatment for CAD is stent implantation, however, the existing therapy is not sufficient due to many reasons. For instance, in-stent restenosis, biocompatibility, controlled degradation rate, protein adsorption, and adequate endothelialization are still the main concerns. In the last two decades, the field of stent technology has been grown rapidly and many new stent types and in vitro testing methods for stent characterization have been developed to minimize the aforementioned issues. In this vicinity, there are still many unaddressed issues: i) the quantitative analysis of corrosion is conducted with simpler samples made of stent material instead of stents, in most cases due to the absence of a mathematical model to calculate the entire stent surface area (ESSA); ii) in vitro stent testing in environments that are very far from actual physiological environments; iii) Evaluation of the influence of in-vitro test conditions on coated metallic stents; iv) absence of flow-induced shear stress (FISS) corrosion model, to mention a few. This thesis presents the novel ESSA model, the fluid dynamic experimental setup with the integration of various sensors and pH control, the influence of in vitro degradation behavior of the titanium oxynitride (TiOxNy) coated stainless steel stents and anodized AZ31 samples, and the FISS corrosion model. The results show some important contributions in this field, however, there is still a huge potential for the development of promising stent characterization solutions., Die koronare Herzkrankheit (KHK) betrifft jeden fünften Menschen auf der Welt. Der Goldstandard bei der Behandlung von KHK ist die Stent-Implantation, doch die bestehende Therapie ist aus vielen Gründen nicht ausreichend. So sind beispielsweise die Restenose im Stent, die Biokompatibilität, die kontrollierte Abbaugeschwindigkeit, die Proteinadsorption und die angemessene Endothelialisierung nach wie vor die Hauptprobleme. In den letzten zwei Jahrzehnten hat sich die Stenttechnologie rasant weiterentwickelt, und es wurden viele neue Stenttypen und In-vitro-Testmethoden zur Stentcharakterisierung entwickelt, um die oben genannten Probleme zu minimieren. In dieser Umgebung gibt es noch viele ungelöste Probleme: i) die quantitative Analyse der Korrosion wird mit einfacheren Proben aus Stentmaterial anstelle von Stents durchgeführt, in den meisten Fällen aufgrund des Fehlens eines mathematischen Modells zur Berechnung der gesamten Stentoberfläche (ESSA); ii) In-vitro-Stent-Tests in Umgebungen, die sehr weit von der tatsächlichen physiologischen Umgebung entfernt sind; iii) Bewertung des Einflusses von In-vitro-Testbedingungen auf beschichtete metallische Stents; iv) Fehlen eines FISS-Korrosionsmodells (flow-induced shear stress), um nur einige zu nennen. In dieser Arbeit werden das neuartige ESSA-Modell, der strömungsdynamische Versuchsaufbau mit der Integration verschiedener Sensoren und pH-Kontrolle, der Einfluss des In-vitro-Degradationsverhaltens der mit Titanoxynitrid (TiOxNy) beschichteten Edelstahlstents und anodisierten AZ31-Proben sowie das FISS-Korrosionsmodell vorgestellt. Die Ergebnisse zeigen einige wichtige Beiträge in diesem Bereich, jedoch gibt es noch ein großes Potenzial für die Entwicklung von vielversprechenden Lösungen zur Charakterisierung von Stents.