Lo studio dei processi biogeochimici che avvengono all’interfaccia acqua-sedimento riveste grande importanza per comprendere quali fattori ambientali siano responsabili di un eventuale modifica nel bilancio del carbonio organico e di altri elementi maggiori o minori e può` fornire un' indicazione su quali siano le aree più sensibili a tali processi. In questo studio sono stati analizzati i meccanismi che guidano la mineralizzazione della sostanza organica in aree caratterizzate da differenti condizioni idrodinamiche, batimetriche e trofiche nel Mediterraneo centrale. In particolare sono state prelevate carote di sedimento e analizzate le acque interstiziali in siti localizzati nell'Adriatico centro-meridionale, caratterizzati da basse profondità, alti tassi di sedimentazione e elevati apporti di sostanza organica, e in siti localizzati nello Ionio centro-settentrionale, caratterizzati da profondità crescenti, minori tassi di sedimentazione e ridotti apporti fluviali. L'analisi dei processi di degradazione della sostanza organica evidenzia differenze regionali tra il bacino adriatico e quello ionico: processi di mineralizzazione ossica e subossica appaiono intensi nei sedimenti adriatici, diversamente il bacino ionico appare caratterizzato principalmente da processi di degradazione ossica della sostanza organica. Inoltre, relativamente ai flussi bentici di Carbonio Inorganico Disciolto (DIC) flussi inversi sono stati registrati nei due bacini: i sedimenti adriatici si comportano come sourse di DIC, mentre i sedimenti Ionici si comportano come dei sink di DIC suggerendo una possibile precipitazione di carbonati nel bacino ionico. / It is known that the burial of organic carbon (OC) in marine sediments is one of the major long-term sinks of reduced carbon on Earth and the long-term sink of particulate OC in marine sediments contribute to moderate atmospheric CO2 levels on geological time scales. For this reason several efforts have been made to understand early diagenetic zonation and evaluate the associated benthic fluxes. In this study we investigate the features controlling the early diagenetic processes in areas of different sedimentation in the central Mediterranean Sea. Sediments core were collected in 7 stations characterized by different bathymetry, hydrological setting and trophic conditions. Northern stations, located in the central and southern Adriatic depressions, are characterized by shallow depths, higher sedimentation rates and higher organic matter inputs. Southern stations, located in the Northern and Central Ionian Sea, are characterized by increasing depths, different provenances of terrigenous sediments, lower productivity, lower sedimentation rates and organic matter inputs. The early diagenesis processes recorded in the Adriatic and Ionian seas showed regional differences between the Adriatic and Ionian basins. Higher inputs of reactive organic matter promote a northern-southern and shallow-deep trend in Adriatic sediments. These sediments are characterized by oxic-suboxic degradation processes and a lowering of remineralization processes in accord with distance from terrestrial inputs is evident. In the Ionian basin the remineralization processes takes place mainly by means of oxic reactions. The inputs of reactive organic matter in this area are lower for the lower productivity of this basin and for the higher distance from fluvial inputs. However, inverse DIC fluxes occur, Adriatic sediments are a net source of DIC while Ionian sediments show a sink of DIC suggesting a possible precipitation of carbonate in the Ionian basin.

The protein silk fibroin (SF) from the silkworm Bombyx mori is a FDA-approved biomaterial used over centuries as sutures wire. Importantly, several evidences highlighted the potential of silk biomaterials obtained by using so-called regenerated silk fibroin (RSF) in biomedicine, tissue engineering and drug delivery. Indeed, by a water-based protocol, it is possible to obtain protein water-solution, by extraction and purification of fibroin from silk fibres. Notably, RSF can be processed in a variety of biomaterials forms used in biomedical and technological fields, displaying remarkable properties such as biocompatibility, controllable biodegradability, optical transparency, mechanical robustness. Moreover, RSF biomaterials can be doped and/or chemical functionalized with drugs, optically active molecules, growth factors and/or chemicals In this view, activities of my PhD research program were focused to standardize the process of extraction and purification of protein to get the best physical and chemical characteristics. The analysis of the chemo-physical properties of the fibroin involved both the RSF water-solution and the protein processed in film. Chemo-physical properties have been studied through: vibrational (FT-IR and Raman-FT) and optical (absorption and emission UV-VIS) spectroscopy, nuclear magnetic resonance (1H and 13C NMR), thermal analysis and thermo-gravimetric scan (DSC and TGA). In the last year of my PhD, activities were focused to study and define innovative methods of functionalization of the silk fibroin solution and films. Indeed, research program was the application of different methods of manufacturing approaches of the films of fibroin without the use of harsh treatments and organic solvents. New approaches to doping and chemical functionalization of the silk fibroin were studied. Two different methods have been identified: 1) biodoping that consists in the doping of fibroin with optically active molecules through the addition of fluorescent molecules in the standard diet used for the breeding of silkworms; 2) chemical functionalization via silylation.

La tesi analizza i rapporti tra l’ordinamento italiano e la Cedu, in particolare la collocazione della Cedu all’interno del sistema delle fonti alla luce della modifica dell’art. 117, comma 1 Cost. Si tratta di un tema molto dibattuto in dottrina, specialmente a seguito dell’entrata in vigore del Trattato di Lisbona. Questa tematica risulta strettamente connessa al profilo dell’interazione tra la Corte di Strasburgo e la Corte costituzionale e i giudici ordinari. L’analisi del profilo statico concernente lo status della Cedu nel sistema italiano deve quindi essere accompagnata dall’esame del profilo dinamico, relativo al ruolo della giurisprudenza della Corte di Strasburgo nell’esperienza dell’ordinamento nazionale. Entrambi i profili di indagine sono esaminati alla luce delle indicazioni provenienti dalla giurisprudenza della Corte costituzionale, della Corte di Cassazione e della Corte di Strasburgo. Prima di essere esaminate singolarmente, queste tematiche richiedono la preliminare ricognizione dei termini della dicotomia tra i due modelli concettuali di riferimento in tema di rapporti interordinamentali: il monismo e il dualismo. Trasferite nel peculiare contesto del sistema Cedu, tali categorie dogmatiche si arricchiscono di ulteriori profili, che esorbitano dalla sistemazione del rapporto tra fonti. La tenuta dei due paradigmi concettuali, che sono nati ed operano nel contesto della teorica delle fonti, deve essere verificata anche rispetto all’attuale fenomeno della produzione europea di diritto giurisprudenziale ed alla capacità paradigmatica assunta dalla giurisprudenza di Strasburgo. Il diritto e le istituzioni giuridiche tendono ad assumere sempre più sembianze giurisdizionali, generando un’osmosi che porta a trasferire il focus dai rapporti interordinamentali ai rapporti tra giurisprudenze. / The research topic relates to the relationship between the Italian legal system and the ECHR, in particular the formal position of the ECHR in the national hierarchy of legal norms, in light of the amendment of Article 117 Const. This issue is very debated among scholars, especially following the entry into force of the Lisbon Treaty. This matter is strictly linked to the problem of the interaction between the Strasbourg Court and the ICC and ordinary judges. In other words, the analysis of the ‘static’ profile concerning the status of the ECHR in the Italian legal order must be accompanied by the examination of the ‘dynamic’ profile, relating to the role of Strasbourg Court’s case-law in the experience of the domestic legal system. Both of these issues follow from the Constitutional case law. Therefore, they will be dealt with in light of the rulings of the ICC, Court of Cassation and Strasbourg Court. Before being examined individually, these topics require the preliminary examination of the terms of the dichotomy between the two theoretic models in matter of relationship between international and national law: the monism and the dualism. Transferred to the peculiar context of the ECHR, these categories are enriched by more dogmatic profiles, which go beyond the sole matter of the relationship between sources of law. The strength of the two theoretical paradigms - that have been born and work in the context of sources of law - must also be checked with reference to the current phenomenon of European production of case law. The law and the legal institutions tend to take more and more jurisdictional shape, generating osmosis leading to the transfer of the focus from relationships between sources of law to the relationships between jurisprudences.

This work is about the role that environment plays in the production of evolutionary significant variations. It starts with an historical introduction about the concept of variation and the role of environment in its production. Then, I show how a lack of attention to these topics may lead to serious mistakes in data interpretation. A statistical re-analysis of published data on the effects of malnutrition on dental eruption, shows that what has been interpreted as an increase in the mean value, is actually linked to increase of variability. In Chapter 3 I present the topic of development as a link between variability and environmental influence, giving a review of the possible mechanisms by which development influences evolutionary dynamics. Chapter 4 is the core chapter of the thesis; I investigated the role of environment in the development of dental morphology. I used dental hypoplasia as a marker of stress, characterizing two groups. Comparing the morphology of upper molars in the two groups, three major results came out: (i) there is a significant effect of environmental stressors on the overall morphology of upper molars; (ii) the developmental response increases morphological variability of the stressed population; (iii) increase of variability is directional: stressed individuals have increased cusps dimensions and number. I also hypothesized the molecular mechanisms that could be responsible of the observed effects. In Chapter 5, I present future perspectives for developing this research. The direction of dental development response is the same direction of the trend in mammalian dental evolution. Since malnutrition triggers the developmental response, and this particular kind of stressor must have been very common in our class evolutionary history, I propose the possibility that environmental stress actively influenced mammals evolution. Moreover, I discuss the possibility of reconsidering the role of natural selection in the evolution of dental morphology.

Il tema relativo al potere di esternazione del Presidente di Assemblea parlamentare rappresenta un aspetto problematico del diritto costituzionale a causa delle sue diverse implicazioni nonché delle numerose intersezioni tra dato costituzionale e legislativo, dottrina e prassi configurando, dunque, un ambito di ricerca di indubbia rilevanza e attualità all’interno del dibattito costituzionalistico.È chiaro che l’analisi di tale problematica necessita dell’assunzione di un punto di vista che non potrà essere strettamente tecnico-giuridica, ma che necessariamente dovrà confrontarsi con elementi della prassi politico-costituzionale. / The issue related to the power of externalization of the Assembly's President represents a problematic aspect of constitutional law due to its different implications and the numerous intersections between constitutional and legislative fact as well, and also doctrine and praxis configuring, so, it is an environment of research made by an undoubtful relevance and actuality of the internal constitutionalist debate. It's clear that the analysis about this statement needs the assuming of a point of view which won't can be just strictly technical -juridical but also and necessarily will have to relate with the elements of the political-constitutional praxis.

The three parts of the job try to offer a recognition of the issues connected the existence of the presidential prerogatives about the legislative activity, and in general terms on the eventual happened transformations, above the last few years, to the role of the President of the Republic inside of the Italian constitutional system. The job start with one methodological premise that aims to value the relative issue to the various methodological approaches that can be followed in the study of presidential thematic: that is, to hold clearly distinguished the plan of the norms from that one of the praxes or to analyze them and to estimate them jointly. The first chapter is dedicated to the analysis of the delineated from Constitution and enriched presidential figure therefore like from beyond sixty years of constitutional literature. The second chapter is dedicated to one of the possible causes from which the evolutions recorded from the presidential figure draw origin in the past few years: that is, the change of the constitutional system of political representation. Such element is analyzed above all in its institutional within, that is to say the model of shape of government represented by the circuit parliament-government. The third chapter directly analyzes the two main issues of the research: on one side the study of the general presidential activity of participation in the political issues, through his communicates; on the other hand, the analysis of some specific case studies of presidential participation during emanation or enactment of the legislative actions deriving by the government and the parliament, between 2006-2013. Moreover, the job is enriched from one important section (attached) of “case studies” containing the result of a research carried out on more than 3000 presidential documents, from 2006 to 2013, published from the offices of the Quirinale. / I tre capitoli in cui è suddiviso il lavoro cercano di offrire una ricognizione delle questioni che ruotano intorno alla sussistenza o meno di prerogative presidenziali riguardo l’attività legislativa, e in generale sulle eventuali trasformazioni avvenute, soprattutto negli ultimi anni, nel ruolo del Presidente della Repubblica all’interno del sistema costituzionale italiano. Il lavoro esordisce con una premessa metodologica con cui si tenta di valorizzare la questione relativa ai diversi approcci metodologici che si possono seguire nello studio delle tematiche presidenziali: ossia, tenere nettamente distinti il piano delle norme da quello delle prassi oppure analizzarli e valutarli congiuntamente. Il primo capitolo è dedicato all’analisi della figura presidenziale così come delineata dalla Costituzione e arricchita dagli oltre sessant’anni di letteratura costituzionale. Vengono quindi analizzate le disposizioni costituzionali di riferimento e viene dato conto delle principali teorie costituzionali espresse dalla letteratura giuridica. Il secondo capitolo è dedicato a quella che viene offerta come una delle possibili cause da cui traggono origine le evoluzioni registrate in questi ultimi anni dalla figura presidenziale: ossia, il mutamento del sistema costituzionale di rappresentanza politica. Tale elemento è analizzato soprattutto nel suo ambito istituzionale, vale a dire il modello di forma di governo rappresentato dal circuito parlamento-governo. Il terzo capitolo entra direttamente nelle due questioni di fondo della ricerca: da un lato lo studio della generale attività presidenziale di intervento nelle questioni politiche, attraverso comunicati o esternazioni; dall’altro lato l’analisi di alcuni specifici casi paradigmatici di intervento presidenziale in sede di emanazione o promulgazione (o, comunque, discussione) degli atti legislativi del governo e del parlamento, accaduti tra il 2006 e il 2013. Inoltre, il lavoro è arricchito da una importante sezione (allegata) di “case studies” contenente il risultato di una ricerca effettuata su oltre tremila documenti presidenziali, dal 2006 al 2013, resi pubblici dagli uffici del Quirinale.

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Traditional morphological examinations are not anymore sufficient for a complete evaluation of tumoral tissue and the use of neoplastic markers is of utmost importance. Neoplastic markers can be classified in: diagnostic, prognostic and predictive markers. Three markers were analyzed. 1) Insulin-like growth factor binding protein 2 (IGFBP2) was immunohistochemically examined in prostatic tissues: 40 radical prostatectomies from hormonally untreated patients with their preoperative biopsies, 10 radical prostatectomies from patients under complete androgen ablation before surgery and 10 simple prostatectomies from patients with bladder outlet obstruction. Results were compared with α-methylacyl-CoA racemase (AMACR). IGFBP2 was expressed in the cytoplasm of untreated adenocarcinomas and, to a lesser extent, in HG-PIN; the expression was markedly lower in patients after complete androgen ablation. AMACR was similarly expressed in both adenocarcinoma and HG-PIN, the level being similar in both lesions; the expression was slightly lower in patients after complete androgen ablation. IGFBP2 may be used a diagnostic marker of prostatic adenocarcinomas. 2) Heparan surface proteoglycan immunohistochemical expression was examined in 150 oral squamous cell carcinomas. Follow up information was available in 93 patients (range: 6-34 months, mean: 19±7). After surgery, chemotherapy was performed in 8 patients and radiotherapy in 61 patients. Multivariate and univariate overall survival analyses showed that high expression of syndecan-1 (SYN-1) was associated with a poor prognosis. In patients treated with radiotherapy, such association was higher. SYN-1 is a prognostic marker in oral squamous cell carcinomas; it may also represent a predictive factor for responsiveness to radiotherapy. 3) EGFR was studied in 33 pulmonary adenocarcinomas with traditional DNA sequencing methods and with two mutation-specific antibodies. Overall, the two antibodies had 61.1% sensitivity and 100% specificity in detecting EGFR mutations. EGFR mutation-specific antibodies may represent a predictive marker to identify patients candidate to tyrosine kinase inhibitors therapy.

Tumor is a lesion that may be formed by an abnormal growth of neoplastic cells. Many factors increase the risk of cancer and different targets are involved in tumor progression. Within this thesis, we have addressed two different biological targets, independently connected with tumor formation, e.g. Hsp90 and androgen receptor. The ATP-dependent chaperone Hsp90 is responsible for the conformational maturation and the renaturation of proteins. “Client” proteins are associated with the cancer hallmarks, as cell proliferation and tumor progression. Consequently, Hsp90 has evolved into promising anticancer target. Over the past decade, radicicol has been identified as potential anticancer agent targeting Hsp90, but it is not active in vivo. With that aim of obtaining radicicol-related derivatives, we developed the design and synthesis of new chalcones analogs. Chalcones, which are abundant in edible plants, own a diverse array of pharmacological activities and are considered a versatile scaffold for drug design. Antiproliferative assays and western blot analysis on the new compounds showed that some of those display an interesting cytotoxic effect and the ability to modulate Hsp90 client proteins expression. Androgen Receptor (AR) hypersensitivity plays crucial role in prostate cancer, which progression is stimulated by androgens. The therapy consists in a combination of surgical or chemical castration, along with antiandrogens treatment. Casodex® (bicalutamide), is the most widespread antiandrogen used in clinic. However, hormonal therapy is time-limited since many patients develop resistance. Commercially available antiandrogens show a common scaffold, e.g. two substituted aromatic rings linked by a linear or a cyclic spacer. With the aim of obtaining novel pure AR antagonists, we developed a new synthetic methodology, which allowed us to introduce, as linker between two suitably chosen aromatic rings, a triazole moiety. Preliminary data suggest that the herein reported new molecules generally decrease PSA expression, thus confirming their potential AR antagonistic activity.

La tesi consiste in una comparazione della disciplina costituzionale della libertà di riunione nell'ordinamento italiano ed in quello turco / The thesis is aimed to compare the italian and turkish constitutional and ordinary dispositions concerning freedom of assembly