Synthesis, characterization and conformational studies of arylbenzylmaleimides

From the discoveries of Pasteur, stereochemistry has played an increasingly important role in the chemical sciences. In particular conformational study of molecules with axial chirality is object of intense research. Through Dynamic-NMR analysis and simulation of the spectra, the energy rotational barriers value of conformers are obtained. When this barrier is high sufficiently, atropisomeric stable compounds can be reached. They can be separated and used in stereo-synthesis and in packing processes. 3,4-bis-aryl maleimides, in which the aromatic groups are sufficiently bulky, generate atropisomeric stable configurations, that can be isolated at room temperature. The assignment of absolute configurations is performed through ECD analysis and comparison with computational calculations. The biological activities of maleimide derivatives widen the field of atropisomers application also in biological systems.

Georges Lemaître: a visionary contribute to the quest of the world model

The aim of this dissertation is to present the sequence of events which brought the scientific community of the early 20th century to conceive an expanding Universe born from a single origin. Among the facts here reported, some are well-known, some others instead are little-known backstories, not so easy neither to obtain nor to trust. Indeed, several matters shown in this thesis, now as then, create a battleground among scientists. Amid the numerous personalities whose contributions are discussed in this work, the main protagonist is surely Georges Lemaître, who managed to combine – without overlapping – his being both a priest and a scientist. The first chapter is dedicated to his biography, from his childhood in Belgium, to his early adulthood between England and the USA, to his success in the scientific community. The second and the third chapter explain how the race to the understanding of a Universe which not only expands, but also originated from a singularity, developed. The Belgian priest’s discoveries, as shown, were challenged by other important scientists, who, in several cases, Lemaître had a friendly relationship with. As a consequence, the fourth and final chapter deals with the multiple relations that the priest managed to build, thanks to his politeness and kindness. Moreover, it is also covered Lemaître’s personal connection with the Church and religion, without forgetting the personalities that influenced him – above all, Saint Thomas Aquinas. As a conclusion to this thesis, two appendices gather not only a summary of Lemaître’s works which are not already described in the chapters, but also the biographies of all the characters presented in this dissertation.

Benchmarking ’Expressing Without Asserting’ approaches on a large Wikidata dump

Semantic Web technologies provide the means to express the knowledge in a formal and standardized manner, enabling machines to automatically derive meaning from the data. Often this knowledge is uncertain or different degrees of certainty may be assigned to the same statements. This is the case in many fields of study such as in Digital Humanities, Science and Arts. The challenge relies on the fact that our knowledge about the surrounding world is dynamic and may evolve based on new data coming from the latest discoveries. Furthermore we should be able to express conflicting, debated or disputed statements in an efficient, effective and consistent way without the need of asserting them. We call this approach 'Expressing Without Asserting' (EWA). In this work we identify all existing methods that are compatible with actual Semantic Web standards and enable us to express EWA. In our research we were able to prove that existing reification methods such as Named Graphs, Singleton Properties, Wikidata Statements and RDF-Star are the most suitable methods to represent in a reliable way EWA. Next we compare these methods with our own method, namely Conjectures from a quantitative perspective. Our main objective was to put Conjectures into stress tests leveraging enormous datasets created ad hoc using art-related Wikidata dumps and measure the performance in various triplestores in relation with similar concurrent methods. Our experiments show that Conjectures are a formidable tool to express efficiently and effectively EWA. In some cases, Conjectures outperform state of the art methods such as singleton and Rdf-Star exposing their great potential. Is our firm belief that Conjectures represent a suitable solution to EWA issues. Conjectures in their weak form are fully compatible with Semantic Web standards, especially with RDF and SPARQL. Furthermore Conjectures benefit from comprehensive syntax and intuitive semantics that make them easy to learn and adapt.