Study of the second hyperpolarizability of poly(3-alkylthiophenes) using the third-harmonic scattering technique

During the past years, the considerable need in the domain of communications for more potent photonic devices has focused the research activities into the nonlinear optical (NLO) materials which can be used for modern optical switches. In this regard, a lot of research activities are focused on the organic materials and conjugated polymers which offer more advantages compared to the inorganic ones. On this matter, poly(3-alkylthiophene) (P3AT), an organic conjugated polymer, can be investigated as potential optical material with in particular the focus on the NLO properties such as the first- and second-hyperpolarizability, β and γ respectively. The activities carried out at the Laboratory of Polymer Synthesis of the KU Leuven, during the master's thesis work, focused on the study of conjugated polymers in order to evaluate their NLO properties for the future purpose of applications in optical systems. In particular, three series of polythiophenes functionalized with an alkyl side chain in the 3-position were synthesized: poly(3-hexylthiophene) (P3HT), poly[3-(2-ethylhexyl)thiophene] (P3EHT) and random copolymer of the two regio-isomers of P3HT. They were made in order to study the influence of molar mass, branching and regio-irregularity on the γ-value. The Kumada catalyst transfer condensative polymerization (KCTCP) and the Pd(RuPhos)-protocol were used for the polymerizations in order to have control over the molar mass of the growing chain and consequently to obtain well-defined and reproducible materials. The P3AT derivatives obtained were characterized by gel permeation chromatography (GPC), spectroscopic techniques (1H-NMR, UV-Vis) and the γ-value was investigated using the third-harmonic scattering (THS) technique. In particular, the THS technique is useful to investigate the optical behavior of the series of polymers in solution.

The creation and use of an international reference glossary specific for horror role-playing games

This thesis focuses on the technical approach to the translation of the Italian horror role-playing game Sine Requie into English. It aims to prove that both the role-playing and horror aspects of the genre are important to convey an enjoyable experience to the players, and that it is possible to create and international reference glossary to better translate the horror genre itself. Following a brief introduction of the history of role-playing games (RPGs), we will look at the RPG technical vocabulary in Sine Requie, and analyze which of these elements can be translated following the great models of the history of role-playing games. A brief introduction will follow regsrding the horror genre and its core characteristics based on the work of worldwide famous horror writer H.P. Lovecraft. Lastly, a description on how the international reference glossary for the horror genre was created will be presented along with a few examples of its practical use.

The use of remote sensing imagery for monitoring recovery in the aftermath of a natural disaster: the Hurricane Katrina Case

Although Recovery is often defined as the less studied and documented phase of the Emergency Management Cycle, a wide literature is available for describing characteristics and sub-phases of this process. Previous works do not allow to gain an overall perspective because of a lack of systematic consistent monitoring of recovery utilizing advanced technologies such as remote sensing and GIS technologies. Taking into consideration the key role of Remote Sensing in Response and Damage Assessment, this thesis is aimed to verify the appropriateness of such advanced monitoring techniques to detect recovery advancements over time, with close attention to the main characteristics of the study event: Hurricane Katrina storm surge. Based on multi-source, multi-sensor and multi-temporal data, the post-Katrina recovery was analysed using both a qualitative and a quantitative approach. The first phase was dedicated to the investigation of the relation between urban types, damage and recovery state, referring to geographical and technological parameters. Damage and recovery scales were proposed to review critical observations on remarkable surge- induced effects on various typologies of structures, analyzed at a per-building level. This wide-ranging investigation allowed a new understanding of the distinctive features of the recovery process. A quantitative analysis was employed to develop methodological procedures suited to recognize and monitor distribution, timing and characteristics of recovery activities in the study area. Promising results, gained by applying supervised classification algorithms to detect localization and distribution of blue tarp, have proved that this methodology may help the analyst in the detection and monitoring of recovery activities in areas that have been affected by medium damage. The study found that Mahalanobis Distance was the classifier which provided the most accurate results, in localising blue roofs with 93.7% of blue roof classified correctly and a producer accuracy of 70%. It was seen to be the classifier least sensitive to spectral signature alteration. The application of the dissimilarity textural classification to satellite imagery has demonstrated the suitability of this technique for the detection of debris distribution and for the monitoring of demolition and reconstruction activities in the study area. Linking these geographically extensive techniques with expert per-building interpretation of advanced-technology ground surveys provides a multi-faceted view of the physical recovery process. Remote sensing and GIS technologies combined to advanced ground survey approach provides extremely valuable capability in Recovery activities monitoring and may constitute a technical basis to lead aid organization and local government in the Recovery management.

Determinazione di amminotioli mediante elettroforesi capillare

The aminothiols are critical cellular components that play numerous and important roles in metabolism as key extracellular reducing agents, critical substrates for proteins synthesis and detoxificants of free radicals and peroxides. Because altered thiols levels in body fluids are linked to specific pathological conditions, their measurement is thus considered very important. One method to determine these compounds is the capillary electrophoresis, a technique that involves the separation of charged molecules on the basis of their movement under the influence of an applied electric field. The instrument used in this work is equipped with an amperometric detector recording the current of the thiols oxidized at the end of the capillary at a BDD electrode. The aim of this work is to find a valid method for the separations of the aminothiols analyzed, in terms of capillary coating and experimental conditions. In order to find an alternative and less expensive electrode than BDD and to increase sensitivity for the detection of the thiols, a modified electrode consisting in a carbon paste electrode containing Cobalt-phthalocyanine has been studied. In this electrode Cobalt-phthalocyanine works as electrocatalyst to enhance the oxidation reaction, meanwhile the graphite acts as conductive mean. This kind of electrode shows great sensibility and low detection limits for the thiols that have a free thiolic group, but it is not sensible to disulfides. The analysis of human plasma point out that the best method found for the capillary electrophoresis is not useful for the detection of aminothiols in a healthy person, because the very low concentrations in which they are present.

Operational Modal Analysis: the CEME Skywalk at UBC, Vancouver

Slender and lighter footbridges are becoming more and more popular to meet the transportation demand and the aesthetical requirements of the modern society. The widespread presence of such particular structures has become possible thanks to the availability of new, lightweight and still capable of carrying heavy loads material . Therefore, these kind of structure, are particularly sensitive to vibration serviceability problems, especially induced by human activities. As a consequence, it has been imperative to study the dynamic behaviour of such slender pedestrian bridges in order to define their modal characteristics. As an alternative to a Finite Element Analysis to find natural frequencies, damping and mode shape, a so-called Operational Modal Analysis is a valid tool to obtain these parameters through an ambient vibration test. This work provides a useful insight into the Operational Modal Analysis technique and It reports the investigation of the CEME Skywalk, a pedestrian bridge located at the University of British Columbia, in Vancouver, Canada. Furthermore, human-induced vibration tests have been performed and the dynamic characteristics derived with these tests have been compared with the ones from the ambient vibration tests. The effect of the dynamic properties of the two buildings supporting the CEME Skywalk on the dynamic behaviour of the bridge has been also investigated.

Identification of stock units of Mullus barbatus (Linnaeus, 1758) in the Italian seas: development of genomic 2b-RAD markers and biological variation analysis.

This thesis is settled within the STOCKMAPPING project, which represents one of the studies that were developed in the framework of RITMARE Flagship project. The main goals of STOCKMAPPING were the creation of a genomic mapping for stocks of demersal target species and the assembling of a database of population genomic, in order to identify stocks and stocks boundaries. The thesis focuses on three main objectives representing the core for the initial assessment of the methodologies and structure that would be applied to the entire STOCKMAPPING project: individuation of an analytical design to identify and locate stocks and stocks boundaries of Mullus barbatus, application of a multidisciplinary approach to validate biological methods and an initial assessment and improvement for the genotyping by sequencing technique utilized (2b-RAD). The first step is the individuation of an analytical design that has to take in to account the biological characteristics of red mullet and being representative for STOCKMAPPING commitments. In this framework a reduction and selection steps was needed due to budget reduction. Sampling areas were ranked according the individuation of four priorities. To guarantee a multidisciplinary approach the biological data associated to the collected samples were used to investigate differences between sampling areas and GSAs. Genomic techniques were applied to red mullet for the first time so an initial assessment of molecular protocols for DNA extraction and 2b-RAD processing were needed. At the end 192 good quality DNAs have been extracted and eight samples have been processed with 2b-RAD. Utilizing the software Stacks for sequences analyses a great number of SNPs markers among the eight samples have been identified. Several tests have been performed changing the main parameter of the Stacks pipeline in order to identify the most explicative and functional sets of parameters.

The contribution of the Finite Volume Point Dilution Method to the determination of solute mass flux in an alluvial aquifer.

Groundwater represents one of the most important resources of the world and it is essential to prevent its pollution and to consider remediation intervention in case of contamination. According to the scientific community the characterization and the management of the contaminated sites have to be performed in terms of contaminant fluxes and considering their spatial and temporal evolution. One of the most suitable approach to determine the spatial distribution of pollutant and to quantify contaminant fluxes in groundwater is using control panels. The determination of contaminant mass flux, requires measurement of contaminant concentration in the moving phase (water) and velocity/flux of the groundwater. In this Master Thesis a new solute flux mass measurement approach, based on an integrated control panel type methodology combined with the Finite Volume Point Dilution Method (FVPDM), for the monitoring of transient groundwater fluxes, is proposed. Moreover a new adsorption passive sampler, which allow to capture the variation of solute concentration with time, is designed. The present work contributes to the development of this approach on three key points. First, the ability of the FVPDM to monitor transient groundwater fluxes was verified during a step drawdown test at the experimental site of Hermalle Sous Argentau (Belgium). The results showed that this method can be used, with optimal results, to follow transient groundwater fluxes. Moreover, it resulted that performing FVPDM, in several piezometers, during a pumping test allows to determine the different flow rates and flow regimes that can occurs in the various parts of an aquifer. The second field test aiming to determine the representativity of a control panel for measuring mass flus in groundwater underlined that wrong evaluations of Darcy fluxes and discharge surfaces can determine an incorrect estimation of mass fluxes and that this technique has to be used with precaution. Thus, a detailed geological and hydrogeological characterization must be conducted, before applying this technique. Finally, the third outcome of this work concerned laboratory experiments. The test conducted on several type of adsorption material (Oasis HLB cartridge, TDS-ORGANOSORB 10 and TDS-ORGANOSORB 10-AA), in order to determine the optimum medium to dimension the passive sampler, highlighted the necessity to find a material with a reversible adsorption tendency to completely satisfy the request of the new passive sampling technique.