Synthetic studies towards the total synthesis of hexacyclinic acid

In the first chapter of this thesis, published works found in the literature about hexacyclinic acid and FR182877 are reported and commented. A quick summary of the previous work done in the Prunet group is also described. In the second and third chapter, a more detailed account of the work undertaken during this PhD was given. Firstly, syntheses of two ABC tricycles incorporating tert-butyl and (trimethylsilyl)ethyl esters were undertaken. These syntheses include two key steps previously developed in the group, a diastereoselective Michael addition and a Snider cyclisation. Multiple conditions for the hydrolysis of the esters were attempted but none of them gave the desired product. The main part of this work is focused on the synthesis of a CDEF model and in particular about the development of the key step, the formation of a nine-membered ring. Several DEF fragments were synthesised in short synthetic sequences and as single isomers. Six different synthetic pathways were developed in total and a novel method, a Michael/elimination reaction, was found to be a very efficient way to close the desired medium-size ring. From the nine-membered ring, regioselective reduction and palladiumcatalysed allylic substitution led to the formation of the CDF tricycle. Final steps of the synthesis were fruitless and led only to decomposition. A synthesis of a chiral C-ring was also developed during this PhD. II Finally, another project was undertaken, not related to hexacyclinic acid. Methodology developed in the group for the diastereoselective formation of trisubstituted alkenes employing a temporary silicon-tethered ring-closing metathesis was extended to homoallylic alcohols. The first steps of the method were similar to the previous methodology but the end-game had to be modified in favour of an oxidation/reduction sequence to successfully obtain the desired products with the correct geometry. In the fourth chapter, procedures and analytical data for the synthesised compounds previously described are reported.

Urban public policies: towards the improvement of landscape ecological system. The case-study of the city of Évora, Portugal.

The Charter of European Planning 2013 presents a Vision for the future of European cities and regions, highlighting the sustainability of cities and the preservation of urban ecosystems, integrating the man-made environment with the natural ecosystems and contribute to the well-being and quality of life of their inhabitants and other stakeholders. Thus, urban public policies are crucial to the improvement of the landscape ecological system, achievable by city planning and design. The paper aims to analyse if public urban policies in Portugal have been integrating strategies and/or guidelines to enhance the ecological system of the landscape. Then, which new perspectives are possible, framed by the recently approved law Bases of Public Policy of Soils, Land Management and Urban Planning (2014). This new law, in contrast with the previous ones, don’t allow reserving land to urbanize, in municipal master plans. Moreover, it is possible to revert land classified for urban purposes in those plans into rustic soils (when it is not yet infra-structured or built). It allows creating new planning and design dynamics, convert several areas and including them in the urban ecological structure, essential to the enhancement of landscape ecological system. This is a filed of work where landscape architecture has huge responsibilities, by associating and harmonize man-made environment with natural systems, enlightening sustainability consistent with conservation and improvement of Nature while contributing to the well-being and quality of life of Man. A sustainability that is ethical, aesthetic, ecological and cultural. The study is supported by a case study – the city of Évora. The ultimate goal is to propose measures to promote larger and better integration of ecological component in urban public policies, framed by the new territorial management law, taking into account and highlighting the specificities of the landscape system – Man and Nature – at the local level.

3D Surveying and Data Management towards the Realization of a Knowledge System for Cultural Heritage

The research activities involved the application of the Geomatic techniques in the Cultural Heritage field, following the development of two themes: Firstly, the application of high precision surveying techniques for the restoration and interpretation of relevant monuments and archaeological finds. The main case regards the activities for the generation of a high-fidelity 3D model of the Fountain of Neptune in Bologna. In this work, aimed to the restoration of the manufacture, both the geometrical and radiometrical aspects were crucial. The final product was the base of a 3D information system representing a shared tool where the different figures involved in the restoration activities shared their contribution in a multidisciplinary approach. Secondly, the arrangement of 3D databases for a Building Information Modeling (BIM) approach, in a process which involves the generation and management of digital representations of physical and functional characteristics of historical buildings, towards a so-called Historical Building Information Model (HBIM). A first application was conducted for the San Michele in Acerboli’s church in Santarcangelo di Romagna. The survey was performed by the integration of the classical and modern Geomatic techniques and the point cloud representing the church was used for the development of a HBIM model, where the relevant information connected to the building could be stored and georeferenced. A second application regards the domus of Obellio Firmo in Pompeii, surveyed by the integration of the classical and modern Geomatic techniques. An historical analysis permitted the definitions of phases and the organization of a database of materials and constructive elements. The goal is the obtaining of a federate model able to manage the different aspects: documental, analytic and reconstructive ones.

Towards the Enabling City: Intermediate Places between Practices and Planning for Social Innovation in Bologna

The research investigates the interaction between social innovation practices and urban planning, assuming as a case study and field of application the city of Bologna, observed from the point of view of the production of urban policies and with respect to the places where it is practiced. Social innovation are localised actions tackling current urban complexities with micro-scale practices of service and urban production, by which new urban actors find answers to social needs, which are less afforded by the market and the public sectors. Planning and social innovation practices are two dimensions working in the city in different but complementary ways, subject to a mismatch. Through the lenses of interaction, the research explores the context of Bologna, a paradigmatic study and application field, a laboratory of innovative policies where a tradition of collective civic initiatives intertwines with a more responsible institutional planning framework. After drawing from area-based policies of Berlin and Barcelona, the thesis reads the role of specific intermediate places, mediators in bridging the level of institutions and the practices. Through an inventory and a cross-cutting taxonomy of intermediate places, the research draws the knowledge to inform a new urban model for the city of Bologna, aimed at overtake the mismatches by enabling the practices to act, allowing urban planning to frame them in a cross-fertilisation dimension. The proposed urban diagrammatic model, foresees intermediate places as local socio-urban observatories for research and development, interacting with both institutions and communities. The goal is to critically explore the limits and widen the meaning of the capacity of action of social innovation practices engaging in mutual-learning with the city. The model suggests a new possibility for reflection on urban planning as a more flexible approach, which translates the numerous experiences of the city into alternatives and multiple visions.

Towards the conservation of vulnerable marine large predators: morphometric, molecular and microchemical variation of historical sawfish rostra from Mediterranean collections

Sawfishes (Chondrichthyes, Pristidae) are considered one of the most endangered families among elasmobranchs. Extensive efforts are required worldwide to gather solid information on historical and recent changes in the composition/range of species. In this study, we have implemented an integrative approach to characterize the species diversity and the abundance of historical rostra of sawfishes from museums and private collections of the Mediterranean area. The identification at the species level of 172 dried rostra was carried out through the integration of both traditional and geometric morphometric techniques with molecular tools, allowing the assessment of a robust methodical approach to discriminate species. In addition, we analysed 35 rostral teeth to clarify the past distribution of sawfish species considering the isotopic composition of oxygen and carbon. The morphometric, molecular, and geographical characterization of samples was accompanied by the preliminary evaluation of growth structures and the inspection of the strontium isotope composition in two teeth to unravel movement patterns of individuals across different salinities of water. Results were integrated with currently available data from public repositories and showed that the historical specimens belonged to four nominal species: Pristis zijsron (81), Anoxypristis cuspidata (39), P. pristis (30), and P. pectinata (22). An identification error of 5.41% emerged in the morphological distinction of rostra between juvenile individuals of P. pectinata and P. zijsron. The new approach of carbon and oxygen isotopes, implemented for the first time in these taxa, permitted the identification of the high-probability habitat preferences of these benthopelagic elasmobranchs in about 50% of the analysed specimens. Using this multidisciplinary approach, we successfully assigned the numerous museum rostra with lacking data to a given species and identified their candidate geographical origin, retrieving novel information and data for understanding the species distribution and ecology of past, sometimes locally/regionally extinct sawfish faunas.

The EU’s foreign policy towards the Western Balkans during the Juncker Commission. The cases of Bosnia Herzegovina and Serbia.

In February 2018, four years after the President of the Commission Jean Claude Juncker explicitly deprioritised the enlargement dossier, the European Commission relaunched the enlargement strategy to the region of the Western Balkans. This occurred despite the persistent polarisation around the topic among the EU Member States and the still-present struggles, when not outright regression, of some of the countries in pursuing the demanded reforms. This thesis carries out a multilevel foreign policy analysis of EU foreign policy toward the region of the Western Balkans during the period of the Juncker Commission, through the cases of Bosnia Herzegovina and Serbia. Drawing from Actorness theory (Bretherton and Vogler 2006), combined with perspectives from new institutional leadership (Smeets and Beach 2020), and new intergovernmentalism (Moravcsik 2018; Bickerton et al. 2015), this study seeks to explain the relaunch of enlargement by examining three dimensions: the international context and the role of non-EU actors such as China, Russia, and Turkey; the EU context, through the interaction of the significant EU Member States and Institutions; finally, the local context, through the analysis of the changes in the local perception of the EU and the considered non-EU actors. This study posits two interconnected points: first, that the changes in the international context, specifically the increased presence of non-EU actors such as China, Russia, and Turkey in the region, acted as triggering factors for the relaunch of the strategy. In addition, it argues that this relaunch was successful due to the peculiar combination of Germany’s interests and leadership within the Council, coupled with the Commission’s priorities.

Multi-functional electrocatalysts for CO2 reduction reaction: towards the modulation of selectivity

The electrocatalytic reduction of CO2 (CO2RR) is a captivating strategy for the conversion of CO2 into fuels, to realize a carbon neutral circular economy. In the recent years, research has focused on the development of new materials and technology capable of capturing and converting CO2 into useful products. The main problem of CO2RR is given by its poor selectivity, which can lead to the formation of numerous reaction products, to the detriment of efficiencies. For this reason, the design of new electrocatalysts that selectively and efficiently reduce CO2 is a fundamental step for the future exploitation of this technology. Here we present a new class of electrocatalysts, designed with a modular approach, namely, deriving from the combination of different building blocks in a single nanostructure. With this approach it is possible to obtain materials with an innovative design and new functionalities, where the interconnections between the various components are essential to obtain a highly selective and efficient reduction of CO2, thus opening up new possibilities in the design of optimized electrocatalytic materials. By combining the unique physic-chemical properties of carbon nanostructures (CNS) with nanocrystalline metal oxides (MO), we were able to modulate the selectivity of CO2RR, with the production of formic acid and syngas at low overpotentials. The CNS have not only the task of stabilizing the MO nanoparticles, but the creation of an optimal interface between two nanostructures is able to improve the catalytic activity of the active phase of the material. While the presence of oxygen atoms in the MO creates defects that accelerate the reaction kinetics and stabilize certain reaction intermediates, selecting the reaction pathway. Finally, a part was dedicated to the study of the experimental parameters influencing the CO2RR, with the aim of improving the experimental setup in order to obtain commercial catalytic performances.

Investigation on the role of polymeric ligands in heterogeneous nanocatalysis towards the development of hybrid metal-polymer catalysts

The relationship between catalytic properties and the nature of the active phase is well-established, with increased presence typically leading to enhanced catalysis. However, the costs associated with acquiring and processing these metals can become economically and environmentally unsustainable for global industries. Thus, there is potential for a paradigm shift towards utilizing polymeric ligands or other polymeric systems to modulate and enhance catalytic performance. This alternative approach has the potential to reduce the requisite amount of active phase while preserving effective catalytic activity. Such a strategy could yield substantial benefits from both economic and environmental perspectives. The primary objective of this research is to examine the influence of polymeric hydro-soluble ligands on the final properties, such as size and dispersion of the active phase, as well as the catalytic activity, encompassing conversion, selectivity towards desired products, and stability, of colloidal gold nanoparticles supported on active carbon. The goal is to elucidate the impact of polymers systematically, offering a toolbox for fine-tuning catalytic performances from the initial stages of catalyst design. Moreover, investigating the potential to augment conversion and selectivity in specific reactions through tailored polymeric ligands holds promise for reshaping catalyst preparation methodologies, thereby fostering the development of more economically sustainable materials.

Towards the circularity of outdoor lighting systems

In recent years, there has been increasing attention to lighting energy efficiency, due to economics - lower energy costs - and environmental reasons - maninduced climate change. Driven by strict energy-efficiency requirements, the lighting industry started to replace the traditional lamps with LED lighting solutions, ignoring the limits of their maintenance and recycling. Faced with an increasing global population, rising resource consumption and associated negative environmental impacts, shifting from a traditional economic linear model to a more sustainable paradigm of growth is now becoming increasingly urgent. Whereas the topic of circular economy has been widely investigated in literature in the past, little attention has been reserved for the different evaluation tools to assess and improve product circularity and how companies can become more resource-efficient. Hence, the present thesis investigates the implementation of a circular economy in the lighting industry through the use of circularity indicators and ecodesign strategies. Concerning the real luminaire products, the role of the luminaire in the circular economy and recycling industry is explored, highlighting the limits of their End-of-life process. The main conclusions of the thesis reveal the significance of initial product development, reuse, remanufacturing and repair strategies in a transition towards a circular economy.

Towards the kinetic resolution of mechanically planar chiral rotaxanes

In this work, we reported the synthesis and characterization of two [2]rotaxanes endowed with a central ammonium group and two triazolium recognition stations on either side, acting as complexation sites for a dibenzo-24-crown-8 ether macrocycle. These mechanically interlocked architectures were obtained through the interlocking of a functionalized achiral macrocycle with Cs symmetry (where the symmetry element is a mirror plane corresponding to plane of the ring) and a C∞v symmetric axle (where a mirror plane and a C∞ principal axis are aligned along the axle length). We took advantage of the reversible acid/base triggered molecular shuttling of the ring between two lateral triazolium units to switch the rotaxanes between prochiral and mechanically planar chiral forms, which exists as two rapidly-interconverting co-conformers. We exploited the reactivity of the central amino group to attach an optically pure chiral substituent, with the goal of demonstrating the enantiomeric nature of the co-conformers and to obtain a non-zero diastereomeric excess in the resulting diastereomeric products through a dynamic kinetic resolution. To this end, two enantiopure reagents were chosen that could perform clean and fast reaction with amines: a sulfonyl chloride and an acyl chloride. Only the acyl chloride successfully produced an amide in high yield with the deprotonated rotaxane. The group added to the central amine station acted as a stopper against the shuttling of the macrocycle along the axis, thus preventing the fast interconversion of the two mechanically planar enantiomers. We analysed the results through static and dynamic NMR spectroscopic techniques by varying temperature and solvent used. Indeed, the presence of diastereomers was recorded alongside the configurational isomers resulting from the slow rotation of the CN-CO bond of the amide moiety, thus paving the way for a dynamic kinetic resolution.

Towards the sustainable production of methyl methacrylate: A comparative analysis of industrial chemical production processes using life cycle assessment methodology

Increasing environmental awareness has been a significant driving force for innovations and process improvements in different sectors and the field of chemistry is not an outlier. Innovating around industrial chemical processes in line with current environmental responsibilities is however no mean feat. One of such hard to overhaul process is the production of methyl methacrylate (MMA) commonly produced via the acetone cyanohydrin (ACH) process developed back in the 1930s. Different alternatives to the ACH process have emerged over the years and the Alpha Lucite process has been particularly promising with a combined plant capacity of 370,000 metric tonnes in Singapore and Saudi Arabia. This study applied Life Cycle Assessment methodology to conduct a comparative analysis between the ACH and Lucite processes with the aim of ascertaining the effect of applying principles of green chemistry as a process improvement tool on overall environmental impacts. A further comparison was made between the Lucite process and a lab-scale process that is further improvement on the former, also based on green chemistry principles. Results showed that the Lucite process has higher impacts on resource scarcity and ecosystem health whereas the ACH process has higher impacts on human health. On the other hand, compared to the Lucite process the lab-scale process has higher impacts in both the ecosystem and human health categories with lower impacts only in the resource scarcity category. It was observed that the benefits of process improvements with green chemistry principles might not be apparent in some categories due to some limitations of the methodology. Process contribution analysis was also performed and it revealed that the contribution of energy is significant, therefore a sensitivity analysis with different energy scenarios was performed. An uncertainty analysis using Monte Carlo analysis was also performed to validate the consistency of the results in each of the comparisons.

O marketing interno na ótica dos gestores de recursos humanos

Na sociedade atual as organizações estão cada vez mais conscientes do valor que têm os seus recursos humanos. Na Era da grande concorrência e mutações constantes dos serviços, lidera quem primar pela diferença, e sem dúvida que quem faz a diferença são os bons colaboradores. São estes talentos que as empresas querem atrair, motivar, desenvolver e reter. As organizações intentam aplicar o marketing interno, em detrimento das técnicas tradicionais de motivação e gestão dos colaboradores, sendo que aquelas procuravam ações e comportamentos nos colaboradores que possibilitassem atingir os objetivos da organização. O marketing interno assenta na ideia de que antes de satisfazer as necessidades e expectativas dos clientes externos, a organização deve preocupar-se em satisfazer as necessidades e expectativas dos clientes internos. O marketing interno possui ferramentas que utilizadas no seio da organização e de forma estratégica, podem ser cruciais para uma postura cada vez mais adequada, bem como para o comprometimento para com a empresa e desempenho dos colaboradores. Este projeto de investigação busca analisar a implementação do marketing interno, pelo próprio olhar dos gestores de recursos humanos de empresas portuguesas, tendo como objetivo central perceber a importância dada pelos gestores de recursos humanos ao marketing interno. Para tal recorreu-se à metodologia qualitativa, com recurso a entrevistas semiestruturadas, as quais serão analisadas através da análise de conteúdo, nomeadamente a análise temática ou categorial.

A comunicação do compromisso para com o desenvolvimento sustentável, das organizações portuguesas certificadas em qualidade, ambiente e segurança

Dissertação de mestrado em Engenharia Industrial (área de especialização em Qualidade, Segurança e Manutenção)