Molecular modelling of organic functional materials

The investigation of the mechanisms lying behind the (photo-)chemical processes is fundamental to address and improve the design of new organic functional materials. In many cases, dynamics simulations represent the only tool to capture the system properties emerging from complex interactions between many molecules. Despite the outstanding progresses in calculation power, the only way to carry out such computational studies is to introduce several approximations with respect to a fully quantum mechanical (QM) description. This thesis presents an approach that combines QM calculations with a classical Molecular Dynamics (MD) approach by means of accurate QM-derived force fields. It is based on a careful selection of the most relevant molecular degrees of freedom, whose potential energy surface is calculated at QM level and reproduced by the analytic functions of the force field, as well as by an accurate tuning of the approximations introduced in the model of the process to be simulated. This is made possible by some tools developed purposely, that allow to obtain and test the FF parameters through comparison with the QM frequencies and normal modes. These tools were applied in the modelling of three processes: the npi* photoisomerisation of azobenzene, where the FF description was extended to the excited state too and the non-adiabatic events were treated stochastically with Tully fewest switching algorithm; the charge separation in donors-acceptors bulk heterojunction organic solar cells, where a tight-binding Hamiltonian was carefully parametrised and solved by means of a code, also written specifically; the effect of the protonation state on the photoisomerisation quantum yield of the aryl-azoimidazolium unit of the axle molecule of a rotaxane molecular shuttle. In each case, the QM-based MD models that were specifically developed gave noteworthy information about the investigated phenomena, proving to be a fundamental key for a deeper comprehension of several experimental evidences

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

Development of a Computer-Based methodology for tolerance selection and optimization applied to the automotive sector

The design optimization of industrial products has always been an essential activity to improve product quality while reducing time-to-market and production costs. Although cost management is very complex and comprises all phases of the product life cycle, the control of geometrical and dimensional variations, known as Dimensional Management (DM), allows compliance with product and process requirements. Hence, the tolerance-cost optimization becomes the main practice to provide an effective application of Design for Tolerancing (DfT) and Design to Cost (DtC) approaches by enabling a connection between product tolerances and associated manufacturing costs. However, despite the growing interest in this topic, a profitable application in the industry of these techniques is hampered by their complexity: the definition of a systematic framework is the key element to improving design optimization, enhancing the concurrent use of Computer-Aided tools and Model-Based Definition (MBD) practices. The present doctorate research aims to define and develop an integrated methodology for product/process design optimization, to better exploit the new capabilities of advanced simulations and tools. By implementing predictive models and multi-disciplinary optimization, a Computer-Aided Integrated framework for tolerance-cost optimization has been proposed to allow the integration of DfT and DtC approaches and their direct application for the design of automotive components. Several case studies have been considered, with the final application of the integrated framework on a high-performance V12 engine assembly, to achieve both functional targets and cost reduction. From a scientific point of view, the proposed methodology provides an improvement for the tolerance-cost optimization of industrial components. The integration of theoretical approaches and Computer-Aided tools allows to analyse the influence of tolerances on both product performance and manufacturing costs. The case studies proved the suitability of the methodology for its application in the industrial field, providing the identification of further areas for improvement and refinement

Light & Electron beam - the perfect combination for the observation and application of photo active materials

The aim of the present PhD thesis is to investigate the properties of innovative nanomaterials for energy conversion. The materials have been deeply studied by means of a wide spectrum of different techniques based on both light and electron sources, in order to get an insight into the correlation between the properties of each material and the activity towards different energy conversion applications. The activity has been carried out in the framework of a collaboration between the “G.Ciamician” Chemistry Department of the University of Bologna and the CNR-IMM Bologna. Four main topics have been explored: in the first part, luminescent silicon nanocrystals (SiNCs) have been discussed, suggesting a new approach to improve their optical properties as active material in complementary optoelectronic devices and photovoltaic cells. The luminescence of SiNCs have been exploited to increase the efficiency of conventional photovoltaic cells by means of an innovative architecture. Specifically, SiNCs were shown to be very promising light emitters in luminescent solar concentrators (LSC). The second part of the work has been focused on the study of high phosphorescent molecular chromophores, suggesting a new approach in their use as optical sensors successfully applied to the field of polymeric materials. This is due to the enhanced emission of light that appears in rigid, constrained or crystalline state, that is commonly called: "Aggregation-Induced Emission (AIE)". Such phenomenon is characteristic for molecular structures such as persulfurated benzene chromophores, hereafter named asterisks. The last two parts were focused on conventional and in-situ Transmission Electron Microscopy (TEM) morphological and structural characterization of photoactive and catalytic materials for energetic applications and in particular water splitting

Forest responses to global change drivers: insights from temperate and tropical ecosystems

Forests, often likened to the lungs of our planet, are at the forefront of climate mitigation strategies. Understanding how major changes affecting the atmosphere (i.e., climate and pollutants) affect ecological and ecophysiological processes underpinning forest functioning is paramount to the preservation of essential ecosystem services they provide. In the era of global change, this thesis encompasses three scientific studies that together contribute to advancing our understanding of the intricate ecophysiological responses of both temperate and tropical forest ecosystems to diverse global change drivers. The initial two papers, focus on the impact of atmospheric nitrogen (N) deposition on two temperate forest ecosystems. These studies employ a long-term manipulative experiment, where the application of N fertilizer simulates the increase in N deposition. The first study investigates forest health under elevated N deposition by employing foliar nutrient and photosynthetic pigment concentrations as stress indicators. The second paper integrates measurements of N concentration and its isotopic composition across various forest compartments, coupled with molecular analyses of soil nitrogen functional genes, to characterize processes underpinning the N cycle. The third paper, delves into water and nutrient balances in a tropical montane cloud forest (TMCF). It underscores the imperative to address the knowledge gap on tropical forest ecosystems, which may be compromised by climate change, such as alterations in precipitation water regimes and rising temperatures. This study utilizes carbon (C) and N stable isotopes in soil and plant tissues to evaluate water-use efficiency and nutrient dynamics, highlighting the potential vulnerability of TMCFs to evolving climatic conditions. These studies articulate the challenges faced by forests. From the effects of N deposition on nutrient concentrations and N dynamics in temperate forests to the ecohydrological balance in the TMCFs, these insights deepen our comprehension of the complex interplay between human-induced changes and the resilience of forest ecosystems

Clinical efficacy of high dose brachytherapy with non-sealed 188Re (rhenium) resin in patients with "difficult to treat" basal cell carcinoma unfit for dermatologic surgery

Il carcinoma basocellulare(BCC) è il Non Melanoma Skin Cancers (NMSC) più frequente. I BCC considerando i criteri proposti dall’Associazione Europea di Dermato-Oncologia possono essere classificati in “easy-to-treat” e “difficult-to-treat”. La definizione di “difficult-to-treat” considera: (i)la difficoltà chirurgica a preservare la funzionalitá anatomica/estetica;(ii)i margini scarsamente definiti come nel sottotipo sclerodermiforme;(iii)area cutanea precedentemente sottoposta a radioterapia;(iv) multiple comorbidità del paziente. Lo scopo di questo studio retrospettivo é quello di valutare l’efficacia terapeutica della brachiterapia con la resina con 188renio nei pazienti affetti da BCC “difficult-to-treat” considerando i seguenti parametri: il tipo istologico, la sede anatomica trattata, la dimensione del BCC e i BCC naive o versus i pluritrattati. Sono stati inclusi nello studio i pazienti affetti da BCC “difficult-to-treat” e con spessore di infiltrazione inferiore ai 3 mm. Tra ottobre 2017 e dicembre 2022, sono stati arruolati 64 pazienti con etá media di 81 anni affetti da 82 BCC “difficult-to-treat”: 60 erano BCC nodulari, 9 sclerodermiformi e 13 superficiali. Il follow-up medio é risultato di 22 mesi. Tutte le lesioni che al follow-up con videodermatoscopia post trattamento con188renio risultavano sospette per recidiva di BCC sono state analizzate con biopsie multiple. La brachiterapia con l’applicazione della resina al 188Renio si é dimostrata una metodica estremamente efficace con una risoluzione del 93% dei BCC “difficult to treat” con un tempo medio alla recidiva di 23 mesi. Non sono state riscontrate differenze statisticamente significative di risposta alla brachiterapia considerando: (i)l’area anatomica trattata, (ii)la dimensione del tumore, (iii)i BCC precedentemente trattati versus i naive. Al contrario l’istotipo sclerodermiforme é risultato correlato a un rischio di recidiva piú alto rispetto al nodulare(p=0,03). L’analisi multivariata ha confermato che il BCC sclerodermiforme ha un rischio di recidiva 7 volte superiore rispetto al BCC nodulare(modello di Cox HR 7,2) e la recidiva si verifica circa 12 settimane prima.Basal cell carcinoma (BCC) is the most frequent non-melanoma skin cancer. The European Association of Dermato-Oncology (EADO) classification divides BCCs into 2 categories, “easy-to-treat” (common) and “difficult-to- treat”. The definition of "difficult-to-treat" considers: (i)the surgical difficulty in preserving the anatomical/aesthetic functionality; (ii) poorly defined margins as in the sclerodermiform subtype; (iii) prior radiotherapy; (iv) patient’s comorbidities interfering with surgery. The aim of this retrospective study is to evaluate the clinical efficacy of a single application of high-dose standardized brachytherapy using an unsealed 188Re in the management of “difficult to treat” BCC and to evalute the risk factors of recurrences considering the histological type, the anatomical site treated, the size of the BCC and naïve BCC or versus multi-treated BCC. Patients with "difficult-to-treat" BCC and with infiltration thickness less than 3 mm were included in the study. Between October 2017 and December 2022, 64 consecutive patients, affected by 82 histologically proven high-risk BCCs, were enrolled: 60 were nodular, 9 sclerodermiform and 13 superficial BCCs. The average follow-up was 22 months. All lesions that at follow-up with videodermoscopy were found to be suspicious for BCC recurrence were subjected to multiple skin biopsies. Brachytherapy with the application of 188 Rhenium resin has proven to be an extremely effective method with a resolution of 93% of "difficult to treat" BCCs with an average time to recurrence of 23 months. No statistically significant differences in response to brachytherapy were found considering: (i) the anatomical area treated, (ii) the size of the tumor, (iii) previously treated versus naive BCCs. On the contrary, the scleroderma histotype was correlated with a higher risk of recurrence compared to the nodular one (p=0.03). Multivariable analysis confirmed that sclerodermiform BCC has a 7-fold higher risk of recurrence than nodular BCC (Cox model HR 7.2) and recurrence occurs approximately 12 weeks earlier

Waste prevention: policy instruments and business model innovation

Waste prevention (WP) is a strategy which helps societies and individuals to strive for sufficiency in resource consumption within planetary boundaries alongside sustainable and equitable well-being and to decouple the concepts of well-being and life satisfaction from materialism. Within this dissertation, some instruments to promote WP are analysed, by adopting two perspectives: firstly, the one of policymakers, at different governance levels, and secondly, the one of business in the electrical and electronic equipment (EEE) sector. At a national level, the role of WP programmes and market-based instruments (extended producer responsibility, pay-as-you-throw schemes, deposit-refund systems, environmental taxes) in boosting prevention of municipal solid waste is investigated. Then, focusing on the Emilia-Romagna Region (Italy), the performances of the waste management system are assessed over a long period, including some years before and after an institutional reform of the waste management governance regime. The impact of a centralisation (at a regional level) of both planning and economic regulation of the waste services on waste generation and WP is analysed. Finally, to support the regional decision-makers in the prioritisation of publicly funded projects for WP, a framework for the sustainability assessment, the evaluation of success, and the prioritisation of WP measures was applied to some projects implemented by Municipalities in the Region. Trying to close the research gap between engineering and business, WP strategies are discussed as drivers for business model (BM) innovation in EEE sector. Firstly, an innovative approach to a digital tracking solution for professional EEE management is analysed. New BMs which facilitate repair, reuse, remanufacturing, and recycling are created and discussed. Secondly, the impact of BMs based on servitisation and on producer ownership on the extension of equipment lifetime is analysed, by performing a review of real cases of organizations in the EEE sector applying result- and use-oriented BMs

The relatedness multiplication of the unrelated ones. An ethnography of parenting and filiation expectations around the legal category of "unaccompanied foreign minor" in Italy.

Sulla spinta dell’approvazione della legge italiana 47/2017 “Disposizioni in materia di misure di protezione dei minori stranieri non accompagnati”, questo lavoro è teso ad affrontare le complesse aspettative genitoriali e parentali sviluppatesi intorno al processo di categorizzazione MSNA di cui questa legge è diventata approdo giuridico. Le controverse aspettative di accompagnamento legatesi alla denominazione di “non accompagnato”, prese come aspetto scontato e assiomatico in molta parte della letteratura scientifica che utilizza l’acronimo, sono state qui intese come un nodo ambiguo e questionabile. Attraverso una ricerca e una metodologia antropologico-etnografica queste rappresentazioni contradditorie sono esplorate a partire da un “crocevia di campi” da queste interessati in un territorio amministrativo dell’Italia Settentrionale variamente frequentato tra 2018 e 2021. Insieme ad ambienti, metodi e sfide della ricerca locale, una prima sezione situa storicamente e contestualmente la categoria MSNA come fenomeno in sé piuttosto che come efficace espressione descrittiva di soggetti. Le due sezioni successive, dedicate rispettivamente alla neo-realtà di tutela volontaria e a quella di una comunità socio-educativa/di tipo familiare rivolta a persone di minore età, interrogano invece questi ambienti come spazi e tempi di elaborazione prima e negoziazione poi di rappresentazioni e pratiche relazionali e parentali molteplici.Impelled by the approval of Italian Law 47/2017 “Provisions on protection measures for unaccompanied foreign minors”, this work aims to address the complex parental and kinship expectations that have developed around the “MSNA” (UFM, English acronym) categorisation process ‒ to which this law is the latest juridical landmark. Here, I have understood as ambiguous and questionable the controversial “accompaniment expectations” that have often gone along with the term “unaccompanied” and have been taken for granted in much of the scientific literature resorting to this acronym. Through anthropological-ethnographic research and methodology, these incongruous representations are explored from the “crossroads of fields” that affect them in an administrative territory of Northern Italy, variously frequented between 2018 and 2021. Together with the presentation of local research environments, methods, and challenges, the first section historically and contextually situates the MSNA category as a phenomenon itself rather than an effective subjects’ description. The next two sections are devoted to the exploration, respectively, of the neo-reality of volunteer guardianship, and of a more traditional socio-educational/family-type facility designed for minors’ reception. These latest parts interrogate these environments as spaces and times of negotiation about multiple kinship representations and practice

Impact of gentrification processes in rural landscapes: a methodology for landscape assessment towards sustainable rural development

With an increasing demand for rural resources and land, new challenges are approaching affecting and restructuring the European countryside. While creating opportunities for rural living, it has also opened a discussion on rural gentrification risks. The concept of rural gentrification encircles the influx of new residents leading to an economic upgrade of an area making it unaffordable for local inhabitants to stay in. Rural gentrification occurs in areas perceived as attractive. Paradoxically, in-migrants re-shape their surrounding landscape. Rural gentrification may not only cause displacement of people but also landscape values. Thus, this research aims to understand the twofold role of landscape in rural gentrification theory: as a possible driver to attract residents and as a product shaped by its residents. To understand the potential gentrifiers’ decision process, this research has provided a collection of drivers behind in-migration. Moreover, essential indicators of rural gentrification have been collected from previous studies. Yet, the available indicators do not contain measures to understand related landscape changes. To fill this gap, after analysing established landscape assessment methodologies, evaluating the relevance for assessing gentrification, a new Landscape Assessment approach is proposed. This method introduces a novel approach to capture landscape change caused by gentrification through a historical depth. The measures to study gentrification was applied on Gotland, Sweden. The study showed a population stagnating while the number of properties increased, and housing prices raised. These factors are not indicating positive growth but risks of gentrification. Then, the research applied the proposed Landscape Assessment method for areas exposed to gentrification. Results suggest that landscape change takes place on a local scale and could over time endanger key characteristics. The methodology contributes to a discussion on grasping nuances within the rural context. It has also proven useful for indicating accumulative changes, which is necessary in managing landscape values

Training competencies in managing Open Innovation processes. A case study.

Per comprende più a fondo il problema che le aziende affrontare per formare le persone in grado di gestire processi di innovazione, in particolare di Open Innovation (OI), è stato realizzato nel 2021 uno studio di caso multiplo di un percorso di educazione non formale all’OI realizzato dalla società consortile ART-ER e rivolto ai dottorandi degli atenei emiliano-romagnoli. Nella seconda fase di tale percorso formativo, per rispondere alle sfide di OI lanciate dalle aziende, sono stati costituiti 4 tavoli di lavoro. A ciascun tavolo di lavoro hanno preso parte 3/4 dottorandi, due referenti aziendali, un consulente e un operatore di ART-ER. Il campione complessivo era costituito da 14 dottorandi; 8 referenti aziendali di quattro aziende; 4 membri di una società di consulenza e 4 operatori della società consortile ART-ER. Il seguente interrogativo di ricerca ha guidato l’indagine: l’interazione tra i soggetti coinvolti in ciascun tavolo di lavoro – considerato un singolo caso - si configura come una Comunità di Pratica in grado di favorire lo sviluppo di apprendimenti individuali funzionali a gestire i processi di OI attivati nelle imprese? I dati sono stati raccolti attraverso una ricerca documentale a tavolino, focus group, interviste semistrutturate e un questionario semistrutturato online. L’analisi dei dati è stata effettuata mediante un’analisi qualitativa del contenuto in più fasi con l’ausilio del software MAXQDA. I risultati dimostrano che in tre casi su quattro, i tavoli di lavoro si sono configurati come una Comunità di Pratica. In questi tre tavoli inoltre è emerso lo sviluppo di alcune aree di competenza funzionali alla gestione dei processi di OI. Nella conclusione sono state presentate alcune proposte per la riprogettazione delle future edizioni del percorso formativo.To better understand the problem companies face in training people capable of managing innovation processes, in particular Open Innovation (OI), in 2021, a multiple case study of a non-formal training course – organized by the ART-ER consortium and aimed at doctoral students of Emilia-Romagna universities – was carried out. In the second phase of this training course, four working groups were set up to respond to OI challenges launched by companies. Three/four PhD students, two company representatives, a consultant and an ART-ER operator took part in each work table. The overall sample consisted of 14 PhD students, eight company representatives from four companies, four consultancy company members, and four ART-ER consortium company operators. The following research question guided the investigation: has the interaction between the subjects involved in each work table - considered a single case - configured as a Community of Practice capable of favouring the development of individual learning functional to managing the processes of OI activated in companies? The data was collected through desk research, focus groups, semi-structured interviews and a semi-structured online questionnaire. The data analysis was carried out through a qualitative analysis of the content in several stages with the help of the MAXQDA software. The results show that the working groups were configured as a Community of Practice in three out of four cases. In these three tables, the development of some areas of competence functional to the management of OI processes also emerged. In conclusion, some proposals for redesigning future editions of the training course were presented