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"Don Juan of Borbón and Braganza and Carlism between 1840 and 1887"
No full textLa presente investigación tiene como objeto de estudio determinar las causas que llevaron al infante de España don Juan de Borbón y Braganza (1822-1887) -hijo del pretendiente carlista al trono de España don Carlos de Borbón-, a abrazar el liberalismo. Es por ello por lo que se aborda toda la trayectoria vital del príncipe, un personaje clave para entender el devenir del movimiento carlista en la segunda mitad del s. XIX. Fruto del estricto régimen educativo bajo el que fue formado durante su adolescencia, fue cultivando una animadversión hacia todo aquello que se comprendía dentro del orden tradicional del Antiguo Régimen, lo que ya en su madurez le llevaría a ir acercándose paulatinamente hacia las tesis liberales. Para 1860, cuando recayeron sobre él los derechos dinásticos, don Juan había renunciado ya a los principios doctrinales del tradicionalismo, circunstancia que ocasionó una crisis sin precedentes dentro del movimiento legitimista. No obstante, en la última etapa de su vida don Juan se reconcilió tanto con su familia como con el carlismo.The purpose of this research is to determine the causes which led the Spanish infant, don Juan de Borbón y Braganza (1822-1877)- son of the Carlista claimant don Carlos de Borbón- to embrace Liberalism. That is the reason why the whole path life of the prince is approached, a key character to understand the development of the Carlista Movement in the second half of the XIX century. Fruit of the strict educational regime under which he was formed during his adolescence, he cultivated a rejection of everything comprised within the traditional order of the Ancient Regime, what would lead him to the gradual approach to the liberal thesis in his maturity. By 1860, when all the dynastic rights fell on him, don Juan had already resigned to the doctrinal principles of Traditionalism, circumstance which caused an unprecedented crisis within the Legitimist Movement.Lo scopo di questa ricerca è determinare le cause che portarono il principe di Spagna don Juan de Borbón y Braganza (1822-1887) - figlio del pretendente carlista al trono di Spagna don Carlos de Borbón - ad abbracciare il liberalismo. Per questo motivo viene discussa l'intera vita del principe, una figura chiave per comprendere lo sviluppo del movimento carlista nella seconda metà del XIX secolo. A causa del rigido regime educativo in cui fu educato durante l'adolescenza, coltivò un'ostilità verso tutto ciò che rientrava nell'ordine tradizionale dell'Ancien Régime, che nella maturità lo avrebbe portato ad avvicinarsi gradualmente alle tesi liberali. Nel 1860, quando gli spettarono i diritti dinastici, don Juan aveva già rinunciato ai principi dottrinali del tradizionalismo, circostanza che provocò una crisi senza precedenti all'interno del movimento legittimista. Tuttavia, nell'ultima fase della sua vita don Juan si riconciliò sia con la famiglia che con il carlismo
Image-guided surgery in the treatment of rectal cancer: the impact of virtual and augmented reality in clinical practice.
No full textAim: To enhance minimally invasive surgery for rectal cancer using Augmented Reality (AR) to overlay preoperative 3D models onto intraoperative endoscopic images. Methods: Magnetic resonance neurography and computer tomography images were segmented to create a 3D virtual pelvic model, including rectum, nerves, vessels, and ureters. The pelvic structures were reconstructed as separate units, with the option to make them transparent. To address the persistent challenge of real-time instrument occlusion during intraoperative AR overlays, a binary segmentation ConvNext U-Net architecture was utilized. Initially, the neural network was pre-trained on a publicly available dataset of labelled laparoscopic surgical procedures. Subsequently, it was fine-tuned using an in-house dataset, specifically collected and labelled to enhance robustness during live surgeries. By identifying the pixel corresponding to the surgical instruments, the overlay was masked, ensuring that the instruments remained visible above the virtual model during the intraoperative phase. The abdominal aorta at the level of the bifurcation of the iliac arteries and the right iliac artery which intersects the ureter were used as anchor points to accurately superimpose the 3D model onto the real-time surgical image. Application of AR to retroperitoneal structures were preferred because they are fixed and less susceptible to deformation due to pneumoperitoneum. The critical and high-risk points of anterior rectum resection were identified to tailor the use of AR technology and restrict its application to the specific surgical steps where it is most needed. Results: The AR-assisted procedure was performed successfully in the operating room on two cases of laparoscopic rectal resection. During the AR-assisted procedures, the surgeon's ability to identify key pelvic anatomical structures, such as vessels, ureters, and nerves, was assessed. Conclusion: The study confirms the feasibility of using AR during rectal surgery and suggests that it could improve surgical safety by improving the identification of anatomical structures
Biological estimate of safe packaging through 3D-Bioprinted models
No full textFood packaging is critical for product safety, integrity, and efficient handling from production to consumers. However, food contact materials (FCMs) can release toxic chemicals into food, posing health risks such as endocrine disruption, cancer, and cardiovascular issues. Current toxicological testing focuses on individual substances, overlooking the complexity of chemical mixtures and non-intentionally added substances (NIAS). Currently, in vitro assays and animal testing are used, but they face limitations in replicating human systems and ethical challenges, emphasizing the need for innovative testing methods. Three-dimensional (3D) bioprinting offers a promising alternative by creating tissue-like constructs for more accurate toxicity screening. Using bioinks like methacrylated gelatin (GelMA) and collagen, this thesis explored ways to improve the mechanical stability, biocompatibility, and printability of hydrogels. An interpenetrating polymeric network (IPN) of GelMA and collagen was developed, exhibiting enhanced stability under dynamic conditions. Tyrosine-modified alginate hydrogels were also studied for enzymatic crosslinking, providing a safer and cell-friendly bioprinting approach. Additionally, a novel polymerization method, Frontal Polymerization (FP), was applied to synthesize semi-IPN hydrogels with tunable properties. Two 3D bioprinted liver models were developed for toxicity testing. The first combined GelMA-alginate IPN bioink with HepG2 cells, demonstrating stability and metabolic activity under dynamic conditions. The second model used decellularized liver extracellular matrix (dECM) with GelMA, showing superior metabolic activity and hepatotoxicity assessment accuracy compared to 2D cultures. This project characterized plastic packaging materials, identified migrating substances, and optimized hydrogels for 3D bioprinting. The advancements in hydrogel formulations and bioprinted liver models contribute to safer packaging assessments and more accurate toxicity testing, paving the way for improved biomedical applications and tissue engineering
Conceptualization and development of an intelligent decision support system for supply chain risk management in the automotive sector
No full textThe rapid rise of artificial intelligence in recent years has presented transformative opportunities for industries, including the automotive sector. Concurrently, the increasing complexity of global supply chains has introduced significant challenges, particularly in managing supply chain risks in this sector. In this context, intelligent decision support systems, which extend traditional decision support systems by incorporating artificial intelligence features, have shown great potential in addressing these challenges by offering data-driven insights and solutions. To this end, this thesis adopted a design science research approach to develop prescriptive knowledge on how to build an intelligent decision support system tailored to managing supply chain risk management activities within the automotive sector. The methodology involved extensive literature reviews combined with experimental design conducted in collaboration with an Italian automotive company. The research yielded several key contributions. First, a comprehensive framework was developed to guide the high-level design of an intelligent decision support system for supply chain risk management. Additionally, a generalized reference data model was created to inform the design of the database management system, which supports such an intelligent decision support system. Furthermore, valuable knowledge was generated on how to design predictive and prescriptive models within the model-based management system. Lastly, empirical results from a case study in the automotive sector demonstrated the tangible benefits of adopting intelligent decision support systems for managing supply chain risks
Development of copper-based Layered Double Hydroxides and derived oxides as innovative materials for photoelectrochemical CO2 conversion
No full textThe rising levels of atmospheric CO2 demand urgent, sustainable solutions to mitigate climate change. Photoelectrochemical (PEC) CO2 conversion, inspired by artificial photosynthesis, harnesses solar energy to transform CO2 into valuable fuels and chemicals, reducing emissions while enabling the production of renewable, carbon-neutral energy carriers to meet increasing global energy needs. Willing to contribute to the advancement of photoelectrochemical CO2 conversion through the exploration of novel photoelectroactive materials and operational conditions, this work present the development of copper-based Layered Double Hydroxides (Cu-LDHs) and derived Oxides (Cu-LDOs) as photocathode’s material for simultaneous light-absorption and CO2 catalytic conversion. By exploiting the unique properties of this class of compounds, i.e. variability in composition and CO2 affinity, photoelectrochemical CO2 conversion into C1-3 oxygenated products have been successfully performed in a PEC system. Taking advantage of reproducible and scalable synthetic procedures to produce both powders and photoelectrodes with 1 cm2 active area, i.e. coprecipitation and screen-printing technique, two different compositions of LDH, namely Cu/Mg/Al and Cu/Mg/Fe were obtained. Furthermore, full characterization of structure/morphology, photoelectrochemical, and catalytic properties allowed a deep understanding of the role of trivalent metal element within LDH structure on photocathodes performances and PEC CO2RR outcome. Moreover, LDH materials have been exploited as precursors for Layered Double Oxides which resulted a fruitful strategy to couple light absorbing, active sites, and reactant concentrating functionalities with CuMgAl-LDO photoelectrocatalyst giving the highest amount of acetic acid (0.84 µmol h-1 cm-2) among the investigated catalysts in this work, with remarkable faradaic efficiency of 60%. Besides, efforts in the optimization of reaction system have been attempted exploiting a PEC flow electrolyzer with larger active area Cu-LDHs-based electrodes (i.e. 10 cm2) made by an alternative deposition technique (i.e. spray coating). Here catalyst’s loading and conductive support choice have been assessed to guarantee the best compromise between catalytic performances and (photo)electroactivity
Evaluation of biostimulants and mycorrhizae to improve phytomanagement potential of lignocellulosic crops
No full textPhytomanagement of metal(loid)-contaminated sites involves cultivating high-yielding lignocellulosic crops to achieve two main goals: biomass production for bioenergy and progressive land decontamination. This approach is a sustainable and cost-effective alternative to conventional physico-chemical remediation techniques, which can negatively impact soil structure and fertility and are impractical for large-scale application. Contaminated sites commonly suffer from additional degradation factors which limit conventional crop cultivation. Biostimulants and microorganisms offer a promising strategy to enhance crop productivity while maintaining the cost-effectiveness and simplicity of phytomanagement systems. However, most studies on plant-biostimulant interactions focus on high-profit food crops, with limited research on lignocellulosic species. Moreover, existing studies are mostly conducted in controlled environments, often using metal-spiked soils without field validation. This thesis investigates the potential of biostimulants to enhance the phytomanagement efficiency of three promising lignocellulosic crops: Sorghum bicolor, Cannabis sativa, and Miscanthus × giganteus. Three biostimulants were tested: mycorrhizae (M), protein hydrolysates (B1), and humic substances (B2), applied alone or in combination. The study involved an upscaling from pot to field conditions, providing a progressive selection of crop and biostimulant combinations. Miscanthus × MB2 combination emerged as the most effective strategy and was further investigated in controlled environment, showing reduced Cu bioavailability (-21% in soil pore water) and increased root dry weight density (almost tripled). This enhanced root proliferation led to a 23% increase in shoot biomass from the second year in the field. Furthermore, the Arungro crop model was recalibrated to incorporate MB2 effects on Miscanthus productivity, confirming aboveground biomass as the key factor for phytoextraction potential. In conclusion, miscanthus cultivation paired with mycorrhizae and humic substances is a viable phytomanagement strategy to couple processable biomass production with progressive contaminant stripping and metal phytostabilization. It can be further implemented through the use of crop models that can simulate miscanthus productivity and metal-uptkae dynamics
Designing inclusive school environments and curriculum based on the Universal Design for Learning Approach
No full textLa Pedagogia Speciale, radicata nei principi della Pedagogia Istituzionale, promuove l’inclusione scolastica attraverso il riconoscimento della diversità e dell’equità come valori fondamentali. Una delle sfide attuali più complesse della scuola odierna è quella di rispondere alle diversità di bisogni, interessi, profili di apprendimento e di funzionamento degli alunni e delle alunne, con sistemi scolastici capaci di articolarsi in maniera flessibile e in relazione alle esigenze di ciascuno secondo la prospettiva dell’Educazione Inclusiva. In questo contesto, l’Universal Design for Learning (UDL) emerge come un modello efficace per rendere l’apprendimento accessibile a tutti, con evidenze scientifiche che ne dimostrano l’impatto positivo su studenti e insegnanti. Questa ricerca si inserisce in questo dibattito, esplorando la percezione degli studenti rispetto all’applicazione dell’UDL in Italia, un ambito ancora poco indagato. Sviluppato attraverso la metodologia della Ricerca-Azione-Formazione, secondo un approccio mixed methods, lo studio ha coinvolto 30 insegnanti e 185 studenti di scuola primaria in due Istituti Comprensivi di Reggio Emilia e Bologna. L’obiettivo principale è stato quello di progettare e sperimentare un curricolo inclusivo basato sui principi UDL, valutandone l’efficacia. In particolare, la ricerca ha esplorato la percezione degli studenti riguardo al benessere scolastico, alla motivazione all'apprendimento, alla partecipazione in classe e alla vita scolastica, oltre che l'incremento dei livelli di apprendimento e la promozione dell'inclusione degli alunni con disabilità, utilizzando strumenti quantitativi e qualitativi nelle diverse fasi pre e post-intervento. I risultati mostrano un incremento significativo del benessere percepito dagli studenti, una maggiore motivazione allo studio e partecipazione alla vita scolastica e un miglioramento nei livelli di apprendimento. Inoltre, l’approccio UDL ha favorito l’inclusione e la partecipazione attiva degli alunni con disabilità, contribuendo al raggiungimento degli obiettivi didattici ed educativi definiti nel Piano Educativo Individualizzato.Special Pedagogy, rooted in the principles of Institutional Pedagogy, promotes school inclusion by recognizing diversity and equity as fundamental values. One of the most complex challenges facing contemporary education is addressing the diverse needs, interests, learning profiles, and functional characteristics of students through flexible educational systems that adapt to individual requirements, in line with the perspective of Inclusive Education. In this context, the Universal Design for Learning (UDL) emerges as an effective model for ensuring accessible learning for all, with scientific evidence highlighting its positive impact on both students and teachers. This study contributes to this debate by investigating students’ perceptions of UDL implementation in Italy, an area that remains underexplored. Developed through the Action-Research-Training methodology and employing a mixed-methods approach, the study involved 30 primary school teachers and 185 students from two Comprehensive Institutes in Reggio Emilia and Bologna. The primary objective was to design and implement an inclusive curriculum based on UDL principles, assessing its effectiveness. Specifically, the research examined students’ perceptions of school well-being, learning motivation, classroom participation, and overall school life, as well as the enhancement of learning outcomes and the promotion of inclusion for students with disabilities. Quantitative and qualitative tools were applied at various stages of the pre- and post-intervention phases. The results indicate a significant increase in students' perceived well-being, greater motivation to study, and improved participation in school activities, alongside enhanced learning outcomes. Furthermore, the UDL approach has proven to foster the inclusion and active participation of students with disabilities, contributing to the achievement of educational and didactic objectives outlined in the Individualized Educational Plan (IEP)
Development of novel organocatalytic strategies for the asymmetric synthesis of chiral hydrazides
No full textChirality is a fundamental property of molecules that describes their asymmetry, resulting in two non-superimposable mirror images known as enantiomers. This phenomenon plays a crucial role in various fields, particularly in chemistry and pharmacology, where the spatial arrangement of atoms can significantly influence a compound's biological activity and therapeutic efficacy. The study of chirality encompasses the development of asymmetric synthesis methods, enabling the selective production of one enantiomer over another. In this regard, we pursuit the asymmetric synthesis of N-N atropisomers, initially discovered in the 1930s, that have recently gained attention due to their potential in drug development and biological activity. Our research contributes to this emerging field through an extensive computational study of the distinct rotational barriers associated with N-N atropisomeric hydrazides, which provides critical insights into their stability and reactivity. We also focused on the synthesis of enantio- and diastereo-enriched tetrasubstituted hydrazides, expanding the toolkit for creating chiral frameworks essential in pharmaceuticals. Moreover, we explored the synthesis of chiral enantiopure allylic hydrazides, which are of significant interest in medicinal chemistry. The asymmetric variant of the Tsuji-Trost reaction remains the most developed approach for generating these precious scaffolds; on the other side, advancements in electrophilic amination have been limited. To address this gap, we presented a novel method for synthesizing enantioenriched allylic hydrazides by employing azodicarboxylate as the electrophilic nitrogen source and allylic boronates as the donor, facilitated by a catalytic amount of chiral diol. Additionally, as side project conducted abroad, in the Nottingham University in the Silvi lab, photoredox catalysis has been employed as a sustainable and efficient approach to derivatize readily available feedstock like olefines in valuable compounds as 1,3 diols
Understory herb-layer dynamics and conservation strategies in the Casentinesi Forests National Park, Central Italy
No full textThis thesis aims to enhance the conservation of forest biodiversity by exploring the dynamics of understory herb-layer vascular plants in the National Park "Foreste Casentinesi, Monte Falterona and Campigna." The investigation focuses on i) the influence of elevation on inter- and intraspecific trait variation; ii) the temporal changes in taxonomic and functional diversity in relation to forest management practices; and iii) the role of dark diversity in understanding alien plant species and invasion risks. In Chapter I, I examined how elevation affects intraspecific trait variation and temporal turnover in understory herb-layer vascular plants, revealing insights into trait convergence and habitat filtering. Chapter II focused on the changes in taxonomic and functional diversity in an undisturbed forest over a decade, highlighting shifts in species composition and functional traits. Chapter III explored dark diversity and community completeness, assessing how unobserved species influence invasion risks posed by alien species. Our findings indicate that elevation significantly influences intraspecific trait variability, with higher elevations exhibiting greater trait convergence and distinct community compositions. The analysis of taxonomic and functional diversity over time demonstrated substantial changes, reflecting altered habitat quality and ecosystem stability following a strict protection regime, which has allowed natural processes to remain undisturbed. Dark diversity provided insights into potential community gaps and how unobserved species may influence invasion risk and habitat integrity. This research underscores the importance of incorporating intraspecific trait variation, functional diversity metrics, and dark diversity into conservation frameworks for forest understory vascular plants. By providing a more comprehensive understanding of community dynamics, functional traits complement existing biodiversity assessments and support the development of effective conservation strategies, ultimately enhancing forest biodiversity resilience in the face of ongoing environmental changes
Governing sustainable cities in the European multilevel context: the contribution of Città metropolitane
No full textL'elaborato analizza il crescente ruolo delle città nel contesto delle politiche europee. Per quanto la preminenza del principio di sovranità degli Stati abbia condotto ad una tendenziale disinteresse del diritto internazionale ed europeo verso gli enti locali, la moderna attenzione verso lo sviluppo sostenibile ed il contrasto al cambiamento climatico ha imposto un parziale mutamento di paradigma. La consapevolezza della necessità di coinvolgere le città nella sfida della transizione verde ha portato al proliferare di documenti ed atti non vincolanti dedicati alla vivibilità dei contesti urbani; cui si affianca la sempre più frequente destinazione di risorse per lo sviluppo urbano sostenibile. Il testo prosegue interrogandosi sulla capacità dell’ordinamento locale italiano di rispondere a tali stimoli, evidenziando criticità legate all'assenza di un ente di governo delle città, allo storico deficit strategico sull’evoluzione dei contesti urbani e all’attuale debolezza amministrativa e finanziaria degli enti locali. Viene riscontrata la capacità del dibattito europeo di incidere sulle evoluzioni del sistema locale italiano. Ciò è testimoniato, sul piano ordinamentale, da alcune innovazioni presenti nella legge Delrio; sul piano politico, dal crescente interesse per lo sviluppo territoriale sostenibile, cui anche il PNRR dedica attenzione. Lo scritto individua nelle Città metropolitane il soggetto istituzionale capace di rispondere a tale bisogno di governo dei fenomeni urbani in chiave sostenibile e multilivello, passando per il coordinamento tra attori istituzionali e non del territorio. L’analisi si concentra così sulle potenzialità della normativa delle Città metropolitane, senza tralasciare le contraddizioni che ne hanno limitato il pieno sviluppo. La parte conclusiva, anche grazie al confronto con l'esperienza spagnola di governo metropolitano, avanza proposte di riforma volte a rilanciare l'identità delle Città metropolitane, valorizzando la capacità di tali enti di definire politiche di sviluppo strategiche, integrate e sostenibili, nel segno della differenziazione territoriale.The paper analyzes the growing role of cities in the context of European policies. Although the primacy of the principle of State sovereignty has resulted in a tendency for international and European law to be indifferent to local authorities, the modern focus on sustainable development and combating climate change has forced a partial paradigm shift. The awareness of the need to engage cities in the challenge of the green transition has led to the proliferation of non-binding documents and acts dedicated to the livability of urban contexts; matched by the increasing allocation of resources for sustainable urban development. The paper goes on questioning the capacity of the Italian local system to respond to these impulses, highlighting critical issues related to the absence of a governing body for cities, the historical strategic deficit on the evolution of the urban contexts and the current administrative and financial weakness of local authorities. This is evidenced, on the normative side, by some innovations in the Delrio law; on the political side, by the growing interest in sustainable territorial development, to which even the PNRR devotes attention. The paper identifies the Città metropolitane as the institutional entity capable of responding to this need to govern the urban phenomena from a sustainable and multilevel perspective, enhancing cooperation between institutional and non-institutional actors in the territory. The analysis thus focuses on the potential of the regulatory framework of the Città metropolitane, not forgetting the contradictions that have limited its full development. The final part, partly thanks to the comparison with the Spanish experience of metropolitan government, presents reform proposals aimed at revitalizing the identity of Metropolitan Cities, boosting the ability of these entities to define strategic, integrated and sustainable development policies under the sign of territorial differentiation