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Public Baths in Late Antique Greece. Architecture, functions and social space transformations
No full textIl presente lavoro si propone di concentrare la propria attenzione sulle terme pubbliche di età tardoantica – considerando l’insieme della letteratura scientifica disponibile e la necessità di un aggiornamento metodologico – comprese nelle provinciae dell’Hellas e di Creta, secondo i confini che possono essere tracciati sulla base del Synekdemos di Hierocles (§ 1). Il territorio di queste provinciae tardoantiche corrisponde all’incirca alle moderne regioni amministrative della Grecia Occidentale, della Grecia Centrale, dell’Attica e del Peloponneso per l’Ellade e dell’isola di Creta. In aggiunta all’indagine sulle caratteristiche architettoniche degli impianti, si è tentato di porre in rilievo le trasformazioni funzionali verificatesi in esse durante e dopo il loro utilizzo primario (§ 2). Oltre che sui singoli edifici (§ 2.1), l’indagine si è rivolta al contesto topografico di appartenenza. Le osservazioni raccolte sull’insieme del territorio descritto sono state inoltre messe a confronto con alcuni casi di studio rappresentati dalle città di Salonicco, Atene, Patrasso, Corinto e Gortina (§ 3). Si è cercato infine di sintetizzare i risultati emersi dalla ricerca, per contestualizzare il fenomeno termale tardoantico nell’ambito del suo sviluppo architettonico, dei mutamenti politici e urbanistici, dell’influenza del processo di cristianizzazione sulla società del periodo (§ 4).The present work aims to focus on the public baths of Late Antiquity - considering the body of scientific literature available and the need for methodological updating - included in the provinciae of Hellas and Creta, according to the geographical borders that can be traced on the basis of the Synekdemos of Hierocles (§ 1). The territory of these late antique provinciae roughly corresponds to the modern administrative regions of Western Greece, Central Greece, Attica and the Peloponnese for Hellas and the island of Creta. In addition to the investigation of the architectural characteristics of the facilities, an attempt was made to highlight the functional transformations that occurred in them during and after their primary use (§ 2). In addition to the individual buildings (§ 2.1), the investigation turned to their topographical context. The observations gathered on the entire territory described were also compared with some case studies represented by the cities of Thessaloniki, Athens, Patras, Corinth and Gortyn (§ 3). Finally, an attempt was made to synthesise the results of the research in order to contextualise the late antique thermal phenomenon within the context of its architectural development, political and urban changes, and the influence of the Christianisation process on the society of the period (§ 4)
Organic photosensitizers and nanostructured semiconductors for photoredox catalysis and artificial photosynthesis
No full textOver the course of evolution, Nature has elegantly learned to use light to drive chemical reactions. On the other hand, humans have only recently started learning how to play with this powerful tool to carry out chemical transformations. In particular, a step forward was possible thanks to molecules and materials that can absorb light and trigger a series of processes that can drive chemical reactions.
However, scarce elements are extensively employed in the design of most of these compounds and considerations on their scarcity and toxicity have sparked interest on alternatives based on earth-abundant elements. In this framework, the focus of this thesis has been the development and employment of heavy-metal free chromophores and of earth-abundant oxides.
The first chapter regards the functionalization of boron-dipyrromethenes (BODIPYs) so as to allow access to their triplet excited state and tune their redox potentials, which was achieved thanks to the design of orthogonal donor-acceptor dyads. The BODIPY dyads were used to promote a photoredox reaction, and the mechanism of the reaction was clarified.
In the second chapter, organic chromophores that display thermally-activated delayed fluorescence (TADF) were studied. These were used to perform enantioselective photoredox reactions, and a mechanistic investigation allowed to elucidate the fate of these photosensitizers in the reaction. Thanks to their stronger reducing power, it was possible to demonstrate the employability of TADF dyes in artificial photosynthesis, as well.
Last, the oxidation of biomass-derived compounds was studied in a photoelectrochemical cell. For this purpose, hematite photoanodes were synthesized in collaboration with Prof. Caramori’s group at the University of Ferrara (Italy) and they were tested in the presence of a redox mediator. In addition to this, the possibility of repurposing a copper(II) water oxidation catalyst for the oxidation of biomass was investigated in collaboration with Prof. Llobet’s group at ICIQ (Tarragona, Spain)
Aquivion-based spray freeze-dried composite catalysts for the cascade conversion of furfural to γ-valerolactone
No full textFurfural is one of the most promising biomass derived platform molecules. It is to this day produced in volumes above 300 ktons per year from the hydrolysis and dehydration of hemicellulose, one of the main components of lignocellulosic biomass. While the majority of the yearly production is destined to selective reduction to furfuryl alcohol for the production of furan resins, these molecules hold great potential for the production of more valuable chemicals, fuels, fuel additives and solvents. Among these products are alkyl levulinates and γ-valerolactone. To convert furfural to these target products, a cascade process involving Lewis acidity-catalysed reduction steps and Brønsted acidity-catalysed steps. In order to develop catalysts capable of promoting the one-pot domino reaction from furfural to γ-valerolactone, the two kinds of acidity must both be present. To this end, in this work, the spray freeze-drying technique is employed to combine the high activity and strong Brønsted acidity of Aquivion with the structural properties and Lewis acidity of different supporting metal oxide, forming composite catalysts. The flexibility of the spray freeze-drying technique and the modulable composition of the catalysts allowed a thorough study of the complex network of equilibria underlying the cascade reaction, while achieving high selectivities towards the final product
Dissecting and resetting SETD2/H3K36ME3 deficiency in chronic myeloid leukemia
No full textChronic myeloid leukemia (CML) is characterized by the presence of the BCR::ABL1 fusion gene, leading to a constitutively active tyrosine kinase that drives the disease. Genomic instability is a hallmark of CML, contributing to disease progression and treatment resistance. A study identified SETD2, a histone methyltransferase, as frequently dysfunctional in advanced-phase CML, resulting in reduced trimethylation of Histone H3 at lysine 36 (H3K36Me3). This loss is associated with poor prognosis and increased genetic instability.
Investigations revealed that SETD2 dysfunction is caused by post-translational modifications mediated by Aurora kinase A and MDM2, leading to proteasome-mediated degradation. Aurora kinase A phosphorylates SETD2, while MDM2 ubiquitinates it, targeting it for degradation. Inhibition of MDM2 and Aurora kinase A restored SETD2 expression and activity, suggesting potential therapeutic targets.
Loss of SETD2 and H3K36Me3 impairs DNA repair mechanisms, favoring error-prone repair pathways over faithful ones, exacerbating genetic instability. Reintroduction of SETD2 into deficient cells restored DNA repair pathways, preserving genomic integrity.
Analysis of CD34+ progenitor cells from CML patients showed reduced SETD2 levels compared to healthy individuals, correlating with decreased clonogenic capacity. Notably, SETD2 loss is not detectable at diagnosis but emerges during disease progression, indicating its role as an early indicator of CML advancement.
Therapeutically, inhibitors targeting Aurora kinase A, MDM2, and the proteasome showed efficacy in cells expressing SETD2, particularly in those with low SETD2 levels. Proteasome inhibitors induced apoptosis and DNA damage in SETD2-deficient cells, highlighting their potential for CML treatment. In conclusion, SETD2 acts as a tumor suppressor in CML, with its dysfunction contributing to genetic instability and disease progression. Targeting the mechanisms of SETD2 loss presents promising therapeutic avenues for controlling CML proliferation and restoring genomic integrity
Law and economics of environmental damage assessment
No full textGiven the limitations of traditional tools to remedy and prevent the harm to natural resources, environmental liability provisions started to be increasingly introduced to address pollution caused by events such as oil spills and toxic leakages, in addition to regulations, administrative and criminal sanctions. The past decades have seen an unprecedented development of environmental economic scholarship to inform not only ex ante benefit-cost analyses for policies and projects, but also the ex-post valuation of environmental accidents. Starting from the 1970s, new techniques to value the damage beyond market-based losses have been proposed and gradually finetuned. However, an emerging tendency in the law is represented by the restoration-based compensation of environmental damage that seems to avoid the contentious and more time-consuming use of methods designed for non-use values (e.g., stated preference). This thesis wants to provide a snapshot of the existing gap between liability laws, on the one hand, and the economic scholarship, on the other. The specific research question is whether remedies for environmental damage at the international, regional and national levels are providing polluters with optimal care incentives to minimise the environmental costs of accidents while, at the same time, ensuring cost-effective restoration. Some best practices emerged at some levels of the law and in some countries, but many challenges remain. They mainly relate to the notion of environmental damage, the role of the economic valuation in the law and the judicial practice, the multiple levels and branches of law intertwined in one single polluting event and the private interests of all parties involved in the environmental damage assessment. Despite this complexity and trying to abstract from details, this research puts forward a novel theory of remedies for environmental damage that wishes to provide a smart solution to attain more efficient deterrence and adequate remediation
Investigating ecosystem structure and function in restored coastal saltmarshes: a macro to micro-scale approach
No full textCoastal saltmarsh ecosystems are increasingly degraded by human activities, driving restoration efforts worldwide. However, the effectiveness of these efforts remains poorly understood. This PhD thesis explores the impact of restoration on sediment and ecosystem functioning across macro to microbial scales in natural and restored saltmarshes in Venice Lagoon (Italy), and Hunter River and Georges River estuaries (Australia). Findings revealed that despite variations in microbial community composition, restored saltmarshes exhibited comparable macro- and micro-scale ecosystem functioning to natural counterparts. These results emphasize the significance of restoration approaches and monitoring duration in achieving successful restoration outcomes
Persistent breeding-induced endometritis in mares: effects on early pregnancy endocrinology and innovative therapies
No full textMany mares are susceptible to persistent breeding-induced endometritis (PBIE), an important cause of reduced fertility. The exact influence of PBIE on the production of progesterone is not yet fully understood. The first study focused on measuring progesterone concentrations and luteal tissue area in non-bred mares, those bred becoming pregnant, and those bred but failing to become pregnant. It involved 52 cycles from 14 mares, monitored up to 10 days post-ovulation. Progesterone concentrations and luteal tissue area varied with time (P=0.001) but not with group (P>0.05). The second study aimed to determine the associations of the duration of estrus endometrial edema and the presence of intrauterine fluid accumulation with progesterone secretions. A total of 174 estrous cycles from 128 mares were included. Post breeding uterine fluid accumulation was associated with a decrease (p=0.009) in progesterone concentrations, and longer periods of uterine edema were associated with higher (p=0.0003) progesterone concentrations at the first pregnancy diagnosis (15 days post-ovulation).
Focusing on the treatment of PBIE in mares, traditionally multiple methods are involved, often including unnecessary use of broad-spectrum antibiotics. Recognizing the urgent need for new treatments, the last part of this PhD thesis explored the use of platelet lysate (PL, derived from freeze-thawing platelets after concentration) as an innovative therapy for mares susceptible to PBIE. A total of 14 mares underwent an untreated cycle (Ctr) followed by a treated cycle with PL. A significant decrease (P0.05), but the difference was clinically interesting. Therefore, the treatment with PL in mares susceptible to PMIE reduced the inflammatory response after breeding
New green bone substitutes from marine resources
No full textThe bone substitutes needs to favor osseointegration, therefore theirs composition need to be similar to the human bone mineral phase, which is HA. The conversion through chemical synthesis of calcium carbonate from marine waste in HA is used. However, currently the use of high temperatures lead to important energy and environmental impact. Here, a new mild-wet synthesis of CaCO3 from marine (cuttlefish bones, mussels and clamshells) waste is proposed to obtain green HA. The mild-wet synthesis was applied for 48h with different DAP concentrations and the addition of organic solvents. The converted materials were characterized to optimize the conversion rates. Their biological behavior was tested on L929 cells and their viability was evaluated by the Alamar Blue assay. The IJD-made coatings fabrication with HA-converted powders. In addition, other materials were used for coatings fabrications to compare their features with marine-derived nanocoatings. The conversion of powders was more efficient with the use of 1M DAP was the best concentration and the addition of organic solvents had increased the HA formed. The resulted powder had a spherical shape with undefined edges and Ca/P similar to biogenic HA. The use of 50 and 25% conditioned medium from converted powders increased the viability and proliferation. Nanostructured coatings in cuttlefish bone and mussel-derived HA were obtained with IJD, and by the SEM observation they were composed of globular aggregates and covered uniformly and homogenously the substrate surface. The chemical composition of the coatings obtained was similar to the starting sputtering targets as observed by FT-IR and EDS analyses. For the other CaP materials used, all the coatings obtained in the different materials were composed by globular aggregates and the chemical composition was similar to the starting materials. Regarding the different HA, coatings obtained from natural-derived HA possessed higher similarity to human bone mineral part
Sustainable human development: the work placement of vulnerable persons in a digitization and circular economy's perspective
No full textIl lavoro rappresenta un elemento cruciale nel percorso di riabilitazione e nel consolidamento della recovery nelle persone con Disturbo da Uso di Sostanze (DUS). Nel panorama italiano, le Cooperative Sociali di tipo A e B che operano nel campo delle dipendenze patologiche svolgono un ruolo prezioso per la cura, la riabilitazione e il reinserimento lavorativo di persone con DUS, promuovendo l’acquisizione di competenze professionali e trasversali e offrendo talvolta opportunità di impiego diretto, in linea con i principi di sostenibilità sociale. La letteratura suggerisce che le Cooperative Sociali possano contribuire anche alla sostenibilità ambientale, ma tale potenziale risulta poco esplorato, soprattutto nelle realtà operanti in area dipendenze. Il presente lavoro propone un’analisi del contributo delle cooperative sociali di tipo A e B alla sostenibilità sociale e ambientale, attraverso uno studio pilota condotto presso la Cooperativa Sociale Cento Fiori di Rimini. A seguito di una fase esplorativa iniziale, volta alla conoscenza del contesto, è stato implementato un disegno misto convergente parallelo in cui sono stati raccolti dati qualitativi e quantitativi. 21 interviste individuali hanno esplorato principalmente i percorsi di reinserimento lavorativo erogati dalla cooperativa dalla prospettiva di diversi testimoni privilegiati. Un questionario anonimo online, costruito a partire dal quadro teorico dell’Employee Green Behavior, ha invece indagato in che misura i dipendenti della cooperativa sentano pregnante il tema della sostenibilità, soprattutto ambientale, e quanto si applichino in comportamenti sostenibili. I risultati evidenziano l’impegno della Cooperativa Sociale Cento Fiori nel promuovere percorsi di reinserimento lavorativo inclusivi e personalizzati, ma anche la necessità di rafforzare il legame tra sostenibilità sociale e ambientale nella cultura organizzativa. A partire dalle evidenze emerse e dalle buone prassi individuate nella letteratura, questo lavoro propone alcune linee guida per supportare i professionisti del sociale nel migliorare i propri interventi e promuovere una cultura condivisa della sostenibilità nelle loro organizzazioni.Employment plays a crucial role in the rehabilitation process and in consolidating recovery among individuals with Substance Use Disorders (SUD). In the Italian context, Type A and Type B Social Cooperatives operating in the field of addiction provide valuable contributions to care, rehabilitation, and vocational reintegration for people with SUD. These cooperatives promote the development of both professional and transversal skills and, in some cases, offer direct employment opportunities, in line with the principles of social sustainability. Although existing literature suggests that Social Cooperatives may also contribute to environmental sustainability, this potential remains underexplored, particularly within organizations addressing substance use issues. This study presents an analysis of the contribution of Type A and B Social Cooperatives to both social and environmental sustainability, through a pilot study conducted at the Cooperativa Sociale Cento Fiori in Rimini. Following an initial exploratory phase aimed at understanding the context, a convergent parallel mixed methods design was implemented, collecting both qualitative and quantitative data. A total of 21 individual interviews explored the cooperative’s vocational reintegration programs from the perspective of various key informants. In parallel, an anonymous online questionnaire, developed based on the theoretical framework of Employee Green Behavior, examined how strongly cooperative employees perceive sustainability, particularly environmental sustainability, and to what extent they engage in sustainable behaviors. The results highlight Cooperativa Sociale Cento Fiori’s commitment to promoting inclusive and personalized vocational reintegration pathways, while also revealing the need to strengthen the integration of social and environmental sustainability within the organizational culture. Based on the findings and best practices identified in the literature, this study offers a set of guidelines to support social work professionals in enhancing their interventions and fostering a shared culture of sustainability within their organizations
Resilience and green regeneration in climate change and post-pandemic scenarios: bioengineered indoor farming systems for medicinal plants
No full textCatharanthus roseus produces valuable anticancer compounds, vinblastine (VBL) and vincristine (VCR), but in low quantities. To address this, VBL and VCR are semi synthesized from the more abundant precursors, vindoline (VDL) and catharanthine (CAT). This thesis explores bioengineered indoor strategies, including different LED light spectra, plasma-activated water (PAW), and biostimulants (BS), to enhance production of these compounds. Three studies were conducted in an indoor farming system. The first examined the impact of red (R) and white (W) LED light and PAW on VDL and CAT levels. R light moderately increased VDL and CAT, but its impact became significant when combined with PAW. Both VDL and CAT levels rose with plant age and were maximized under prolonged R light + PAW exposure. The second study assessed the total monomeric precursors (MPs: VDL + CAT) concentration and VBL levels. R light significantly enhanced MPs, particularly when combined with PAW. In contrast, white (W) light significantly stimulated VBL biosynthesis. Under W light, PAW increased VBL levels at both early and late growth stages; under R light, it reduced early-stage VBL but boosted it in later stages. Extended W light exposure alone also achieved high VBL levels. The third study evaluated combinations of R, W, blue (B), and red-blue (RB) light with a BS. VDL was found in both roots and leaves, with roots showing higher concentrations. R light combined with BS significantly boosted both mean concentrations and total yields of VDL and CAT. Over time, total yields increased significantly. In conclusion, this research shows that plant age, light quality and other elicitors significantly influence alkaloid production. These bioengineered approaches, along with optimized harvesting times, offer promising strategies for improving pharmaceutical compound production in medicinal plants, such as C. roseus