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Non-ambient solid-state characterization of crystalline molecular organic semiconductors
Get PDFThe research project is focused on the investigation of the polymorphism of crystalline molecular material for organic semiconductor applications under non-ambient conditions, and the solid-state characterization and crystal structure determination of the different polymorphic forms. In particular, this research project has tackled the investigation and characterization of the polymorphism of perylene diimides (PDIs) derivatives at high temperatures and pressures, in particular N,N’-dialkyl-3,4,9,10-perylendiimide (PDI-Cn, with n = 5, 6, 7, 8). These molecules are characterized by excellent chemical, thermal, and photostability, high electron affinity, strong absorption in the visible region, low LUMO energies, good air stability, and good charge transport properties, which can be tuned via functionalization; these features make them promising n-type organic semiconductor materials for several applications such as OFETs, OPV cells, laser dye, sensors, bioimaging, etc. The thermal characterization of PDI-Cn was carried out by a combination of differential scanning calorimetry, variable temperature X-ray diffraction, hot-stage microscopy, and in the case of PDI-C5 also variable temperature Raman spectroscopy. Whereas crystal structure determination was carried out by both Single Crystal and Powder X-ray diffraction. Moreover, high-pressure polymorphism via pressure-dependent UV-Vis absorption spectroscopy and high-pressure Single Crystal X-ray diffraction was carried out in this project. A data-driven approach based on a combination of self-organizing maps (SOM) and principal component analysis (PCA) is also reported was used to classify different π-stacking arrangements of PDI derivatives into families of similar crystal packing.
Besides the main project, in the framework of structure-property analysis under non-ambient conditions, the structural investigation of the water loss in Pt- and Pd- based vapochromic potassium/lithium salts upon temperature, and the investigation of structure-mechanical property relationships in polymorphs of a thienopyrrolyldione endcapped oligothiophene (C4-NT3N) are reported
In vitro application of biocontrol agents to improve the safety and quality of grapevine products
Get PDFPathogenic fungi are responsible for vine diseases affecting the grapevine yield and the organoleptic quality of the final wine products. Using of biocontrol agents can represent a sustainable alternative to the use of synthetic fungicides whose intense use can have negative effects on the ecosystem and cause increase resistant pathogen population to synthetic agents.
The principal aim of my PhD thesis was the isolation and characterization of new yeast strains and Bacillus subtilis SV108 as biocontrol agent and the comprehension of the mechanism of their antimicrobial action.
Accordingly, twenty wild yeast and one selected bacterium isolated among 62 samples, isolated from different Italian and Malaysian regions and molecularly identified, were evaluated in a preliminary screening test on agar. Results showed the highest effects on inhibiting mycelial growth by Starmerella bacillaris FE08.05, Metschnikowia pulcherrima GP8 and Hanseniaspora uvarum GM19. On the other side, Bacillus subtilis SV108 showed the ability of inhibit the mycelial growth of selected fungi by producing antimicrobial compounds on Malt Extract Broth medium recovered by sodium dodecyl sulphate polyacrylamide gel electrophoresis (SDS-PAGE) and identified by electrospray ionization (ESI) tandem mass spectrometer Triple TOF 5600. Moreover, in order to analyze the volatile fraction of compounds, the quantitative analysis of the VOCs profiles was performed by GC/MS/SPME. The analysis highlighted the presence of isoamyl and phenylethyl alcohols and an overall higher presence of low-chain fatty acids and volatile ethyl esters.
All the data collected suggest that the tested yeasts, found among the epiphytic microbiota associated with grape berries, can be potentially effective for the biological control of pathogenic moulds. On the other hand, the proteomic study conducted on B. subtilis SV108 revealed that there are two cyclic antifungal peptides which can explain the antimicrobial effect of Bacillus subtilis SV108 acting as biocontrol agent against fungal pathogens in grapevine
Civil liability ex delicto - article 112 of the Spanish Penal Code as a consolidation of the utilitarian paradigm of civil liability in criminal proceedings. Analysis, interpretation and proposed integration of the contents of the precept.
Get PDFEsta Tesis Doctoral analiza en profundidad el artículo 112 CP y propone una interpretación acorde con su naturaleza privadaThis Doctoral Thesis analyses Article 112 PC and proposes an interpretation in accordance with its private nature
Novel developments of atropisomeric organic molecules. Design of atropisomeric drugs, fluorescent compounds and investigation of reaction mechanisms.
Get PDFIn recent years, the study of restricted rotation bonds in organic compounds has aroused increasing interest. The reason is that this characteristic can lead to obtaining new properties in organic compounds. In this research thesis, an intense investigation was carried out using DFT calculations and experimental evaluation of the barriers to rotational energies, in order to discover new properties deriving from the restricted rotation bonds. Research has been developed in various fields of organic chemistry, ranging from drugs (the atropisomeric atorvastatin in Chapter 3) to luminescent compounds (aryls amino borane in Chapter 4). Furthermore, an organocatalytic central to axial conversion mechanism was investigated through DFT calculations, finding out interesting outcomes (Chapter 5). Finally, a project in collaboration with Dr. Farran and Prof. Vanthuyne of the Aix-Marseille University was done to investigate the interactions in transition states of rotational barriers
Rebooting the constitutional debate: deliberative constitutionalism in the European Union
Get PDFThe aim of my thesis is to investigate the possibility and necessity to rethink a constitutional framework and debate in a transnational polity such as the European Union. My effort focuses on a promising theory called deliberative constitutionalism, which carries on new insights on how democracy and constitutions relate each other. The EU is a unique political entity which poses unanswered questions about its political legitimacy and constitutional foundation, if a Constitution will ever be possible. Going beyond the classical conception of the national and sovereign ‘people’, we keep wondering how citizens may deliberate and discuss about their rights and political communities across borders, in what could be defined as a transnational civic society. The development of the latter brings with it necessary constitutional changes, if not an evolution of constitutionalism itself. Chapter 1 deals with defining the theoretical framework, which develops the distinctiveness of the deliberative constitutional paradigm not only with respect to other more 'classical' models of democracy, but also with respect to other deliberative models that have marked the constructivist debate. Chapter 2 presents a conceptual history of constituent power, mainly studying the evolution of the constitution-sovereignty-constituent power dialectic, up to contemporary theories that explain the negation, separation, union or plurality of a transnational constituent with respect to its national counterparts. Chapter 3 develops the discourse of constitutional pluralism, through its main claims and strands that especially pertain to Neil Walker's (2002, 2016) institutional and epistemic claims. Chapter 4 applies a deliberative constitutionalist framework to the case of the European Union. Through the exposition of DC normative tenets, a form of self-learning process is proposed that can reconcile the heterarchical arrangement of constitutional claims and the new demand for legitimacy, as well as the relationship between European peoples and European citizens
Domestic architecture and material culture in the Latin colonies of Ariminum and Bononia (3rd-1st century BC)
Get PDFIl tema affrontato nella presente ricerca sono le trasformazioni intercorse nella vita quotidiana tra il III e il I secolo a.C. in due colonie latine, Ariminum e Bononia, attraverso le evidenze archeologiche. Vengono indagate su scala locale le conseguenze di un fenomeno di grande portata, la colonizzazione romano-latina, mettendo a fuoco le forme dell’abitare, le tradizioni artigianali e le pratiche alimentari. La principale base documentaria sono le testimonianze archeologiche di edilizia domestica e le ceramiche, rinvenute nelle aree di abitato di Rimini e Bologna e nei territori limitrofi. Per cogliere a pieno le trasformazioni intercorse, vengono passate in rassegna le principali caratteristiche del popolamento, dell'architettura domestica e delle ceramiche precedenti la colonizzazione romano-latina. Le due colonie, le abitazioni e le ceramiche sono considerate, inoltre, nel contesto territoriale più ampio, volgendo lo sguardo anche all'area medio-adriatica e alla Cispadana. Allo stesso tempo, sono continui i riferimenti all'Italia medio-tirrenica, poiché permettono di comprendere molte delle evidenze archeologiche e dei processi storici in esame. Il primo capitolo tratta della colonizzazione romano-latina, calata nelle realtà di Rimini e Bologna. La domanda a cui si vuole rispondere è: chi erano gli abitanti delle due colonie? A questo proposito, si affronta anche la questione degli insediamenti precoloniali. Nel secondo capitolo si analizzano le abitazioni urbane. Quali furono le principali innovazioni nell'architettura domestica introdotte dalla colonizzazione? Come cambiarono le forme dell’abitare ad Ariminum e Bononia in età repubblicana? Il terzo capitolo si concentra sulla ceramica per la preparazione e il consumo del cibo nei contesti di abitato. Come cambiarono nelle due città le pratiche alimentari e le tradizioni artigianali utilizzate nella produzione di ceramiche? L'ultimo capitolo discute alcuni quadri teorici applicati ai fenomeni descritti nei capitoli precedenti (romanizzazione, acculturazione, identità, globalizzazione). L'ultimo paragrafo entra nel merito delle trasformazioni avvenute nella vita quotidiana di Ariminum e Bononia.The topic is the transformations occurred in everyday life between the 3rd and 1st centuries BC in two Latin colonies, Ariminum and Bononia, through archaeological evidence. In other words, the consequences of large-scale phenomena, the Roman-Latin colonization, are investigated in local scale, focusing on ways of dwelling, craft traditions and food practices. The main documentary base are the archaeological evidence of domestic buildings and ceramics, found in residetial area at Rimini and Bologna, and in the neighbouring territories. In order to understand these transformations, the main features of the population, domestic architecture and pottery before the Roman-Latin colonisation are overviewed. At the same time, the two colonies, the dwellings and the ceramics are considered in the broader territorial context, looking also at mid-Adriatic area and south Po valley. Furthermore, references to mid-Tyrrhenian Italy are continuous, as they provide an understanding of several archaeological evidence and historical processes under investigation. The first chapter discusses the Roman-Latin colonization, focusing on Rimini and Bologna. The question to be answered is: who were the inhabitants of the two colonies? In this regard, the matter of pre-colonial settlements is also addressed. In the second chapter, urban dwellings are analysed. What were the innovative features introduced by the colonisation in domestic architecture? How did the ways of dwelling change in Ariminum and Bononia during the Republican age? The third chapter focuses on cooking and consumption pottery from colonial settlements. How did food practices and craft traditions used in the production of ceramics change in the two colonies? The final chapter discusses some theoretical frameworks applied to the phenomena described in the previous chapters (romanisation, acculturation, identity, globalization). The last paragraph gets to the heart of the matter of the transformations occurred in everyday life in Ariminum and Bononia
The legal autonomy of the international arbitral award with respect to the seat of the arbitration: an analysis from the New York Convention 1958
Get PDFLa importancia y el efecto práctico de la CNY son indiscutibles desde hace mucho tiempo. La CNY ha regulado, directa o implícitamente, todos los pilares fundamentales del arbitraje internacional, proporcionando un marco jurídico uniforme para el desarrollo de este mecanismo alternativo de resolución de conflictos.
La CNY ha obligado a sus Estados contratantes a reconocer y ejecutar los acuerdos y laudos arbitrales con independencia de sus regulaciones e intereses locales. Así, por su alcance casi universal, la CNY ha alcanzado una relevancia extraordinaria.
Conjuntamente con su relevancia, la CNY ha proporcionado fundamentos adicionales para sostener la existencia de una jurisdicción arbitral autónoma que difiera de los ordenamientos jurídicos de cada Estado Contratante. Este planteamiento ha alcanzado aún mayor relevancia al ser avalado por la doctrina, los profesionales del arbitraje y la jurisprudencia de varios países -siendo su máximo exponente la jurisdicción francesa-.
Atendiendo a las consecuencias prácticas de este debate, esta tesis abordará (CAP 1) una revisión de la CNY y sus principales disposiciones que sugieren el "estatus constitucional" de la CNY, (CAP 2) los modelos filosóficos del arbitraje internacional, (CAP 3) el fenómeno de la ejecución de los laudos arbitrales anulados por los tribunales nacionales, y (CAP 4) la autonomía jurídica del laudo dictado en un arbitraje internacional respecto de la sede del mismo.The importance and practical effect of the CNY is undisputed since long ago. The CNY has regulated, directly or impliedly, all fundamental pillars of international arbitration, providing a uniform legal framework for the development of this alternative dispute resolution mechanism.
The CNY has obliged its Contracting States to recognize and enforce arbitration agreements and awards regardless of their parochial regulations and interests. Thus, because of its almost universal scope, the CNY has reached extraordinary relevance.
Jointly with its relevance, the CNY has provided additional grounds in order to sustain the existence of an autonomous arbitral jurisdiction that would differ from the legal orders of each individual Contracting State. This approach has achieved even more relevance as it has been endorsed by scholars, practitioners and the judiciary of several countries –being its greatest exponent the French jurisdiction.
In the view of the practical consequences of this debate, this thesis will address (CAP 1) a review of the CNY and its main provisions suggesting the “constitutional status” of the CNY, (CAP 2) the philosophical models of international arbitration, (CAP 3) the phenomenon of the enforcement of annulled arbitral awards by the national courts, and (CAP 4) the legal autonomy of the award rendered in an international arbitration from the seat of the arbitration
Effective field theories and their phenomenological applications
Get PDFEffective field theories (EFTs) are ubiquitous in theoretical physics and in particular in field theory descriptions of quantum systems probed at energies much lower than one or few characterizing scales. More recently, EFTs have gained a prominent role in the study of fundamental interactions and in particular in the parametriasation of new physics beyond the Standard Model, which would occur at scales Λ, much larger than the electroweak scale. In this thesis, EFTs are employed to study three different physics cases. First, we consider light-by-light scattering as a possible probe of new physics. At low energies it can be described by dimension-8 operators, leading to the well-known Euler-Heisenberg Lagrangian. We consider the explicit dependence of matching coefficients on type of particle running in the loop, confirming the sensitiveness to the spin, mass, and interactions of possibly new particles. Second, we consider EFTs to describe Dark Matter (DM) interactions with SM particles. We consider a phenomenologically motivated case, i.e., a new fermion state that couples to the Hypercharge through a form factor and has no interactions with photons and the Z boson. Results from direct, indirect and collider searches for DM are used to constrain the parameter space of the model. Third, we consider EFTs that describe axion-like particles (ALPs), whose phenomenology is inspired by the Peccei-Quinn solution to strong CP problem. ALPs generically couple to ordinary matter through dimension-5 operators. In our case study, we investigate the rather unique phenomenological implications of ALPs with enhanced couplings to the top quark
Chemo-physical and biological mechanisms behind the anticancer activity of plasma activated Ringer's Lactate solution for the treatment of peritoneal carcinosis from primitive epithelial ovarian/tubular tumor
Get PDFCancer research and development of targeting agents in this field is based on robust studies using preclinical models. The failure rate of standardized treatment approaches for several solid tumors has led to the urgent need to fine-tune more sophisticated and faithful preclinical models able to recapitulate the features of in vivo human tumors, with the final aim to shed light on new potential therapeutic targets. Epithelial Ovarian Cancer (EOC) serous histotype (HGSOC) is one of the most lethal diseases in women due to its high aggressiveness (75% of patients diagnosed at FIGO III-IV state) and poor prognosis (less of 50% in 5 years), whose therapy often fails as chemoresistance sets in.
This thesis aimed at using the novel perfusion-based bioreactor U-CUP that provides direct perfusion throughout the tumor tissue seeking to obtain an EOC 3D ex vivo model able to recapitulate the features of the original tumor including the tumor microenvironment and maintaining its cellular heterogeneity. Moreover, we optimized this approach so that it can be successfully applied to slow-frozen tumoral tissues, further extending the usefulness of this tool. We also investigated the effectiveness of Plasma Activated Ringer’s Lactate solution (PA-RL) against Epithelial Ovarian Cancer (EOC) serous histotype in both 2D and 3D cultures using ex-vivo specimens from HGSOC patients. We propose PA-RL as a novel therapy with local intraperitoneal administration, which could act on primary or metastatic ovarian tumors inducing a specific cancer cell death with reduced damage on the surrounding healthy tissues
Investment services and the value added tax: the European regulatory framework and its national implementation
Get PDFIl presente lavoro di ricerca ha ad oggetto i profili fiscali IVA dei servizi di investimento, in ambito sia europeo che nazionale, prestati dalle banche, dalle Sim e da consulenti/società di consulenza finanziaria nei confronti della clientela al dettaglio. Ciò al fine di individuarne il corretto trattamento fiscale nonché le possibili soluzioni agli interrogativi che ancora oggi rimangono aperti, anche alla luce delle indicazioni fornite nel tempo dalla Corte di Giustizia europea.
Constatata la profonda differenza esistente tra la classificazione MiFID dei servizi di investimento e quella fiscale delle operazioni finanziarie, oltre alla mancanza di coordinamento tra le relative normative europee, che non si incontrano neanche nell’attività ermeneutica della Corte di giustizia, si è cercato di interpretare la Direttiva IVA alla luce della normativa di settore (MIFID).
L’analisi della Direttiva IVA e, più in particolare, del trattamento da essa riservato alle operazioni finanziarie è stata, quindi, svolta cercando di ricondurre queste ultime ai (singoli) servizi di investimento (e, quindi, alla Direttiva MiFID) al fine di tracciare un collegamento che né il legislatore comunitario né la CGE hanno individuato.
È, tuttavia, apparso evidente come l’intero sistema dell’IVA, con particolare riferimento alle operazioni finanziarie, si sia ormai consolidato sulle interpretazioni della Corte di giustizia le quali hanno mostrato una elevata resilienza intrinseca.
È, pertanto, auspicabile un intervento legislativo, a livello comunitario, finalizzato a rimettere mano alla Direttiva IVA al fine di fornire criteri più chiari e stringenti per l’applicazione delle disposizioni in essa contenute, con particolare riferimento a quelle relative alle operazioni finanziarie.The present work is devoted to VAT tax profiles of investment services provided by banks, investment firms and financial advisors to retail investors, according to both European and Italian legislation. Its main aim is to identify possible solutions to any issue that still remain unsolved with regard to the investment services’ correct VAT treatment. In doing so indications provided over time by the European Court of Justice (ECJ) have been taken into high consideration.
In light of the great differences between the MiFID classification of investment services and the VAT classification of financial transactions, and given the lack of coordination between the relevant European regulations which do not even meet in the hermeneutic activity of the ECJ, with the present work we have tried to interpret the VAT Directive (for what concerns financial transactions) according to the MiFID legislation.
Therefore the analysis of the VAT Directive and, more specifically, of the financial transactions’ VAT treatment, has been carried out by trying to understand to which (specific) investment services the expression “financial transactions” refers to. In doing so we have tried to identify a link between the VAT Directive and the MiFID Directive that neither the EU legislator nor the ECJ have identified.
The analysis shows that the whole VAT system, with particular regard to financial transactions, has now consolidated on the interpretations of the European Court of Justice which have shown a high intrinsic resilience.
Therefore, it is highly desirable to take legislative action at EU level in order to modify the VAT Directive and to provide clearer and more specific criteria for the application of its provisions with particular regard to those relating to financial transactions