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Towards the first total synthesis of C-arylglucosidic ellagitannins. A biomimetic approach.
No full textL\u27enigmatico statuto dei "Principi Supremi". Un\u27indagine empirica su limiti e «controlimiti» alle modifiche dell\u27ordinamento costituzionale
No full textThis PhD dissertation regards the limitations to constitutional amendments, and the limitations to constitutional changes deriving from the process of European integration. Both these two categories are often conceived under a comprehensive notion called \u27supreme principles of the legal order\u27. The investigation of this category has been the object of vast attention by the legal scholarship, but the results of the best efforts have been significantly diverse. Moving from this fact, the dissertation applied an innovative empirical methodology to this subject, shifting the main focus on the epiphanies of the supreme principles of the legal order in the constitutional law “in action”. This route led to recognising a deep normative indeterminacy of those principles in action, and a sort of logical independence of the concept from the prescription eventually disposing the limitations to constitutional amendments of changes. The next step consisted in building a re-constructive hypothesis, in order to highlight the supreme principles\u27 essential role: that of closing the circle of a constitutional State where no player has the right to say the last word.This PhD dissertation regards the limitations to constitutional amendments, and the limitations to constitutional changes deriving from the process of European integration. Both these two categories are often conceived under a comprehensive notion called \u27supreme principles of the legal order\u27. The investigation of this category has been the object of vast attention by the legal scholarship, but the results of the best efforts have been significantly diverse. Moving from this fact, the dissertation applied an innovative empirical methodology to this subject, shifting the main focus on the epiphanies of the supreme principles of the legal order in the constitutional law “in action”. This route led to recognising a deep normative indeterminacy of those principles in action, and a sort of logical independence of the concept from the prescription eventually disposing the limitations to constitutional amendments of changes. The next step consisted in building a re-constructive hypothesis, in order to highlight the supreme principles\u27 essential role: that of closing the circle of a constitutional State where no player has the right to say the last word
ACETILACETOINO SINTASI DA Bacillus licheniformis NELLA SINTESI STEREOSELETTIVA DI ALCOLI TERZIARI POLIFUNZIONALI
No full textIn this PhD thesis the first application of acetylacetoin synthase (AAS), by B. licheniformis DSM 13, as a biocatalyst for the stereoselective formation of C-C bonds is described. AAS, a thiamine diphosphate (ThDP) dependent enzyme, catalyzes the condensation of dialkyl or alkyl-aryl-1,2-diketones into the corresponding α-hydroxy-β-diketones with the elimination of a carboxylic acid. The reactions were carried out using a single α-diketone as donor and acceptor (homo-coupling) or two different α-diketones (cross-coupling). The AAS enzymatic reaction of a new C-C bond formation is highly chemo-, regio- and enantioselective. The α-hydroxy-β-diketones obtained from the reactions of homo- and cross-coupling were reduced with acetylacetoin reductase (AAR), a dehydrogenase obtained from the same bacterium. The combined use of AAS and AAR allowed the preparation of a new range of optically pure α-alkyl-α,β-dihydroxyketones starting from commercial α-diketones. The stereochemistry of the enantiopure syn-α-alkyl-α,β-dihydroxyketones was assigned on the basis of NOE experiments, while their absolute configuration was determined transforming one of these compounds in the natural product (+)-citreodiol. The absolute configuration of α-alkyl-α, β-dihydroxyketones confirmed the S-stereospecificity of the AAR-reduction and R-stereospecificity of AAS homo and cross-coupling reactions. On the basis of the AAS activity, an alternative synthetic biomimetic route, reminiscent the ThDP-dependent enzymes activity, was studied. Both thiamine hydrochloride and its simplified analogue, thiazolium salt, act as pre-catalysts coupled with an appropriate basis and are able to activate α-diketones such as acyl-anion equivalents that can be transferred to enable ketonic acceptors as α-diketones and α-ketoesters. These carboligation reactions have been optimized in catalytic conditions using polyethylene glycol (PEG400), an eco-friendly reaction medium, that made easier the reaction workup allowing, in addition, the catalyst recycling. A further synthetic application of AAS was the chemo-enzymatic synthesis of the natural aroma of green tea. The chirality of this compound, closely related to its organoleptic properties, is actually studied in our laboratories. The versatility of AAS as biocatalyst for C-C bond forming reactions and the raised interest by its particular applications in organic synthesis promped us to purify the enzyme, with the ultimate goal of identifying the gene encoding for AAS in the genome of B. licheniformis DSM 13.In this PhD thesis the first application of acetylacetoin synthase (AAS), by B. licheniformis DSM 13, as a biocatalyst for the stereoselective formation of C-C bonds is described. AAS, a thiamine diphosphate (ThDP) dependent enzyme, catalyzes the condensation of dialkyl or alkyl-aryl-1,2-diketones into the corresponding α-hydroxy-β-diketones with the elimination of a carboxylic acid. The reactions were carried out using a single α-diketone as donor and acceptor (homo-coupling) or two different α-diketones (cross-coupling). The AAS enzymatic reaction of a new C-C bond formation is highly chemo-, regio- and enantioselective. The α-hydroxy-β-diketones obtained from the reactions of homo- and cross-coupling were reduced with acetylacetoin reductase (AAR), a dehydrogenase obtained from the same bacterium. The combined use of AAS and AAR allowed the preparation of a new range of optically pure α-alkyl-α,β-dihydroxyketones starting from commercial α-diketones. The stereochemistry of the enantiopure syn-α-alkyl-α,β-dihydroxyketones was assigned on the basis of NOE experiments, while their absolute configuration was determined transforming one of these compounds in the natural product (+)-citreodiol. The absolute configuration of α-alkyl-α, β-dihydroxyketones confirmed the S-stereospecificity of the AAR-reduction and R-stereospecificity of AAS homo and cross-coupling reactions. On the basis of the AAS activity, an alternative synthetic biomimetic route, reminiscent the ThDP-dependent enzymes activity, was studied. Both thiamine hydrochloride and its simplified analogue, thiazolium salt, act as pre-catalysts coupled with an appropriate basis and are able to activate α-diketones such as acyl-anion equivalents that can be transferred to enable ketonic acceptors as α-diketones and α-ketoesters. These carboligation reactions have been optimized in catalytic conditions using polyethylene glycol (PEG400), an eco-friendly reaction medium, that made easier the reaction workup allowing, in addition, the catalyst recycling. A further synthetic application of AAS was the chemo-enzymatic synthesis of the natural aroma of green tea. The chirality of this compound, closely related to its organoleptic properties, is actually studied in our laboratories. The versatility of AAS as biocatalyst for C-C bond forming reactions and the raised interest by its particular applications in organic synthesis promped us to purify the enzyme, with the ultimate goal of identifying the gene encoding for AAS in the genome of B. licheniformis DSM 13
IL SOGGETTO RIMOSSO. LE CRITICHE DI SCHELLING ALLA LOGICA E AL SISTEMA DI HEGEL NELLE LEZIONI MONACHESI
No full textThe purpose of this article is to analytically discuss Schelling’s criticisms of Hegel in the Münchener Vorlesungen. The text will analyze the aforementioned criticisms from Schelling’s perspective, focusing on these key points: the choice of method, logic, the structure of his system, and the conception of God. The matter will be investigated constantly by considering Schelling’s judgment of Hegel’s role in the history of philosophy. The red thread running through our analysis will be Hegel’s removal of the subject in the different levels of his theoretical approach
LA DISSOLUZIONE DELL’ATTORE FRA OTTO E NOVECENTO: PERCORSI DI UN’ESTETICA ANTINATURALISTICA
No full textWith the avant-garde movements of the late 19th and early 20th century, the actor\u27s art diverted from its traditional mimetic function and psychological rendering to recover the expressiveness of the body and to experiment with the abstract language of performance. The rejection of the realistic intent of representation gave rise to heterogeneous scenic experiences, which sometimes were linked to Symbolism and Expressionism. In the new avant-garde theatre, the actor can become a plastic-figurative element, the officiant of a rite or the evoker of aspiritual dimension. Acting undertakes audacious expressive paths that totally renewthe theatrical language, paving the way for the theatre of the second half of the 20th century
IL GOLEM. ORIGINE BIBLICA E METAMORFOSI MODERNA
No full textThis essay aims to analyze one of the most fascinating figures of Jewish mythology: the Golem. In contemporary era the clay colossus, this human artifice lends itself to countless interpretations and embodies different meanings: from the robotic automaton to the Zombie, the monster of the horror imaginary able to represent the limits of the human conditions and the anxieties that revolve around these limits
Oltre la natura, l’immagine: Riflessioni su una storia naturale dell’immagine
No full textThis paper aims to discuss what is the connection between nature and historical-cultural expressive forms. Starting from the paradigmatic example of Nach der Natur, written by Winfried Georg Sebald, it supposes a natural model to understanding the life of images and their development. Connecting the Sebaldian aesthetics with two of the most relevant French-language authors in the contemporary aesthetics of image, Georges Didi-Huberman and Marie-José Mondzain, it argues that there is a relationship of interdependence between human history and natural history. In particular, this study tries to bring out the specific historicity of the image connoted as natural history.Il contributo si propone di discutere quale sia il nesso tra la natura e le forme espressive di carattere storico-culturale. Partendo dall\u27esempio paradigmatico di Nach der Natur, scritto da Winfried Georg Sebald, il saggio suppone un modello naturale utile per comprendere la vita delle immagini e il loro sviluppo. Collegando l’estetica sebaldiana con due degli autori di lingua francese più importanti dell\u27estetica contemporanea dell\u27immagine, Georges Didi-Huberman e Marie-José Mondzain, viene descritta la relazione di interdipendenza tra la storia umana e la storia naturale. In particolare, questo studio ha l’obiettivo di far emergere la storicità specifica dell\u27immagine connotata come storia naturale
Greek Primary Education in the Context of the European Life Long Learning Area: the transformations and the new (?) roles
Get PDFThe present paper argues that the adoption of the Lisbon Strategy provided the EU with the tools – mainly the Open Method of Coordination (OMC) – to finally construct a functional European Lifelong Learning (LLL) area spanning all levels and types of education and learning, “from the cradle to the grave”. Accordingly, it puts forward the respective legislative initiatives introduced by the Greek government concerning Primary Education (PE) commenting on both its new roles in the context of the European LLL area and its place in the Greek LLL strategy.Il presente articolo sostiene che l’adozione della strategia di Lisbona debba fornire all’Unione Europea gli strumenti – principalmente l’Open Method of Coordination (OMC) – per realizzare un funzionale sistema europeo di apprendimento permanente (LLL) che abbracci tutti i livelli e le tipologie formative, “dalla culla alla tomba”. Conseguentemente, si affrontano le relative iniziative legislative introdotte dal governo greco in materia di istruzione primaria (PE), commentandone il nuovo ruolo nel contesto sia europeo, sia greco, di LLL