10081 research outputs found
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Frontex and effective remedies: assessing mechanisms of legal protection in a shared enforcement space
No full textEU external border management has become a shared enforcement space, where EU and Member States’ authorities cooperate within a highly integrated and complex legal framework. With the expansion of its mandate, Frontex increasingly acts as the operational arm of national authorities while remaining shielded under the umbrella of EU competences. Within this setting, the division of powers and the attribution of responsibility between the Agency and Member States remain ambiguous, as does the attention given to the corresponding system of legal protection. Against this backdrop, the thesis addresses the research question: to what extent are individuals, particularly third-country nationals, able to enforce their rights and seek protection against breaches arising from EU actions? This thesis contributes to the academic debate on effective remedies for rights violations linked to Frontex’s activities, while also engaging with the broader discourse on judicial protection in the EU’s hybrid administrative system. The analysis extends beyond Frontex to other decentralised agencies operating within the AFSJ, whose remedial frameworks are equally complex. These agencies function within composite administrative structures, where decision-making and enforcement involve both EU and national actors in a deeply interdependent ways. The analysis reveals that the significant expansion of AFSJ agencies’ has not been accompanied by adequate oversight, creating an accountability gap that the EU judiciary alone cannot bridge. The lack of clear allocation of powers and effective accountability mechanisms underscores the urgent need to strengthen judicial protection while exploring alternative remedies, including administrative and extra-legal measures, to effectively address rights violations
Synthesis and manufacturing of customizable β-chitin materials from sea food waste
No full textThis thesis explores the valorization of β-chitin, one of the three polymorphic forms of chitin, the second most abundant biopolymer on earth after cellulose. Despite its abundance, β-chitin remains underutilized due to challenges like poor solubility and handling. Derived primarily from squid pens, β-chitin offers advantages over α-chitin, such as higher reactivity and flexibility. The study developed innovative β-chitin-based materials through chemical and physical approaches. Oxidation with ammonium persulfate introduced carboxylic groups at the C6 position, significantly enhancing water solubility and enabling diverse applications. These included hydrogels with tunable mechanical properties at pH 1, 5, and 7.4, and in the presence of ions such as Ca²⁺, Na⁺, and Mg²⁺; chitin-chitosan composite films with improved stability in acidic environments; and encapsulation carriers for carotenoids that preserved their antioxidant activity through digestion. Additionally, physical methods were employed to create β-chitin foams with thermal insulation properties comparable to expanded polystyrene (EPS). Customizable foams with water-repellent and cushioning properties were achieved, expanding potential applications. The final chapter explored the amorphization and re-crystallization of β-chitin, successfully avoiding transformation into the thermodynamically stable α-polymorph through metal-ion treatments. This research underscores the potential of β-chitin as a sustainable and versatile resource for creating customizable materials. By leveraging waste-derived resources and integrating chemical and physical strategies, this study expands the practical applications of this underutilized biopolymer
Development and characterization of coated PVC synthetic leather additivated with bio-fillers
No full textThe present research work, made in collaboration with Vulcaflex Spa, a leading company in PVC artificial leather production for car interiors, addresses the growing demand in the automotive industry for environmentally friendly materials. Agriculture generates substantial waste, including solid biomass, which presents an opportunity for sustainable resource utilization. This work focuses on developing composite artificial leather incorporating bio-fillers derived from natural waste materials, offering benefits such as cost reduction and increased bio-based content. Many bio-fillers, from different origins and chemical nature, were collected and tested in order to assess the effect of their addition on the workability of plasticized PVC formulations and on the final properties of the multilayer synthetic leather. Moreover, the most promising bio-fillers were fully characterized, including grain size analysis, SEM microscopy, and thermogravimetric analysis (TGA). Furthermore, synthetic leather with different bio-filler concentration were produced and this also highlighted critical considerations regarding their addition, such as the staining of the surface layer after aging and the moisture absorbed by the filler, which may result in defects in the final product. Solutions for these issues were studied and identified. Finally, industrial prototypes were made and their performance were evaluated, which demonstrated to be interesting compared to the standard synthetic leather
Bio-based additives for sustainable polymer and rubber applications: design, synthesis, and functional performance
No full textThe ongoing environmental crisis, exacerbated by human activities, has led to resource depletion and severe pollution of air, soil, and water. Among the contributors, plastic pollution stands out due to its long-term persistence and escalating production. Addressing this issue requires sustainable alternatives to petroleum-based plastics and additives. This PhD research develops and optimizes bio-based plasticizers and additives to reduce the environmental footprint of polymer and rubber industries without compromising performance or scalability.
A core focus of this work is the synthesis of Glycerol Trilevulinate (GT), a bio-based plasticizer derived from renewable feedstocks like glycerol and levulinic acid. GT was designed to enhance the mechanical properties, thermal stability, and processability of polymers such as polylactic acid (PLA) and polyhydroxybutyrate (PHB), which, despite their bio-based origins, face mechanical and processing limitations. Using techniques like solvent casting and molten processing, GT demonstrated significant improvements in flexibility, crystallinity, and thermal behavior, enabling suitability for industrial applications like extrusion, injection molding, and 3D printing. Comparative studies with conventional plasticizers such as DINCH and ATBC highlighted GT's superior biodegradability, migration resistance, and stability, along with its low toxicity profile, underscoring its potential for sustainable polymer systems.
Beyond bioplastics, this thesis explores GT in natural rubber (NR) and epoxidized natural rubber (ENR), enhancing their flexibility, crosslinking behavior, and recyclability. GT combined with hexamethylene diamine (HMDA) enabled the development of a bio-based, reversible crosslinking system for ENR, aligning with circular economy principles. Additionally, the synthesis and application of Triphenyl Acetic Glyceroate (TPAG) for food packaging materials were investigated, offering solutions to improve PLA's mechanical and barrier properties.
This research demonstrates the potential of bio-based additives to reduce reliance on fossil-based resources, minimize plastic waste, and foster sustainable materials for diverse industrial applications
Development and implementation of chemometric and spectroscopic methods for process studies, with particular reference to the Near-Infrared radiation.
No full textNear-infrared spectroscopy (NIRS) is widely used in industry for safety and quality control due to its rapid, non-destructive, and accurate analysis. However, challenges arise from overlapping absorption bands and background noise, necessitating the use of chemometric techniques such as principal component analysis (PCA) and partial least squares (PLS) regression. PCA simplifies spectral data while PLS regression builds predictive models to estimate component concentrations. This study integrates chemometric models with NIRS in the plastic additives (PA) industry, where PA enhance plastic properties like durability and thermal stability. Using PLS regression, eight offline and two online multivariate models were developed for quality control and real-time monitoring, achieving high R² values (>99%) and robust RPD indices (>10), reducing material consumption and enabling quantification of difficult analytes. Given NIRS's compatibility with online processes, models were also applied in polyurethane (PU) production. Specifically, a two-tiered NIR model quantified water content in the A-Component, achieving R² values of 99.8% and 99.7%, and another model monitored the free NCO number in the polyaddition reaction with R² of 99.7%. Additionally, quantum chemical calculations using density functional theory (DFT) and vibrational perturbation theory (VPT2) were conducted to simulate NIR spectra, aiding in spectral feature assignment for molecules like DEHA, DEAA, HOP, and TEMPO-H. These findings enhance the understanding of spectral transitions and support further investigations into PA and PU analysis
Dissecting the crosstalk between glucocorticoids and growth factors: implications for cardiac regenerative therapies
No full textUnlike certain lower vertebrates with remarkable regenerative abilities, humans and other mammals face limitations in regenerating tissues and organs. As a result, myocardial injuries in mammals often lead to heart failure, driven by the irreversible death and loss of cardiomyocytes and the heart's insufficient regenerative capacity to replace them. We recently demonstrated that physiological glucocorticoids reduce cardiomyocyte proliferation and regeneration by activating the Glucocorticoid Receptor (GR). Transcriptomic data from cultured cardiomyocytes treated in vitro with glucocorticoids revealed that glucocorticoids induce the expression of DUSP1 and ERRFI1, which are negative regulators of MAPK/ERK signaling. This pathway is pivotal in mediating the cardiac regenerative effect of RTK-dependent growth factors such as NRG1, FGF1, IGF2, IGF1, as well as RTK-independent growth factors and cytokines like BMP7, OSM, LIF, RANKL, IL6, IL13, IL4, and IL1-β. Glucocorticoids inhibited cardiomyocyte proliferation induced by all these regenerative factors. Using NRG1 as the primary model system for cardiac regenerative factors, we demonstrate that glucocorticoids suppress growth factor-induced ERK phosphorylation, nuclear translocation, and the transcription of Immediate Early Genes (IEGs). Importantly, knock-down experiments targeting Dusp1 and Errfi1 confirmed their specific involvement in corticosterone-induced inhibition of growth factor-induced mitogenic potential. We also observed that the expression of GR targets, including the MAP kinase negative regulators Dusp1 and Errfi1, increases during early postnatal development. Notably, GR antagonism during this period preserved MAPK/ERK pathway activity. In line, inhibition of DUSP1 in post-mitotic cardiomyocytes restored growth factor-induced MAPK pathway activation and proliferation. In post-mitotic cardiomyocytes, antagonizing or ablating the glucocorticoid receptor was sufficient to restore NRG1-induced mitogenic capacity. Finally, GR antagonization combined with NRG1 administration induced cardiomyocytes cell cycle activity and preserved cardiac function in adult mouse models of cardiac damage induced by anthracycline administration. We propose the transient inhibition of GCs/GR activity as a promising strategy for enhancing MAPK-based cardiac regenerative therapies
Revealing hidden biodiversity before losing it: the lichens of the Dolomites and the challenge of global change
No full textMountain ecosystems are critically affected by climate change and anthropogenic pressures. Poikilohydric organisms like lichens, whose physiology is directly coupled to environmental conditions, may face severe extinction risk and habitat reduction. Despite their ecological importance and widespread use as bioindicators, lichens are often underrepresented in conservation policies due to fragmented and insufficient data. The Dolomites, with their unique topography, represent one of the most lichenologically best-known areas in Italy, but the data are scattered in various sources, hampering their accessibility. The Dolichens project addressed this gap by aggregating over 77,000 occurrences spanning 1820 to 2024 for 2071 infrageneric taxa, into an open-access database (https://italic.units.it/dolichens), setting a basis for forthcoming taxonomic, biogeographical, and ecological studies. Thanks to the data aggregation and collection promoted by the project, we compiled the checklists of the lichenized fungi of the Paneveggio-Pale di San Martino Natural Park and the Adamello-Brenta Natural Park. These recent targeted surveys led to the discovery of species new to the region, Italy, and even the science including a soon-to-be-described Lecanora species. Exploiting the Dolichens database, species distribution models were performed to investigate the range shifts of 272 lichens under different climate change scenarios. We predicted a huge habitat suitability loss in the future, particularly for fruticose and cold-adapted species. Contrary to expectations of upward range shifts, species showed complex redistribution patterns, emphasizing the urgent need for targeted conservation actions. Finally, we developed innovative methods to assess lichen diversity in forest ecosystems: simplified approaches targeting functional groups and the indicator species Lobaria pulmonaria (LIFE MODERn), and an AI-driven system for large-scale epiphytic lichen monitoring (Smart Forest Monitoring). This thesis underscores the critical role of data repositories like Dolichens in tracking biodiversity, assessing ecological changes, and directing efforts to mitigate global change impacts on vulnerable organisms like lichens
Multidisciplinary analyses for the study of the venetian lagoon population
No full textIl progetto di ricerca presentato è uno studio multidisciplinare sul panorama bioculturale e i cambiamenti ambientali della laguna di Venezia, analizzati dal passato al presente. L’indagine si concentra su tre siti rappresentativi: Torcello (IX-XII sec.), Piazza San Marco a Venezia (XIV-XV sec.) e Chioggia (XVII-XIX sec.), per un totale di 90 individui analizzati (27 da Torcello, 20 da Venezia, 43 da Chioggia). Le analisi antropologiche hanno permesso di ricostruire la demografia, lo stile di vita e lo status sociale degli abitanti, mentre quelle molecolari e genomiche hanno valutato la conservazione dei reperti in ambiente lagunare umido, studiato le dinamiche di popolamento e confermato la determinazione del sesso. È emersa una forte ascendenza da popolazioni nord-europee, sia per linea materna che paterna, e una vicinanza genetica con popolazioni italiane ed europee medievali, riflettendo le conseguenze della caduta dell’Impero Romano d’Occidente. I dati suggeriscono un quadro multietnico: comunità formate da autoctoni e migranti giunti per motivi politici, commerciali o di fuga, che si integrarono stabilmente nel territorio. Le analisi metagenomiche hanno rilevato patogeni orali, mentre quelle isotopiche indicano una dieta basata su piante C4 (come sorgo e mais) e prodotti ittici, in linea con il contesto ambientale. Il progetto ha incluso anche lo studio dei metalli pesanti, in particolare del metil-mercurio, utile per valutare l’inquinamento storico, anche se i protocolli sono ancora in fase di elaborazione. In conclusione, la ricerca ha arricchito la conoscenza della popolazione veneta medievale e valorizzato il patrimonio culturale della laguna, dimostrando l’importanza di un approccio integrato tra dati biologici, culturali e ambientaliThe research project presented here is a multidisciplinary study of the biocultural landscape and environmental changes in the Venetian Lagoon, analyzed from past to present. The investigation focuses on three representative sites: Torcello (9th–12th century), Piazza San Marco in Venice (14th–15th century), and Chioggia (17th–19th century), with a total of 90 individuals analyzed (27 from Torcello, 20 from Venice, 43 from Chioggia). Anthropological analyses allowed for the reconstruction of demographic patterns, lifestyles, and social status, while molecular and genomic analyses assessed the preservation of remains in the lagoon's humid environment. These methods also helped trace population dynamics and confirmed sex identification made through classical physical anthropology. The genetic data revealed strong ancestry from Northern European populations—both maternal and paternal—and close genetic ties with contemporary Italian and European groups, reflecting the broader impact of the Western Roman Empire’s collapse.
The findings suggest a multiethnic society composed of both local and migrant groups who settled in the region for political, commercial, or survival reasons, eventually integrating into native communities. Metagenomic analyses identified oral pathogens responsible for periodontal diseases, while isotopic data indicated diets rich in C4 plants such as sorghum and maize—typical of the Medieval period and resilient to social and economic crises—as well as fish, consistent with the lagoon environment. The project also included heavy metal analysis, particularly methylmercury, to evaluate historical pollution in communities that relied heavily on fish consumption. However, protocols are still being optimized. Overall, the study has enriched our understanding of the medieval Venetian population, enhanced the cultural heritage of the lagoon, and demonstrated the value of combining biological, cultural, and environmental data to reconstruct the history, migrations, and adaptations of past communities
Innovation in vocational training to meet the challenges of sustainable development
No full textQuesto studio ha affrontato la crescente necessità di innovazione nelle pratiche formative nella formazione professionale, con particolare riferimento all'Istruzione e Formazione Professionale (IeFP). In collaborazione con C.E.F.A.L., l'obiettivo è stato esplorare il fabbisogno formativo delle figure professionali per rispondere alla domanda di innovazione interna (OCSE, 2019; Foschi, 2021; Aleandri & Fiorentini, 2022). L'approccio metodologico adottato è stato di ricerca-azione (Barbier, 2007; Lewin, 1946), utilizzando una metodologia Mixed Methods che ha combinato dati qualitativi e quantitativi. La fase iniziale ha previsto l'uso di interviste semi-strutturate, focus group e osservazioni (Trinchero & Robasto, 2019; Corbetta, 2014) per raccogliere informazioni e identificare le criticità, come la definizione dei ruoli, la comunicazione interna e l’aggiornamento delle strategie didattiche. Sulla base dei dati raccolti, sono stati progettati interventi mirati. Il primo intervento è stato la creazione di un Vademecum, finalizzato a chiarire le mansioni e le responsabilità delle figure professionali coinvolte, con l’obiettivo di definire meglio i ruoli dei protagonisti della formazione (Zaramella, Callini, & Morini, 2001). Un ulteriore intervento ha previsto la creazione di incontri mensili basati su casi studio, per migliorare la comunicazione tra le diverse figure professionali e favorire il confronto su temi educativi critici, creando così una prassi consolidata per affrontare situazioni complesse. Successivamente, è stato sviluppato un percorso formativo per migliorare le competenze delle figure professionali, affrontando le esigenze emerse dall'analisi dei fabbisogni formativi. Per monitorare l'efficacia dell'intervento, è stato somministrato un questionario pre e post-formazione (Pellerey, 2006), finalizzato a valutare le credenze dei partecipanti riguardo all’efficacia delle strategie didattiche e all'importanza della progettazione didattica.This study addressed the growing need for innovation in vocational training practices, with particular reference to Vocational Education and Training (VET). In collaboration with C.E.F.A.L., the objective was to explore the training needs of professional figures to respond to the demand for internal innovation (OECD, 2019; Foschi, 2021; Aleandri & Fiorentini, 2022). The methodological approach adopted was action research (Barbier, 2007; Lewin, 1946), using a Mixed Methods methodology that combined qualitative and quantitative data. The initial phase included semi-structured interviews, focus groups and observations (Trinchero & Robasto, 2019; Corbetta, 2014) to gather information and identify critical areas, such as role definition, Internal communication and updating of educational strategies. Based on the data collected, targeted interventions have been designed. The first intervention was the creation of a Vademecum, aimed at clarifying the tasks and responsibilities of the professional figures involved, with the aim of better defining the roles of the protagonists of the training (Zaramella, Callini, & Morini, 2001). A further intervention has provided for the creation of monthly meetings based on case studies, to improve communication between different professional figures and promote discussion on critical educational issues, thus creating a consolidated practice for dealing with complex situations. Subsequently, a training path was developed to improve the skills of professional figures, addressing the needs identified by the analysis of training needs. To monitor the effectiveness of the intervention, pre and post-training questionnaires were administered (Pellerey, 2006), aiming at assessing participants' beliefs about the effectiveness of educational strategies and the importance of educational design
Renegotiation of contract: between redress opportunities to contingencies and mechanisms to align the agreement
No full textLa presente tesi, nell’ambito dei contratti in cui tra il momento perfezionativo e quello esecutivo intercorre un determinato lasso temporale, indaga criticamente le soluzioni previste dal nostro ordinamento per il caso di eventi sopravvenuti, tali da frustrare il sinallagma contrattuale. In questo senso, lo studio, valorizzando il dinamismo che innerva il contratto, prende le mosse da una necessaria rilettura del principio pacta sunt servanda, alla luce della clausola rebus sic stantibus, considerando le più moderne esigenze che presenta il mercato. L’analisi si muove lungo le coordinate di un tema sul quale, a ben vedere, l’interesse dell’interprete non è mai sopito, ma è tornato in auge con rinnovato vigore a causa delle profonde crisi che hanno recentemente investito (anche) il diritto dei contratti. Viene, in tal guisa, posta in rilievo la progressiva emersione ed affermazione del principio di conservazione del contratto – di particolare importanza non solo nell’interesse delle parti, ma anche nell’interesse generale relativo all’economia degli scambi – sulla base di indici già presenti nel nostro ordinamento giuridico e nel panorama normativo europeo. In questo senso, la clausola generale di buona fede, raccordata al principio di solidarietà espresso dall’art. 2 Cost., riveste un ruolo fondamentale in vista della revisione del contratto, quale soluzione preferibile rispetto alla sua caducazione e, in particolare, per dimostrare la sussistenza, a livello di sistema, di un obbligo di rinegoziazione in capo ai contraenti. Lungo questo percorso, la ricerca, anche in una prospettiva de iure condendo, si è incentrata sui possibili rimedi, esperibili in caso di inadempimento di tale obbligo, che consentano di allineare, comunque, il regolamento pattizio originario alle mutate circostanze nel perseguimento della giustizia contrattuale e nel rispetto dell’autonomia delle parti.This thesis, in the context of long-term contracts, critically investigates the solutions provided by our legal system for the case of supervening events which have an impact on the contractual synallagma. In this sense, the study, enhancing the dynamism that innervates the contract, starts from a necessary reinterpretation of the principle pacta sunt servanda, in the light of the rebus sic stantibus clause, considering the most modern market needs. The analysis investigates a topic on which, in hindsight, the interpreter’s interest has never waned, but has made a comeback with renewed vigour due to the deep crises that have recently invested (also) contract law. Thus, the gradual emergence and affirmation of the principle of contract preservation – particularly relevant not only in the interest of the parties but also in the general interest relating to the trading economy – is highlighted on the basis of indices already present in our legal system and in the European legal scenario. In this sense, the general clause of good faith, strictly linked to the principle of solidarity expressed by Article 2 of the Constitution, plays a key role in the revision of the contract, seen as a preferable solution to its termination and, in particular, to demonstrate the existence, at the system level, of an obligation of renegotiation on contractors.
Along this path, the research, also in a de iure condendo perspective, has focused on the possible remedies which may be exercised in the event of non-fulfilment of the mentioned obligation and which allow the original contractual regulation to be aligned with the changed circumstances pursuing the contractual justice and respecting the autonomy of the parties