Design and development of new green catalytic methodologies for the synthesis of enantiomerically enriched molecules

The following Ph.D work was mainly focused on catalysis, as a key technology, to achieve the objectives of sustainable (green) chemistry. After introducing the concepts of sustainable (green) chemistry and an assessment of new sustainable chemical technologies, the relationship between catalysis and sustainable (green) chemistry was briefly discussed and illustrated via an analysis of some selected and relevant examples. Afterwards, as a continuation of the ongoing interest in Dr. Marco Bandini’s group on organometallic and organocatalytic processes, I addressed my efforts to the design and development of novel catalytic green methodologies for the synthesis of enantiomerically enriched molecules. In the first two projects the attention was focused on the employment of solid supports to carry out reactions that still remain a prerogative of omogeneous catalysis. Firstly, particular emphasis was addressed to the discovery of catalytic enantioselective variants of nitroaldol condensation (commonly termed Henry reaction), using a complex consisting in a polyethylene supported diamino thiopene (DATx) ligands and copper as active species. In the second project, a new class of electrochemically modified surfaces with DATx palladium complexes was presented. The DATx-graphite system proved to be efficient in promoting the Suzuki reaction. Moreover, in collaboration with Prof. Wolf at the University of British Columbia (Vancouver), cyclic voltammetry studies were reported. This study disclosed new opportunities for carbon–carbon forming processes by using heterogeneous, electrodeposited catalyst films. A straightforward metal-free catalysis allowed the exploration around the world of organocatalysis. In fact, three different and novel methodologies, using Cinchona, Guanidine and Phosphine derivatives, were envisioned in the three following projects. An interesting variant of nitroaldol condensation with simple trifluoromethyl ketones and also their application in a non-conventional activation of indolyl cores by Friedel-Crafts-functionalization, led to two novel synthetic protocols. These approaches allowed the preparation of synthetically useful trifluoromethyl derivatives bearing quaternary stereocenters. Lastly, in the sixth project the first γ-alkylation of allenoates with conjugated carbonyl compounds was envisioned. In the last part of this Ph.D thesis bases on an extra-ordinary collaboration with Prof. Balzani and Prof. Gigli, I was involved in the synthesis and characterization of a new type of heteroleptic cyclometaled-Ir(III) complexes, bearing bis-oxazolines (BOXs) as ancillary ligands. The new heteroleptic complexes were fully characterized and in order to examine the electroluminescent properties of FIrBOX(CH2), an Organic Light Emitting Device was realized.

Collaborative Change: Environmental Jolt, Network (Re)Design and Firm Performance

Motivated by the need to understand which are the underlying forces that trigger network evolution, we develop a multilevel theoretical and empirically testable model to examine the relationship between changes in the external environment and network change. We refer to network change as the dissolution or replacement of an interorganizational tie, adding also the case of the formation of new ties with new or preexisting partners. Previous research has paid scant attention to the organizational consequences of quantum change enveloping entire industries in favor of an emphasis on continuous change. To highlight radical change we introduce the concept of environmental jolt. The September 11 terrorist attacks provide us with a natural experiment to test our hypotheses on the antecedents and the consequences of network change. Since network change can be explained at multiple levels, we incorporate firm-level variables as moderators. The empirical setting is the global airline industry, which can be regarded as a constantly changing network of alliances. The study reveals that firms react to environmental jolts by forming homophilous ties and transitive triads as opposed to the non jolt periods. Moreover, we find that, all else being equal, firms that adopt a brokerage posture will have positive returns. However, we find that in the face of an environmental jolt brokerage relates negatively to firm performance. Furthermore, we find that the negative relationship between brokerage and performance during an environmental jolt is more significant for larger firms. Our findings suggest that jolts are an important predictor of network change, that they significantly affect operational returns and should be thus incorporated in studies of network dynamics.

Design And Implementation Of An End-To-End Simulator For The BepiColombo Rotation Experiment

Among the scientific objectives addressed by the Radio Science Experiment hosted on board the ESA mission BepiColombo is the retrieval of the rotational state of planet Mercury. In fact, the estimation of the obliquity and the librations amplitude were proven to be fundamental for constraining the interior composition of Mercury. This is accomplished by the Mercury Orbiter Radio science Experiment (MORE) via a strict interaction among different payloads thus making the experiment particularly challenging. The underlying idea consists in capturing images of the same landmark on the surface of the planet in different epochs in order to observe a displacement of the identified features with respect to a nominal rotation which allows to estimate the rotational parameters. Observations must be planned accurately in order to obtain image pairs carrying the highest information content for the following estimation process. This is not a trivial task especially in light of the several dynamical constraints involved. Another delicate issue is represented by the pattern matching process between image pairs for which the lowest correlation errors are desired. The research activity was conducted in the frame of the MORE rotation experiment and addressed the design and implementation of an end-to-end simulator of the experiment with the final objective of establishing an optimal science planning of the observations. In the thesis, the implementation of the singular modules forming the simulator is illustrated along with the simulations performed. The results obtained from the preliminary release of the optimization algorithm are finally presented although the software implemented is only at a preliminary release and will be improved and refined in the future also taking into account the developments of the mission.

Context-sensitive design in transportation infrastructure: relating tire/pavement noise with wearing course characteristics

A design can be defined as context-sensitive when it achieves effective technical and functional transportation solutions, while preserving and enhancing natural environments and minimizing impacts on local communities. Traffic noise is one of the most critical environmental impacts of transportation infrastructure and it affects both humans and ecosystems. Tire/pavement noise is caused by a set of interactions at the contact patch and it is the predominant source of road noise at the regular traffic speeds. Wearing course characteristics affect tire/pavement noise through various mechanisms. Furthermore, acoustic performance of road pavements varies over time and it is influenced by both aging and temperature. Three experimentations have been carried out to evaluate wearing course characteristics effects on tire/pavement noise. The first study involves the evaluation of skid resistance, surface texture and tire/pavement noise of an innovative application of multipurpose cold-laid microsurfacing. The second one involves the evaluation of the surface and acoustic characteristics of the different pavement sections of the test track of the Centre for Pavement and Transportation Technology (CPATT) at the University of Waterloo. In the third study, a set of highway sections have been selected in Southern Ontario with various types of pavements. Noise measurements were carried out by means of the Statistical Pass-by (SPB) method in the first case study, whereas in the second and in the third one, Close-proximity (CPX) and the On-Board Sound Intensity (OBSI) methods have been performed in parallel. Test results have contributed to understand the effects of pavement materials, temperature and aging on tire/pavement noise. Negligible correlation was found between surface texture and roughness with noise. As a general trend, aged and stiffer materials have shown to provide higher noise levels than newer and less stiff ones. Noise levels were also observed to be higher with temperature increase.