Dithienopyrrole-based materials: development of new polymeric derivatives

The possibility to control molar mass and termination of the growing chain is fundamental to create well-defined, reproducible materials. For this reason, in order to apply polydithienopyrrole (PDTP) as organic conjugated polymer, the possibility of controlled polymerization needs to be verified. Another aspect that is still not completely explored is bound to the optical activity of the PDTP, which bearing appropriate substituents may adopt a helical conformation. The configuration of the helix, built up from achiral co-monomers, can be established in an enantiopure way by using only a small percentage of the chiral monomer co-polymerized with achiral co-monomer. The effect, called “sergeants and soldiers effect”, is expressed by the nonlinear increase of the chiral response vs the ratio of the chiral co-monomer used for the polymerization. To date, this effect is still not completely explored for PDTP. In this framework the project will investigate, firstly, the possibility to obtain a controlled polymerization of PDTP. Then, monomers with different side chains and organometallic functions will be screened for a CTCP-type polymerization. Also a Lewis-acid based cationic polymerization will be performed. Moreover the chemical derivatization of dithienopyrrole DTP is explored: the research is going to concern also block copolymers, built up by DTP and monomers of different nature. The research will be extended also to the investigation of optically active derivates of PDTP, using a chiral monomer for the synthesis. The possibility to develop a supramolecular distribution of the polymeric chains, together with the “sergeants and soldiers effect” will be checked investigating a series of polymers with increasing amounts of chiral monomer.

Computational Analysis Based on Parametric Models of Historic Masonry Vaulted Structures Strengthened by Fiber-Reinforced Composite Materials

Historic vaulted masonry structures often need strengthening interventions that can effectively improve their structural performance, especially during seismic events, and at the same time respect the existing setting and the modern conservation requirements. In this context, the use of innovative materials such as fiber-reinforced composite materials has been shown as an effective solution that can satisfy both aspects. This work aims to provide insight into the computational modeling of a full-scale masonry vault strengthened by fiber-reinforced composite materials and analyze the influence of the arrangement of the reinforcement on the efficiency of the intervention. At first, a parametric model of a cross vault focusing on a realistic representation of its micro-geometry is proposed. Then numerical modeling, simulating the pushover analyses, of several barrel vaults reinforced with different reinforcement configurations is performed. Finally, the results are collected and discussed in terms of force-displacement curves obtained for each proposed configuration.

Knowledge-based Chord Embeddings

This thesis develops AI methods as a contribution to computational musicology, an interdisciplinary field that studies music with computers. In systematic musicology a composition is defined as the combination of harmony, melody and rhythm. According to de La Borde, harmony alone "merits the name of composition". This thesis focuses on analysing the harmony from a computational perspective. We concentrate on symbolic music representation and address the problem of formally representing chord progressions in western music compositions. Informally, chords are sets of pitches played simultaneously, and chord progressions constitute the harmony of a composition. Our approach combines ML techniques with knowledge-based techniques. We design and implement the Modal Harmony ontology (MHO), using OWL. It formalises one of the most important theories in western music: the Modal Harmony Theory. We propose and experiment with different types of embedding methods to encode chords, inspired by NLP and adapted to the music domain, using both statistical (extensional) knowledge by relying on a huge dataset of chord annotations (ChoCo), intensional knowledge by relying on MHO and a combination of the two. The methods are evaluated on two musicologically relevant tasks: chord classification and music structure segmentation. The former is verified by comparing the results of the Odd One Out algorithm to the classification obtained with MHO. Good performances (accuracy: 0.86) are achieved. We feed a RNN for the latter, using our embeddings. Results show that the best performance (F1: 0.6) is achieved with embeddings that combine both approaches. Our method outpeforms the state of the art (F1 = 0.42) for symbolic music structure segmentation. It is worth noticing that embeddings based only on MHO almost equal the best performance (F1 = 0.58). We remark that those embeddings only require the ontology as an input as opposed to other approaches that rely on large datasets.

Correlation between urban form and PM2.5 concentration — Evidence from the New York metropolitan Area and Shanghai city

With the development of the economy and society, air pollution has posed a huge threat to public health around the world, especially to people who live in urban areas. Typically, urban development patterns can be roughly divided into compact cities and urban sprawl. In recent years, the relationship between urban form and air quality (especially PM2.5) is gaining more and more attention from urban planners, environmentalists, and governments. This study is focusing on The New York metropolitan area and Shanghai city, which are both megacities but with different urban spatial forms. For both study areas,there are five main variables to measure the urban form metrics, naming Population Density, Artificial Land Area Per Ten Thousand People, Road Density, Green Land Area Ratio and Artificial Land Area Ratio. In addition, considering the impact of economic activities and public transportation, GDP per capita, Number of bus stop and Number of subway station are used as control variables. Based on the results of regression, a megacity like the New York metropolitan area with urban sprawl shows a low spatial correlation on PM2.5 concentration. Meanwhile, almost all the spatial form indicators effect on PM2.5 concentration is not significant. However, a compact megacity like Shanghai shows a diametrically opposite result. Urban form, especially population density, has a strong relationship with PM2.5 concentration. It can be predicted that a reduction in population density would lead to significant improvements on decrease the PM2.5 concentration in Shanghai. Meanwhile, increasing the ratio of green land and construction area per capita will get a positive influence on reducing PM2.5 concentration as well. Road density is not a significant factor for a megacity in both two urban forms. The way and type of energy used by vehicles on megacities maybe more critical.

Modeling, characterization and microalgal cultivation in an airlift panel photobioreactors.

Microalgae cultures are attracting great attentions in many industrial applications. However, one of the technical challenges is to cut down the capital and operational costs of microalgae production systems, with special difficulty in reactor design and scale-up. The thesis work open with an overview on the microalgae cultures as a possible answer to solve some of the upcoming planet issues and their applications in several fields. After the work offers a general outline on the state of the art of microalgae culture systems, taking a special look to the enclosed photobioreactors (PBRs). The overall objective of this study is to advance the knowledge of PBRs design and lead to innovative large scale processes of microalgae cultivation. An airlift flat panel photobioreactor was designed, modeled and experimentally characterized. The gas holdup, liquid flow velocity and oxygen mass transfer of the reactor were experimentally determined and mathematically modeled, and the performance of the reactor was tested by cultivation of microalgae. The model predicted data correlated well with experimental data, and the high concentration of suspension cell culture could be achieved with controlled conditions. The reactor was inoculated with the algal strain Scenedesmus obliquus sp. first and with Chlorella sp. later and sparged with air. The reactor was operated in batch mode and daily monitored for pH, temperature, and biomass concentration and activity. The productivity of the novel device was determined, suggesting the proposed design can be effectively and economically used in carbon dioxide mitigation technologies and in the production of algal biomass for biofuel and other bioproducts. Those research results favored the possibility of scaling the reactor up into industrial scales based on the models employed, and the potential advantages and disadvantages were discussed for this novel industrial design.

Recycling the city: a sustainable planning framework to reduce, reuse and recycle urban residual spaces

Cities are key locations where Sustainability needs to be addressed at all levels, as land is a finite resource. However, not all urban spaces are exploited at best, and land developers often evaluate unused, misused, or poorly-designed urban portions as impracticable constraints. Further, public authorities lose the challenge to enable and turn these urban spaces into valuable opportunities where Sustainable Urban Development may flourish. Arguing that these spatial elements are at the centre of SUD, the paper elaborates a prototype in the form of a conceptual strategic planning framework, committed to an effective recycling of the city spaces using a flexible and multidisciplinary approach. Firstly, the research focuses upon a broad review of Sustainability literature, highlighting established principles and guidelines, building a sound theoretical base for the new concept. Hence, it investigates origins, identifies and congruently suggests a definition, characterisation and classification for urban “R-Spaces”. Secondly, formal, informal and temporary fitting functions are analysed and inserted into a portfolio meant to enhance adaptability and enlarge the choices for the on-site interventions. Thirdly, the study outlines ideal quality requirements for a sustainable planning process. Then, findings are condensed in the proposal, which is articulated in the individuation of tools, actors, plans, processes and strategies. Afterwards, the prototype is tested upon case studies: Solar Community (Casalecchio di Reno, Bologna) and Hyllie Sustainable City Project, the latter developed via an international workshop (ACSI-Camp, Malmö, Sweden). Besides, the qualitative results suggest, inter alia, the need to right-size spatial interventions, separate structural and operative actors, involve synergies’ multipliers and intermediaries (e.g. entrepreneurial HUBs, innovation agencies, cluster organisations…), maintain stakeholders’ diversity and create a circular process open for new participants. Finally, the paper speculates upon a transfer of the Swedish case study to Italy, and then indicates desirable future researches to favour the prototype implementation.