Studio della reazione di isomerizzazione del d-glucosio

I carboidrati, come il D-glucosio, sono i principali costituenti della biomasse e potrebbero rappresentare un’alternativa concreta alla chimica tradizionale del petrolio per la produzione dei building-blocks, utili quest’ultimi per lo sviluppo della filiera produttiva della chimica industriale. Dal D-glucosio è possibile ottenere epimeri importanti per la medicina o zuccheri largamente utilizzati in campo alimentare come il D-fruttosio tramite isomerizzazione strutturale del D-glucosio. Attualmente, la maggior parte dei metodi di sintesi di questa molecole prevedono l’utilizzo enzimi, o la catalisi omogenea con impiego di grandi quantità di basi e acidi minerali dannosi per l’ambiente. Lo scopo di questo lavoro è stato lo studio di innovativi catalizzatori eterogenei capaci operare in soluzione acquosa la conversione acido catalizzata del D-glucosio in prodotti di epimerizzazione e isomerizzazione strutturale. I catalizzatori dei nostri test sono stati caratterizzati tramite tecniche BET, ATR-IR, DRUv-Vis e XRD. Lo studio, quindi, è stato focalizzato sulle valutazioni delle prestazioni catalitiche di questi sistemi e sull’individuazione, tramite caratterizzazione strumentale, degli ioni costituenti questi solidi responsabili delle alte selettività nelle reazioni di riarrangiamento strutturale del D-glucosio. Gli studi condotti hanno portato alla conclusione che, grazie all’utilizzo di questi sistemi inorganici è possibile ottenere con alte selettività prodotti di riarrangiamento strutturale del D-glucosio, evitando al contempo la degradazione del substrato che in genere accompagna queste reazioni in condizioni di catalisi acida. Ulteriori studi riguardanti questi catalizzatori apriranno con buone probabilità la strada allo sviluppo di un nuovo processo industriale per la sintesi di questi zuccheri derivati, rendendo possibile una via produttiva sostenibile da un punto di vista economico che ambientale.

Feasibility study and flow scheduling optimization of a multi-product pipeline system

The first goal of this study is to analyse a real-world multiproduct onshore pipeline system in order to verify its hydraulic configuration and operational feasibility by constructing a simulation model step by step from its elementary building blocks that permits to copy the operation of the real system as precisely as possible. The second goal is to develop this simulation model into a user-friendly tool that one could use to find an “optimal” or “best” product batch schedule for a one year time period. Such a batch schedule could change dynamically as perturbations occur during operation that influence the behaviour of the entire system. The result of the simulation, the ‘best’ batch schedule is the one that minimizes the operational costs in the system. The costs involved in the simulation are inventory costs, interface costs, pumping costs, and penalty costs assigned to any unforeseen situations. The key factor to determine the performance of the simulation model is the way time is represented. In our model an event based discrete time representation is selected as most appropriate for our purposes. This means that the time horizon is divided into intervals of unequal lengths based on events that change the state of the system. These events are the arrival/departure of the tanker ships, the openings and closures of loading/unloading valves of storage tanks at both terminals, and the arrivals/departures of trains/trucks at the Delivery Terminal. In the feasibility study we analyse the system’s operational performance with different Head Terminal storage capacity configurations. For these alternative configurations we evaluated the effect of different tanker ship delay magnitudes on the number of critical events and product interfaces generated, on the duration of pipeline stoppages, the satisfaction of the product demand and on the operative costs. Based on the results and the bottlenecks identified, we propose modifications in the original setup.

Synthesis of new non-fullerene acceptors based on indacenodithiophene core for organic solar cells

Due to the low cost, lightness and flexibility, Polymer Solar Cell (PSC) technology is considered one of the most promising energy technologies. In the past decades, PSCs using fullerenes or fullerene derivatives as the electron acceptors have made great progress with best power conversion efficiency (PCE) reaching 11%. However, fullerene type electron acceptors have several drawbacks such as complicated synthesis, a low light absorption coefficient and poor tuning in energy levels, which prevent the further development of fullerene-based PSCs. Hence the need to have a new class of electron acceptors as an alternative to conventional fullerene compounds. Non-fullerene acceptors (NFAs) have developed rapidly in the last years and the maximum PCEs have exceeded 14% for single-junction cells and 17% for double-junction tandem cells. By combining an electron-donating backbone, generally with several fused rings with electron-withdrawing units, we can simply construct NFA of the acceptor–donor–acceptor type (A–D–A). Versatile molecular structures have been developed using methods such as acceptor motif engineering and donor motif engineering. However, there are only a few electron-donating backbones that have been proved to be successful. Therefore, it is still necessary to develop promising building blocks to further enrich the structural diversity. An indacenodithiophene (IDT) unit with just five fused rings has a sufficiently rigid coplanar structure, which has been regarded as one of the promising electron-rich units to design high-performance A–D–A NFAs. In this work, performed at the King Abdullah University of Science and Technology in Saudi Arabia, a new nine-cyclic building block (TBIDT) with a two benzothiophene unit was synthesized and used for designing new non-fullerene electron acceptors.

Hidden Schrödinger symmetry in FLRW and Bianchi I minisuperspace models of cosmology and black holes Schwarzschild dynamics

A broad sector of literature focuses on the relationship between fluid dynamics and gravitational systems. This thesis presents results that suggest the existence of a new kind of fluid/gravity duality not based on the holographic principle. The goal is to provide tools that allow us to systematically unearth hidden symmetries for reduced models of cosmology. The focus is on the field space of these models, i.e. the superspace. In fact, conformal isometries of the supermetric leave geodesics in the field space unaltered; this leads to symmetries of the models. An innovative aspect is the use of the Eisenhart-Duval’s lift. Using this method, systems constrained by a potential can be treated as free ones. Moreover, charges explicitly dependent on time, i.e. dynamical, can be found. A detailed analysis is carried out on three basic models of homogenous cosmology: i) flat Friedmann-Lemaître-Robertson-Walker’s isotropic universe filled with a massless scalar field; ii) Schwarzschild’s black hole mechanics and its extension to vacuum (A)dS gravity; iii) Bianchi’s anisotropic type I universe with a massless scalar field. The results show the presence of a hidden Schrödinger’s symmetry which, being intrinsic to both Navier-Stokes’ and Schrödinger’s equations, indicates a correspondence between cosmology and hydrodynamics. Furthermore, the central extension of this algebra explicitly relates two concepts. The first is the number of particles coming from the fluid picture; while the second is the ratio between the IR and UV cutoffs that weighs how much a theory has of “classical” over “quantum”. This suggests a spacetime that emerges from an underlying world which is described by quantum building blocks. These quanta statistically conspire to appear as gravitational phenomena from a macroscopic point of view.