Tetrafenilciclopentadienon-derivati ed analoghi: sintesi, "self-assembly" e caratterizzazione reologica

Gels are materials that are easier to recognize than to define. For all practical purpose, a material is termed a gel if the whole volume of liquid is completely immobilized as usually tested by the ‘tube inversion’ method. Recently, supramolecular gels obtained from low molecular weight gelators (LMWGs) have attracted considerable attention in materials science since they represent a new class of smart materials sensitive to external stimuli, such as temperature, ultrasounds, light, chemical species and so on. Accordingly, during the past years a large variety of potentialities and applications of these soft materials in optoelectronics, as electronic devices, light harvesting systems and sensors, in bio-materials and in drug delivery have been reported. Spontaneous self-assembly of low molecular weight molecules is a powerful tool that allows complex supramolecular nanoscale structures to be built. The weak and non-covalent interactions such as hydrogen bonding, π–π stacking, coordination, electrostatic and van der Waals interactions are usually considered as the most important features for promoting sol-gel equilibria. However, the occurrence of gelation processes is ruled by further “external” factors, among which the temperature and the nature of the solvents that are employed are of crucial importance. For example, some gelators prefer aromatic or halogenated solvents and in some cases both the gelation temperature and the type of the solvent affect the morphologies of the final aggregation. Functionalized cyclopentadienones are fascinating systems largely employed as building blocks for the synthesis of polyphenylene derivatives. In addition, it is worth noting that structures containing π-extended conjugated chromophores with enhanced absorption properties are of current interest in the field of materials science since they can be used as “organic metals”, as semiconductors, and as emissive or absorbing layers for OLEDs or photovoltaics. The possibility to decorate the framework of such structures prompted us to study the synthesis of new hydroxy propargyl arylcyclopentadienone derivatives. Considering the ability of such systems to give π–π stacking interactions, the introduction on a polyaromatic structure of polar substituents able to generate hydrogen bonding could open the possibility to form gels, although any gelation properties has been never observed for these extensively studied systems. we have synthesized a new class of 3,4-bis (4-(3-hydroxy- propynyl) phenyl) -2, 5-diphenylcyclopentadienone derivatives, one of which (1a) proved to be, for the first time, a powerful organogelator. The experimental results indicated that the hydroxydimethylalkynyl substituents are fundamental to guarantee the gelation properties of the tetraarylcyclopentadienone unit. Combining the results of FT-IR, 1H NMR, UV-vis and fluorescence emission spectra, we believe that H-bonding and π–π interactions are the driving forces played for the gel formation. The importance of soft materials lies on their ability to respond to external stimuli, that can be also of chemical nature. In particular, high attention has been recently devoted to anion responsive properties of gels. Therefore the behaviour of organogels of 1a in toluene, ACN and MeNO2 towards the addition of 1 equivalent of various tetrabutylammonium salts were investigated. The rheological properties of gels in toluene, ACN and MeNO2 with and without the addition of Bu4N+X- salts were measured. In addition a qualitative analysis on cation recognition was performed. Finally the nature of the cyclic core of the gelator was changed in order to verify how the carbonyl group was essential to gel solvents. Until now, 4,5-diarylimidazoles have been synthesized.

L'interpretazione autentica nei suoi profili teorici ed applicativi

La trattazione cerca di delineare i confini teorici ed applicativi dell’istituto dell’interpretazione autentica, nella chiara consapevolezza che dietro tale tematica si celi il più complesso problema di una corretta delimitazione tra attività di legis-latio e attività di legis-executio. Il fenomeno delle leggi interpretative costituisce infatti nodo nevralgico e punto di intersezione di tre ambiti materiali distinti, ossia la teoria dell’interpretazione, la teoria delle fonti del diritto e la dottrina di matrice liberale della separazione dei poteri. All’interno del nostro ordinamento, nell’epoca più recente, si è assistito ad un aumento esponenziale di interventi legislativi interpretativi che, allo stato attuale, sono utilizzati per lo più come strumenti di legislazione ordinaria. Sotto questo profilo, il sempre più frequente ricorso alla fonte interpretativa può essere inquadrato nel più complesso fenomeno della “crisi della legge” i cui tradizionali requisiti di generalità, astrattezza ed irretroattività sono stati progressivamente abbandonati dal legislatore parallelamente con l’affermarsi dello Stato costituzionale. L’abuso dello strumento interpretativo da parte del legislatore, gravemente lesivo delle posizioni giuridiche soggettive, non è stato finora efficacemente contrastato all’interno dell’ordinamento nonostante l’elaborazione da parte della Corte costituzionale di una serie di limiti e requisiti di legittimità dell’esegesi legislativa. In tale prospettiva, diventano quindi di rilevanza fondamentale la ricerca e l’esame di strategie e rimedi, giurisdizionali ed istituzionali, tali da arginare l’“onnipotenza” del legislatore interprete. A seguito dell’analisi svolta, è maturata la consapevolezza delle potenzialità insite nella valorizzazione della giurisprudenza della Corte Edu, maggiormente incline a sanzionare l’abuso delle leggi interpretative.

Accesorios de indumentaria del regnum visigodo temprano (siglos V-VI)

Los accesorios metálicos de indumentaria constituyen uno de las fuentes materiales principales para aproximarse a la realidad social, cultural y económica de la población del Mediterráneo tardoantiguo. En el caso de los hallazgos de los siglos V y VI procedentes de la Península Ibérica y del suroeste de Francia, numerosos problemas de documentación han impedido extraer y desarrollar todo su potencial, tanto en lo referente al encuadre tipológico y cronológico de estos objetos como en la consiguiente fase interpretativa. Se hacía necesario acometer un nuevo estudio monográfico que actualizara el panorama de la investigación. El trabajo cataloga, data y clasifica tipológicamente más de cuatro millares de fíbulas y accesorios de cinturón recuperados en casi medio millar de yacimientos localizados en los actuales Portugal, España, Andorra y Francia. El resultado permite aproximarse a las áreas de producción y modalidades de circulación y utilización de cada uno de los tipos individualizados. Una veintena de indumentarias distintas, definidas por combinaciones de distintos tipos de accesorios en contextos funerarios, ha sido identificada. Parte de éstas constituye la base principal de un sistema cronológico organizado en seis fases distintas que cubren una cronología situada aproximadamente entre las últimas décadas del siglo IV y las últimas décadas del siglo VI. La investigación acomete asimismo el análisis de la implantación de los accesorios y de las indumentarias relacionadas con ellos en el paisaje tardoantiguo de Hispania y la Galia. El resultado permite reconstruir secuencias regionales de evolución indumentaria y establecer relaciones entre diversas tipologías de contextos funerarios y habitativos y los tipos de indumentaria previamente definidos. Los resultados permiten renovar la mirada sobre este tipo de objetos y el lugar que ocuparon en la vida cotidiana de muchos de los habitantes del regnum visigodo temprano.

Servizi di posizionamento e potenzialità degli atti di aggiornamento cartografico in coordinate assolute ETRF2000

Il contesto nazionale è cambiato recentemente per l’introduzione del nuovo Sistema Geodetico coincidente con quello Europeo (ETRS89, frame ETRF00) e realizzato dalle stazioni della Rete Dinamica Nazionale. Sistema geodetico, associato al cartografico UTM_ETRF00, divenuto per decreto obbligatorio nelle Pubbliche Amministrazioni. Questo cambiamento ha consentito di ottenere rilevamenti dei dati cartografici in coordinate assolute ETRF00 molto più accurate. Quando i dati così rilevati vengono utilizzati per aggiornamenti cartografici perdono le coordinate originarie e vengono adattati a particolari cartografici circostanti. Per progettare una modernizzazione delle mappe catastali e delle carte tecniche finalizzata a consentire l’introduzione degli aggiornamenti senza modificarne le coordinate assolute originarie, lo studio è iniziato valutando come utilizzare sviluppi di strutturazione dei dati topografici presenti nel Database Geotopografico, modellizzazioni 3D di fabbricati nelle esperienze catastali INSPIRE, integrazioni in ambito MUDE tra progetti edilizi e loro realizzazioni. Lo studio è proseguito valutando i servizi di posizionamento in tempo reale NRTK presenti in Italia. Inoltre sono state effettuate sperimentazioni per verificare anche in sede locale la precisione e l’affidabilità dei servizi di posizionamento presenti. La criticità della cartografia catastale deriva sostanzialmente dal due fatti: che originariamente fu inquadrata in 850 Sistemi e successivamente fu trasformata in Roma40 con una esigua densità di punti rimisurati; che fino al 1988 fu aggiornata con modalità non rigorose di bassa qualità. Per risolvere tali criticità si è quindi ipotizzato di sfruttare le modalità di rilevamento NRTK per aumentare localmente la densità dei punti rimisurati e reinquadrare le mappe catastali. Il test, realizzato a Bologna, ha comportato un’analisi preliminare per individuare quali Punti Fiduciali considerare coerenti con le specifiche cartografiche per poi utilizzarli e aumentare localmente la densità dei punti rimisurati. La sperimentazione ha consentito la realizzazione del progetto e di inserire quindi i prossimi aggiornamenti senza modificarne le coordinate ETRF00 ottenute dal servizio di posizionamento.

Hydrodynamic induced by an array of wave energy converters. Experimental and numerical analysis

The thesis analyses the hydrodynamic induced by an array of Wave energy Converters (WECs), under an experimental and numerical point of view. WECs can be considered an innovative solution able to contribute to the green energy supply and –at the same time– to protect the rear coastal area under marine spatial planning considerations. This research activity essentially rises due to this combined concept. The WEC under exam is a floating device belonging to the Wave Activated Bodies (WAB) class. Experimental data were performed at Aalborg University in different scales and layouts, and the performance of the models was analysed under a variety of irregular wave attacks. The numerical simulations performed with the codes MIKE 21 BW and ANSYS-AQWA. Experimental results were also used to calibrate the numerical parameters and/or to directly been compared to numerical results, in order to extend the experimental database. Results of the research activity are summarized in terms of device performance and guidelines for a future wave farm installation. The device length should be “tuned” based on the local climate conditions. The wave transmission behind the devices is pretty high, suggesting that the tested layout should be considered as a module of a wave farm installation. Indications on the minimum inter-distance among the devices are provided. Furthermore, a CALM mooring system leads to lower wave transmission and also larger power production than a spread mooring. The two numerical codes have different potentialities. The hydrodynamics around single and multiple devices is obtained with MIKE 21 BW, while wave loads and motions for a single moored device are derived from ANSYS-AQWA. Combining the experimental and numerical it is suggested –for both coastal protection and energy production– to adopt a staggered layout, which will maximise the devices density and minimize the marine space required for the installation.

Methodologies for Synthesizable Programmable Devices based on Multi-Stage Switching Networks

Nowadays the rise of non-recurring engineering (NRE) costs associated with complexity is becoming a major factor in SoC design, limiting both scaling opportunities and the flexibility advantages offered by the integration of complex computational units. The introduction of embedded programmable elements can represent an appealing solution, able both to guarantee the desired flexibility and upgradabilty and to widen the SoC market. In particular embedded FPGA (eFPGA) cores can provide bit-level optimization for those applications which benefits from synthesis, paying on the other side in terms of performance penalties and area overhead with respect to standard cell ASIC implementations. In this scenario this thesis proposes a design methodology for a synthesizable programmable device designed to be embedded in a SoC. A soft-core embedded FPGA (eFPGA) is hence presented and analyzed in terms of the opportunities given by a fully synthesizable approach, following an implementation flow based on Standard-Cell methodology. A key point of the proposed eFPGA template is that it adopts a Multi-Stage Switching Network (MSSN) as the foundation of the programmable interconnects, since it can be efficiently synthesized and optimized through a standard cell based implementation flow, ensuring at the same time an intrinsic congestion-free network topology. The evaluation of the flexibility potentialities of the eFPGA has been performed using different technology libraries (STMicroelectronics CMOS 65nm and BCD9s 0.11μm) through a design space exploration in terms of area-speed-leakage tradeoffs, enabled by the full synthesizability of the template. Since the most relevant disadvantage of the adopted soft approach, compared to a hardcore, is represented by a performance overhead increase, the eFPGA analysis has been made targeting small area budgets. The generation of the configuration bitstream has been obtained thanks to the implementation of a custom CAD flow environment, and has allowed functional verification and performance evaluation through an application-aware analysis.

Sviluppo di metodologie innovative di supporto decisionale alla progettazione basate su indicatori di prestazione

Il progetto di ricerca è finalizzato allo sviluppo di una metodologia innovativa di supporto decisionale nel processo di selezione tra alternative progettuali, basata su indicatori di prestazione. In particolare il lavoro si è focalizzato sulla definizione d’indicatori atti a supportare la decisione negli interventi di sbottigliamento di un impianto di processo. Sono stati sviluppati due indicatori, “bottleneck indicators”, che permettono di valutare la reale necessità dello sbottigliamento, individuando le cause che impediscono la produzione e lo sfruttamento delle apparecchiature. Questi sono stati validati attraverso l’applicazione all’analisi di un intervento su un impianto esistente e verificando che lo sfruttamento delle apparecchiature fosse correttamente individuato. Definita la necessità dell’intervento di sbottigliamento, è stato affrontato il problema della selezione tra alternative di processo possibili per realizzarlo. È stato applicato alla scelta un metodo basato su indicatori di sostenibilità che consente di confrontare le alternative considerando non solo il ritorno economico degli investimenti ma anche gli impatti su ambiente e sicurezza, e che è stato ulteriormente sviluppato in questa tesi. Sono stati definiti due indicatori, “area hazard indicators”, relativi alle emissioni fuggitive, per integrare questi aspetti nell’analisi della sostenibilità delle alternative. Per migliorare l’accuratezza nella quantificazione degli impatti è stato sviluppato un nuovo modello previsionale atto alla stima delle emissioni fuggitive di un impianto, basato unicamente sui dati disponibili in fase progettuale, che tiene conto delle tipologie di sorgenti emettitrici, dei loro meccanismi di perdita e della manutenzione. Validato mediante il confronto con dati sperimentali di un impianto produttivo, si è dimostrato che tale metodo è indispensabile per un corretto confronto delle alternative poiché i modelli esistenti sovrastimano eccessivamente le emissioni reali. Infine applicando gli indicatori ad un impianto esistente si è dimostrato che sono fondamentali per semplificare il processo decisionale, fornendo chiare e precise indicazioni impiegando un numero limitato di informazioni per ricavarle.

Aureobasidium pullulans as biological control agent: modes of action

The postharvest phase has been considered an environment very suitable for successful application of biological control agents (BCAs). However, the tri-interaction between fungal pathogen, host (fruit) and antagonist is influenced by several parameters such as temperature, oxidative stresses, oxygen composition, water activity, etc. that could be determining for the success of biocontrol. Knowledge of the modes of action of BCAs is essential in order to enhance their viability and increase their potentialities in disease control. The thesis focused on the possibility to explain the modes of action of a biological control agent (BCA): Aureobasidium pullulans, in particular the strains L1 and L8, control effective against fruit postharvest fungal pathogen. In particular in this work were studied the different modes of action of BCA, such as: i) the ability to produce volatile organic compounds (VOCs), identified by SPME- gas chromatography-mass spectrometry (GC-MS) and tested by in vitro and in vivo assays against Penicillium spp., Botrytis cinerea, Colletotrichum acutatum; ii) the ability to produce lytic enzymes (exo and endo chitinase and β-1,3-glucanase) tested against Monilinia laxa, causal agent of brown rot of stone fruits. L1 and L8 lytic enzymes were also evaluated through their relative genes by molecular tools; iii) the competition for space and nutrients, such as sugars (sucrose, glucose and fructose) and iron; the latter induced the production of siderophores, molecules with high affinity for iron chelation. A molecular investigation was carried out to better understand the gene regulation strictly correlated to the production of these chelating molucules. The competition for space against M. laxa was verified by electron microscopy techniques; iv) a depth bibliographical analysis on BCAs mechanisms of action and their possible combination with physical and chemical treatments was conducted.

Internazionalizzazione e traduzione: Un'esperienza presso l'azienda TR Turoni S.R.L.

This dissertation was conducted within the project Language Toolkit, which has the aim of integrating the worlds of work and university. In particular, it consists of the translation into English of documents commissioned by the Italian company TR Turoni and its primary purpose is to demonstrate that, in the field of translation for companies, the existing translation support tools and software can optimise and facilitate the translation process. The work consists of five chapters. The first introduces the Language Toolkit project, the TR Turoni company and its relationship with the CERMAC export consortium. After outlining the current state of company internationalisation, the importance of professional translators in enhancing the competitiveness of companies that enter new international markets is highlighted. Chapter two provides an overview of the texts to be translated, focusing on the textual function and typology and on the addressees. After that, manual translation and the main software developed specifically for translators are described, with a focus on computer-assisted translation (CAT) and machine translation (MT). The third chapter presents the target texts and the corresponding translations. Chapter four is dedicated to the analysis of the translation process. The first two texts were translated manually, with the support of a purpose-built specialized corpus. The following two documents were translated with the software SDL Trados Studio 2011 and its applications. The last texts were submitted to the Google Translate service and to a process of pre and post-editing. Finally, in chapter five conclusions are drawn about the main limits and potentialities of the different translations techniques. In addition to this, the importance of an integrated use of all available instruments is underlined.

Traduzione tecnica e internazionalizzazione d'impresa: Il caso di Technologica S.r.l.

This dissertation is part of the Language Toolkit project which is a collaboration between the School of Foreign Languages and Literature, Interpreting and Translation of the University of Bologna, Forlì campus, and the Chamber of Commerce of Forlì-Cesena. This project aims to create an exchange between translation students and companies who want to pursue a process of internationalization. The purpose of this dissertation is demonstrating the benefits that translation systems can bring to businesses. In particular, it consists of the translation into English of documents supplied by the Italian company Technologica S.r.l. and the creation of linguistic resources that can be integrated into computer-assisted translation (CAT) software, in order to optimize the translation process. The latter is claimed to be a priority with respect to the actual translation products (the target texts), since the analysis conducted on the source texts highlighted that the company could streamline and optimize its English language communication thanks to the use of open source CAT tools such as OmegaT. The work consists of five chapters. The first introduces the Language Toolkit project, the company (Technologica S.r.l ) and its products. The second chapter provides some considerations about technical translation, its features and some misconceptions about it. The difference between technical translation and scientific translation is then clarified and an overview is offered of translation aids such as those used for computer-assisted translation, machine translation, termbases and translation memories. The third chapter contains the analysis of the texts commissioned by Technologica S.r.l. and their categorization. The fourth chapter describes the translation process, with particular attention to terminology extraction and the creation of a bilingual glossary based on a specialized corpus. The glossary was integrated into the OmegaT software in order to facilitate the translation process both for the present task and for future applications. The memory deriving from the translation represents a sort of hybrid resource between a translation memory and a glossary. This was found to be the most appropriate format, given the specific nature of the texts to be translated. Finally, in chapter five conclusions are offered about the importance of language training within a company environment, the potentialities of translation aids and the benefits that they would bring to a company wishing to internationalize itself.

User centered retrofit: The case of kadk campus, Copenhagen, (dk)

The following research thesis is about a retrofit project made in Denmark, Copenhagen, and carried out on one of the buildings belonging to the Royal Danish Academy. The key assumption and base of the entire research process is that, up to now, the standard procedure in retrofit cases like this provides as comparative method between de facto and design, the use of Energy Simulation software. These programs generally divide the space into different thermal zones, assigning to each of them different levels of employment, activities, set-point temperatures set for cooling and heating analysis and so on, but always providing average and constant values, usually taken in the middle point of the single thermal zone. Therefore, the project and its research path stems from the attempt to investigate the potentialities of this kind of designing for retrofit process, as previously anticipated not antithetical but complementary to that classic energy-based retrofit, thus passing from the building scale, and all its thermal zones, to the users' scale, related to humans and microclimates. The main software used in this process is Autodesk Simulation CFD. The idea behind the project is that in certain situations, for example, it will not be necessary to add throughout insulation layers (previously parameterized and optimized with Design Builder), and that even in Winter conditions, due maybe to the users' activities, the increased level of clothing (clo) and the heat produced by equipments, thermal comfort could be achieved also in areas characterized by considerably lower MRT. After the analysis of the State of Art and its simulations, the project has still been supported by the tool itself, the CFD Software, in an iterative process aimed at achieving visible improvements in terms of MRT, on spaces with different needs and characteristics, both in Winter and Summer regimes.

Marx and the Bible: José Miranda’s Critique of the Philosophy of Oppression

This paper critically examines the liberation theology of José Porfirio Miranda, as expressed in his Marx and the Bible (1971), with a focus on the central idea (and subtitle) of this work: the “Critique of the Philosophy of Oppression.” Miranda’s critique is examined via certain key tropes such as “power,” “justice,” and “freedom,” both in the context of late twentieth-century Latin American society, and in the state of the “post-Christian” and “post-Marxist” world more generally, vis-à-vis contemporary liberal justice theory. Close examination of the potentialities, paradoxes and subtle evasions in Miranda’s critique leads not to the conclusion that Miranda does not go far enough in his application of Christian principles to justice theory.

On the road through the Bolivian Amazon: a multi-level land governance analysis of deforestation

Previous studies have shown that collective property rights offer higher flexibility than individual property and improve sustainable community-based forest management. Our case study, carried out in the Beni department of Bolivia, does not contradict this assertion, but shows that collective rights have been granted in areas where ecological contexts and market facilities were less favourable to intensive land use. Previous experiences suggest investigating political processes in order to understand the criteria according to which access rights were distributed. Based on remote sensing and on a multi-level land governance framework, our research confirms that land placed under collective rights, compared to individual property, is less affected by deforestation among Andean settlements. However, analysis of the historical process of land distribution in the area shows that the distribution of property rights is the result of a political process based on economic, spatial, and environmental strategies that are defined by multiple stakeholders. Collective titles were established in the more remote areas and distributed to communities with lower productive potentialities. Land rights are thus a secondary factor of forest cover change which results from diverse political compromises based on population distribution, accessibility, environmental perceptions, and expected production or extraction incomes.

Registros discursivos postmodernos : Rajatabla, de Luis Britto García, o la estética del fragmento

Enmarcada en el ámbito amplio del pensamiento posmoderno y, en lo literario, dentro del fenómeno que la crítica ha denominado posboom, Luis Britto García ha construido una de las obras más fascinantes de la literatura venezolana actual, donde predominan un humor ácido y corrosivo, una imaginación desbordada que no sabe de fronteras, una acentuada erudición y un agudo sentido crítico. Este artículo se centra en el análisis de las posibilidades genéricas de su obra Rajatabla, publicada a comienzos de la década del 70. Su particular modo de construcción a partir de la suma de breves enunciados, su polifacético diseño estructural y la amplitud semántica que logra un universo asfixiante y apocalíptico plantean una serie de problemas en torno a su posible clasificación genérica para el que resulta esclarecedor el concepto de minificción.

Inserción ocupacional y prácticas laborales en microemprendimientos juveniles : Análisis de algunas experiencias promovidas por programas sociales en la Ciudad de Resistencia (Provincia de Chaco)

Los microemprendimientos productivos surgen en la última década como una opción alternativa para el tratamiento de la problemática laboral de los jóvenes en América Latina. En este trabajo realizamos una discusión sobre el alcance y las características de este tipo de intervenciones, analizando sus potencialidades y sus limitaciones en contextos con elevados índices de pobreza y mercados de trabajo deprimidos. En el texto, luego de realizar una breve revisión del estado del arte sobre el tema, presentamos los avances de un estudio en el que analizamos los primeros resultados de un programa implementado, hace algunos años, en la Ciudad de Resistencia (Provincia del Chaco) con dicho objetivo