Studio di fattibilità di un impianto di condizionamento tramite sistema geotermico: il caso ospedale nuovo di Imola

L’obiettivo dell’elaborato è analizzare la fattibilità tecnica ed economica di un impianto di prelievo d’acqua da falda artesiana per lo scambio termico nell’impianto frigorifero centralizzato dell’ospedale civile nuovo di Imola. Esso provvede a fornire acqua refrigerata a tutte le unità di trattamento aria (u.t.a.) del complesso ospedaliero ed è finalizzato a garantire per ogni locale le specifiche condizioni igrometriche , nonchè il benessere degli operatori e dei pazienti della struttura. Il lavoro di progettazione ha riguardato il dimensionamento di componenti e reti idrauliche con l’ausilio del software “EPANET” (programma per la simulazione di reti idrauliche). L’idea che ha guidato il presente elaborato è stata la creazione di un “ciclo” dell’acqua tale per cui l’acqua di scarto delle torri evaporative viene utilizzata per l’irrigazione degli orti nei pressi dei quale sorge il pozzo e successivamente, va ad alimentare la falda stessa. Le scelte progettuali hanno quindi dovuto considerare questo importante vincolo e sono state tese alla minimizzazione dei consumi d’acqua e , quindi, alla sostenibilità ambientale dell’intero impianto. In generale, infatti non è detto che la soluzione economicamente più vantaggiosa lo sia anche dal punto di vista ambientale. La soluzione adottata con rilancio dell’acqua agli orti limita il prelievo medio giornaliero d’acqua di falda di 20 m3/gg durante il periodo estivo. E’stato dimostrato come il progetto sia tecnicamente fattibile e generi valore per l’impresa con indice di rendimento IR(VAN/Capitale investito) pari a 1,29 per i primi 20 anni e pari a 2,06 per n anni di funzionamento dell’impianto con un tempo di recupero del capitale investito pari a sei anni.

Centro integrato socioculturale e religioso a Toscanella di Dozza

Il progetto per la cittadina di Toscanella, nasce dalla volontà di dare risposta ad un’esigenza locale di crescita e riqualificazione del centro storico. L'area in oggetto riguarda gran parte della cittadina di Toscanella. Uno degli obiettivi principali è quello di rivalutare ed integrare tale sito alla luce dell'espansione demografica degli ultimi decenni, integrandolo con servizi attualmente mancanti. Punti programmatici del progetto sono: - La realizzazione di un parco fluviale che permetta il recupero e la riqualificazione del tratto di riva del rio Sabbioso compreso tra via Nenni e via Caduti del lavoro; - Un nuovo centro religioso con locali parrocchiali, chiesa e casa canonica, richiesti per inadeguatezza degli attuali; - nuovo centro polifunzionale che comprenda spazi per lo spettacolo e le arti in generale, spazi per l'attività fisica e ricettività minori (bar, spazi comuni...).

Strutture a pareti portanti in C. A. caratterizzate da elevate prestazioni sismiche

Per quanto riguarda le costruzioni in conglomerato cementizio armato gettato in opera, i sistemi strutturali più comunemente utilizzati sono quelli a telaio (con trasmissione di momento flettente), a setti portanti o una combinazione di entrambi. A partire dagli anni ’60, numerosissimi sono stati gli studi relativamente al comportamento sismico di strutture in c.a. a telaio. Lo stesso si può affermare per le costruzioni costituite da pareti miste a telai. In particolare, l’argomento della progettazione sismica di tali tipologie di edifici ha sempre riguardato soprattutto gli edifici alti nei quali, evidentemente, l’impiego delle pareti avveniva allo scopo di limitarne la elevata deformabilità. Il comportamento sismico di strutture realizzate interamente a pareti portanti in c.a. è stato meno studiato negli anni, nonostante si sia osservato che edifici realizzati mediante tali sistemi strutturali abbiano mostrato, in generale, pregevoli risorse di resistenza nei confronti di terremoti anche di elevata intensità. Negli ultimi 10 anni, l’ingegneria sismica si sta incentrando sull’approfondimento delle risorse di tipologie costruttive di cui si è sempre fatto largo uso in passato (tipicamente nei paesi dell’Europa continentale, in America latina, negli USA e anche in Italia), ma delle quali mancavano adeguate conoscenze scientifiche relativamente al loro comportamento in zona sismica. Tali tipologie riguardano sostanzialmente sistemi strutturali interamente costituiti da pareti portanti in c.a. per edifici di modesta altezza, usualmente utilizzati in un’edilizia caratterizzata da ridotti costi di realizzazione (fabbricati per abitazioni civili e/o uffici). Obiettivo “generale” del lavoro di ricerca qui presentato è lo studio del comportamento sismico di strutture realizzate interamente a setti portanti in c.a. e di modesta altezza (edilizia caratterizzata da ridotti costi di realizzazione). In particolare, le pareti che si intendono qui studiare sono caratterizzate da basse percentuali geometriche di armatura e sono realizzate secondo la tecnologia del cassero a perdere. A conoscenza dello scrivente, non sono mai stati realizzati, fino ad oggi, studi sperimentali ed analitici allo scopo di determinare il comportamento sismico di tali sistemi strutturali, mentre è ben noto il loro comportamento statico. In dettaglio, questo lavoro di ricerca ha il duplice scopo di: • ottenere un sistema strutturale caratterizzato da elevate prestazioni sismiche; • mettere a punto strumenti applicativi (congruenti e compatibili con le vigenti normative e dunque immediatamente utilizzabili dai progettisti) per la progettazione sismica dei pannelli portanti in c.a. oggetto del presente studio. Al fine di studiare il comportamento sismico e di individuare gli strumenti pratici per la progettazione, la ricerca è stata organizzata come segue: • identificazione delle caratteristiche delle strutture studiate, mediante lo sviluppo/specializzazione di opportune formulazioni analitiche; • progettazione, supervisione, ed interpretazione di una estesa campagna di prove sperimentali eseguita su pareti portanti in c.a. in vera grandezza, al fine di verificarne l’efficace comportamento sotto carico ciclico; • sviluppo di semplici indicazioni (regole) progettuali relativamente alle strutture a pareti in c.a. studiate, al fine di ottenere le caratteristiche prestazionali desiderate. I risultati delle prove sperimentali hanno mostrato di essere in accordo con le previsioni analitiche, a conferma della validità degli strumenti di predizione del comportamento di tali pannelli. Le elevatissime prestazioni riscontrate sia in termini di resistenza che in termini di duttilità hanno evidenziato come le strutture studiate, così messe a punto, abbiano manifestato un comportamento sismico più che soddisfacente.

Il ruolo del collicolo superiore nell'orientamento spaziale

This thesis was aimed at verifying the role of the superior colliculus (SC) in human spatial orienting. To do so, subjects performed two experimental tasks that have been shown to involve SC’s activation in animals, that is a multisensory integration task (Experiment 1 and 2) and a visual target selection task (Experiment 3). To investigate this topic in humans, we took advantage of neurophysiological finding revealing that retinal S-cones do not send projections to the collicular and magnocellular pathway. In the Experiment 1, subjects performed a simple reaction-time task in which they were required to respond as quickly as possible to any sensory stimulus (visual, auditory or bimodal audio-visual). The visual stimulus could be an S-cone stimulus (invisible to the collicular and magnocellular pathway) or a long wavelength stimulus (visible to the SC). Results showed that when using S-cone stimuli, RTs distribution was simply explained by probability summation, indicating that the redundant auditory and visual channels are independent. Conversely, with red long-wavelength stimuli, visible to the SC, the RTs distribution was related to nonlinear neural summation, which constitutes evidence of integration of different sensory information. We also demonstrate that when AV stimuli were presented at fixation, so that the spatial orienting component of the task was reduced, neural summation was possible regardless of stimulus color. Together, these findings provide support for a pivotal role of the SC in mediating multisensory spatial integration in humans, when behavior involves spatial orienting responses. Since previous studies have shown an anatomical asymmetry of fibres projecting to the SC from the hemiretinas, the Experiment 2 was aimed at investigating temporo-nasal asymmetry in multisensory integration. To do so, subjects performed monocularly the same task shown in the Experiment 1. When spatially coincident audio-visual stimuli were visible to the SC (i.e. red stimuli), the RTE depended on a neural coactivation mechanism, suggesting an integration of multisensory information. When using stimuli invisible to the SC (i.e. purple stimuli), the RTE depended only on a simple statistical facilitation effect, in which the two sensory stimuli were processed by independent channels. Finally, we demonstrate that the multisensory integration effect was stronger for stimuli presented to the temporal hemifield than to the nasal hemifield. Taken together, these findings suggested that multisensory stimulation can be differentially effective depending on specific stimulus parameters. The Experiment 3 was aimed at verifying the role of the SC in target selection by using a color-oddity search task, comprising stimuli either visible or invisible to the collicular and magnocellular pathways. Subjects were required to make a saccade toward a target that could be presented alone or with three distractors of another color (either S-cone or long-wavelength). When using S-cone distractors, invisible to the SC, localization errors were similar to those observed in the distractor-free condition. Conversely, with long-wavelength distractors, visible to the SC, saccadic localization error and variability were significantly greater than in either the distractor-free condition or the S-cone distractors condition. Our results clearly indicate that the SC plays a direct role in visual target selection in humans. Overall, our results indicate that the SC plays an important role in mediating spatial orienting responses both when required covert (Experiments 1 and 2) and overt orienting (Experiment 3).

Nuove tecniche per l'allevamento massale di Ditteri del genere Coenosia Meigen

The species of the genus Coenosia Meigen are polyphagous predators both in the larval and in the adult stage. In Europe five Coenosia species of the ‘tigrina group’ are naturally present in greenhouses, where they can establish for long periods. As their wide preys range includes important pests of protected crops, as Aleyrodidae, Sciaridae and Agromyzidae, Coenosia species are considered promising potential biological control agents. A method for rearing Coenosia species in vivo was developed for the first time in 1993 in Germany, where C. attenuata, C. strigipes and C. humilis were bred on Bradysia paupera (Diptera Sciaridae), reared on Fusarium spp. cultivated on wood fibre. Although this method was partially simplified afterwards, it is still too complex and expensive for a mass production. This research aimed at simplifying this rearing procedure and making it cheaper, in the perspective of an eventual mass production. Studies on potential preys were conducted, to determine their suitability for C. attenuata larvae and adults and to develop rearing methods. Biology and rearing methods of Bradysia paupera Tuomikoski, Scatella stagnalis Fallén and Drosophila melanogaster Meigen (Diptera: Sciaridae, Ephydridae, Drosophilidae) were compared. B. paupera resulted the most suitable prey for rearing C. attenuata in vivo. The Sciarid fly was effectively reared on damp coconut fibre with fresh Agaricus bisporus (J.E. Lange) Pilát, thus simplifying the existing method. After preliminary trials with different potential preys, attempts to rear C. attenuata in vivo on B. paupera and D. melanogaster were made. The best results were obtained with B. paupera, reared on coconut fibre and A. bisporus, but the method needs further improvement. Trials of in vitro rearing of C. attenuata were also made: as no specific diet for Coenosia species is reported in literature, different potentially suitable media were tested. Among these, a specific diet for Diptera Tachinidae resulted a good starting point for further studies and improvements. The biology of C. attenuata adults captured in greenhouses was also studied, by observing both groups and isolated individuals. Data on lifespan, daily number of preys per adult, daily number of laid eggs and hatching rate were recorded, and the effects of different foods on these parameters were analyzed. The following foods were compared: D. melanogaster adults only, as preys for C. attenuata; D. melanogaster adults and a water-honey solution; the water-honey solution only. Honey resulted an effective food integration for C. attenuata, increasing lifespan and the number of egg laying females. It is possible that in greenhouses Coenosia adults complete the preys diet with nectar and/or honeydew. Moreover, the integration with honey reduced the daily preys consumption. This may allow to prevent cannibalism among Coenosia adults in the rearing conditions, where high population densities are required. A survey of the Coenosia species naturally present in Lombardy greenhouses was conducted. The species C. attenuata, C. strigipes, C. tigrina and C. atra were detected. C. attenuata resulted the most common, recorded in most greenhouses and for consecutive years. Besides, the presence of potential preys, weeds and the crops were recorded in each greenhouse. Nevertheless, it is difficult to determine the relation between these parameters and the presence of Coenosia species.

Effetti dell'integrazione visuo-acustica in pazienti con disturbo di campo visivo

Human brain is provided with a flexible audio-visual system, which interprets and guides responses to external events according to spatial alignment, temporal synchronization and effectiveness of unimodal signals. The aim of the present thesis was to explore the possibility that such a system might represent the neural correlate of sensory compensation after a damage to one sensory pathway. To this purpose, three experimental studies have been conducted, which addressed the immediate, short-term and long-term effects of audio-visual integration on patients with Visual Field Defect (VFD). Experiment 1 investigated whether the integration of stimuli from different modalities (cross-modal) and from the same modality (within-modal) have a different, immediate effect on localization behaviour. Patients had to localize modality-specific stimuli (visual or auditory), cross-modal stimulus pairs (visual-auditory) and within-modal stimulus pairs (visual-visual). Results showed that cross-modal stimuli evoked a greater improvement than within modal stimuli, consistent with a Bayesian explanation. Moreover, even when visual processing was impaired, cross-modal stimuli improved performance in an optimal fashion. These findings support the hypothesis that the improvement derived from multisensory integration is not attributable to simple target redundancy, and prove that optimal integration of cross-modal signals occurs in processing stage which are not consciously accessible. Experiment 2 examined the possibility to induce a short term improvement of localization performance without an explicit knowledge of visual stimulus. Patients with VFD and patients with neglect had to localize weak sounds before and after a brief exposure to a passive cross-modal stimulation, which comprised spatially disparate or spatially coincident audio-visual stimuli. After exposure to spatially disparate stimuli in the affected field, only patients with neglect exhibited a shifts of auditory localization toward the visual attractor (the so called Ventriloquism After-Effect). In contrast, after adaptation to spatially coincident stimuli, both neglect and hemianopic patients exhibited a significant improvement of auditory localization, proving the occurrence of After Effect for multisensory enhancement. These results suggest the presence of two distinct recalibration mechanisms, each mediated by a different neural route: a geniculo-striate circuit and a colliculus-extrastriate circuit respectively. Finally, Experiment 3 verified whether a systematic audio-visual stimulation could exert a long-lasting effect on patients’ oculomotor behaviour. Eye movements responses during a visual search task and a reading task were studied before and after visual (control) or audio-visual (experimental) training, in a group of twelve patients with VFD and twelve controls subjects. Results showed that prior to treatment, patients’ performance was significantly different from that of controls in relation to fixations and saccade parameters; after audiovisual training, all patients reported an improvement in ocular exploration characterized by fewer fixations and refixations, quicker and larger saccades, and reduced scanpath length. Similarly, reading parameters were significantly affected by the training, with respect to specific impairments observed in left and right hemisphere–damaged patients. The present findings provide evidence that a systematic audio-visual stimulation may encourage a more organized pattern of visual exploration with long lasting effects. In conclusion, results from these studies clearly demonstrate that the beneficial effects of audio-visual integration can be retained in absence of explicit processing of visual stimulus. Surprisingly, an improvement of spatial orienting can be obtained not only when a on-line response is required, but also after either a brief or a long adaptation to audio-visual stimulus pairs, so suggesting the maintenance of mechanisms subserving cross-modal perceptual learning after a damage to geniculo-striate pathway. The colliculus-extrastriate pathway, which is spared in patients with VFD, seems to play a pivotal role in this sensory compensation.

Radioattività naturale nei prodotti ceramici: valutazioni teoriche e sperimentali degli effetti ambientali e sanitari

I materiali zirconiferi, in particolare i silicati di zirconio e l’ossido di zirconio, vengono ampiamente utilizzati in diverse applicazioni industriali: fra queste, l’industria delle piastrelle ceramiche e di produzione dei materiali refrattari ne consuma quantitativi consistenti. Misure di spettrometria gamma condotte su diversi campioni di materiale zirconifero (farine di zirconio e sabbie zirconifere) utilizzati nell’industria ceramica per la produzione del gres porcellanato e delle piastrelle smaltate, hanno messo in evidenza valori di concentrazione di attività superiori a quelli presenti mediamente sulla crosta terrestre (35, 30 Bqkg-1 per il 238U e il 232Th, rispettivamente [Unscear, 2000]). L’aggiunta del materiale zirconifero nella preparazione delle piastrelle ceramiche in particolare di quelle smaltate (in una percentuale in peso pari al 10-20%) del gres porcellanato (in una percentuale in peso di 1-10%) e delle lamine di gres porcellanato “sottile” (in una percentuale in peso dell’ordine del 30%), conferisce al prodotto finale un alto grado di bianco, buone caratteristiche meccaniche ed un elevato effetto opacizzante, ma comporta anche un arricchimento in radionuclidi naturali. L’obiettivo principale di questo lavoro di tesi è stato quello di mettere a punto una metodologia (teorica e sperimentale) per valutare l’incremento di esposizione che possono ricevere un lavoratore standard di una industria ceramica ed una persona del pubblico che soggiorna in un ambiente rivestito con piastrelle. Da un lato, la presenza di radioattività nelle sabbie zirconifere, utilizzate come materie prime per la produzione di piastrelle, porta a considerare il problema dell’incremento di esposizione che può subire un lavoratore impiegato in ambiente di lavoro dove sono stoccati e manipolati consistenti quantitativi di materiale, dall’altro il contenuto di radioattività nel prodotto finito porta a considerare l’esposizione per una persona della popolazione che soggiorna in una stanza rivestita con materiale ceramico. Le numerose misure effettuate, unitamente allo sviluppo dei modelli necessari per valutare le dosi di esposizione per le persone del pubblico e dei lavoratori impiegati nel processo di produzione di piastrelle ceramiche, hanno permesso di mettere a punto una procedura che fornisce le garanzie necessarie per dichiarare accettabili le condizioni di lavoro nelle industrie ceramiche e più in generale il rispetto delle norme radioprotezionistiche per gli occupanti di ambienti rivestiti con piastrelle italiane.

Analisi spaziale dei dati entomologici in ambiente GIS: prospettive di utilizzo nell'agricoltura di precisione

Scopo della ricerca è stato definire le dinamiche spazio-temporali degli insetti studiati mediante l’impiego di tecniche geostatistiche. La ricerca è stata condotta su due casi studio, il primo riguardante tre specie di Elateridi di elevata importanza economica su scala aziendale, il secondo inerente al monitoraggio di Diabrotica virgifera virgifera (diabrotica del mais) su scala regionale. Gli scopi specifici dei due casi studio sono stati: Caso studio 1 a) Monitorare l’entità della popolazione di Elateridi su scala aziendale mediante approccio geostatistico. b) Elaborazione di mappe di distribuzione spaziale interfacciabili all’ambiente GIS. c) Individuare i fattori predisponenti l’infestazione. d) Verificare la necessità dell’impiego di mezzi chimici per il controllo delle specie dannose. e) Proporre strategie alternative volte alla riduzione dell’impiego di trattamenti geodisinfestanti. Caso studio 2 a) Studiare la distribuzione spaziale su scala regionale la popolazione del fitofago D. virgifera virgifera. b) Applicare a livello regionale una griglia di monitoraggio efficace per studiarne la diffusione. c) Individuare le aree a rischio e studiare i fattori predisponenti l’infestazione e diffusione. d) Ottimizzare ed economizzare il piano di monitoraggio.

Biomimetic Materials for Biomedical Applications

Objects with complex shape and functions have always attracted attention and interest. The morphological diversity and complexity of naturally occurring forms and patterns have been a motivation for humans to copy and adopt ideas from Nature to achieve functional, aesthetic and social value. Biomimetics is addressed to the design and development of new synthetic materials using strategies adopted by living organisms to produce biological materials. In particular, biomineralized tissues are often sophisticate composite materials, in which the components and the interfaces between them have been defined and optimized, and that present unusual and optimal chemical-physical, morphological and mechanical properties. Moreover, biominerals are generally produced by easily traceable raw materials, in aqueous media and at room pressure and temperature, that is through cheap process and materials. Thus, it is not surprising that the idea to mimic those strategies proper of Nature has been employed in several areas of applied sciences, such as for the preparation of liquid crystals, ceramic thin films computer switches and many other advanced materials. On this basis, this PhD thesis is focused on the investigation of the interaction of biologically active ions and molecules with calcium phosphates with the aim to develop new materials for the substitution and repair of skeletal tissue, according to the following lines: I. Modified calcium phosphates. A relevant part of this PhD thesis has been addressed to study the interaction of Strontium with calcium phosphates. It was demonstrated that strontium ion can substitute for calcium into hydroxyapatite, causing appreciable structural and morphological modifications. The detailed structural analysis carried out on the nanocrystals at different strontium content provided new insight into its interaction with the structure of hydroxyapatite. At variance with the behaviour of Sr towards HA, it was found that this ion inhibits the synthesis of octacalcium phosphate. However, it can substitute for calcium in this structure up to 15 atom %, in agreement with the increase of the cell parameters observed on increasing ion concentration. A similar behaviour was found for Magnesium ion, whereas Manganese inhibits the synthesis of octacalcium phosphate and it promotes the precipitation of dicalcium phosphate dehydrate. It was also found that Strontium affects the kinetics of the reaction of hydrolysis of α-TCP. It inhibits the conversion from α-TCP to hydroxyapatite. However, the resulting apatitic phase contains significant amounts of Sr2+ suggesting that the addition of Sr2+ to the composition of α-TCP bone cements could be successfully exploited for its local delivery in bone defects. The hydrolysis of α-TCP has been investigated also in the presence of increasing amounts of gelatin: the results indicated that this biopolymer accelerates the hydrolysis reaction and promotes the conversion of α-TCP into OCP, suggesting that its addition in the composition of calcium phosphate cements can be employed to modulate the OCP/HA ratio, and as a consequence the solubility, of the set cement. II. Deposition of modified calcium phosphates on metallic substrates. Coating with a thin film of calcium phosphates is frequently applied on the surface of metallic implants in order to combine the high mechanical strength of the metal with the excellent bioactivity of the calcium phosphates surface layers. During this PhD thesis, thank to the collaboration with prof. I.N. Mihailescu, head of the Laser-Surface-Plasma Interactions Laboratory (National Institute for Lasers, Plasma and Radiation Physics – Laser Department, Bucharest) Pulsed Laser Deposition has been successfully applied to deposit thin films of Sr substituted HA on Titanium substrates. The synthesized coatings displayed a uniform Sr distribution, a granular surface and a good degree of crystallinity which slightly decreased on increasing Sr content. The results of in vitro tests carried out on osteoblast-like and osteoclast cells suggested that the presence of Sr in HA thin films can enhance the positive effect of HA coatings on osteointegration and bone regeneration, and prevent undesirable bone resorption. The possibility to introduce an active molecule in the implant site was explored using Matrix Assisted Pulsed Laser Evaporation to deposit hydroxyapatite nanocrystals at different content of alendronate, a bisphosphonate widely employed in the treatments of pathological diseases associated to bone loss. The coatings displayed a good degree of crystallinity, and the results of in vitro tests indicated that alendronate promotes proliferation and differentiation of osteoblasts even when incorporated into hydroxyapatite. III. Synthesis of drug carriers with a delayed release modulated by a calcium phosphate coating. A core-shell system for modulated drug delivery and release has been developed through optimization of the experimental conditions to cover gelatin microspheres with a uniform layer of calcium phosphate. The kinetics of the release from uncoated and coated microspheres was investigated using aspirin as a model drug. It was shown that the presence of the calcium phosphate shell delays the release of aspirin and allows to modulate its action.

Emotional engagement and orienting: the effects of picture size on affective response

For their survival, humans and animals can rely on motivational systems which are specialized in assessing the valence and imminence of dangers and appetitive cues. The Orienting Response (OR) is a fundamental response pattern that an organism executes whenever a novel or significant stimulus is detected, and has been shown to be consistently modulated by the affective value of a stimulus. However, detecting threatening stimuli and appetitive affordances while they are far away compared to when they are within reach constitutes an obvious evolutionary advantage. Building on the linear relationship between stimulus distance and retinal size, the present research was aimed at investigating the extent to which emotional modulation of distinct processes (action preparation, attentional capture, and subjective emotional state) is affected when reducing the retinal size of a picture. Studies 1-3 examined the effects of picture size on emotional response. Subjective feeling of engagement, as well as sympathetic activation, were modulated by picture size, suggesting that action preparation and subjective experience reflect the combined effects of detecting an arousing stimulus and assessing its imminence. On the other hand, physiological responses which are thought to reflect the amount of attentional resources invested in stimulus processing did not vary with picture size. Studies 4-6 were conducted to substantiate and extend the results of studies 1-3. In particular, it was noted that a decrease in picture size is associated with a loss in the low spatial frequencies of a picture, which might confound the interpretation of the results of studies 1-3. Therefore, emotional and neutral images which were either low-pass filtered or reduced in size were presented, and affective responses were measured. Most effects which were observed when manipulating image size were replicated by blurring pictures. However, pictures depicting highly arousing unpleasant contents were associated with a more pronounced decrease in affective modulation when pictures were reduced in size compared to when they were blurred. The present results provide important information for the study of processes involved in picture perception and in the genesis and expression of an emotional response. In particular, the availability of high spatial frequencies might affect the degree of activation of an internal representation of an affectively charged scene, and might modulate subjective emotional state and preparation for action. Moreover, the manipulation of stimulus imminence revealed important effects of stimulus engagement on specific components of the emotional response, and the implications of the present data for some models of emotions have been discussed. In particular, within the framework of a staged model of emotional response, the tactic and strategic role of response preparation and attention allocation to stimuli varying in engaging power has been discussed, considering the adaptive advantages that each might represent in an evolutionary view. Finally, the identification of perceptual parameters that allow affective processing to be carried out has important methodological applications in future studies examining emotional response in basic research or clinical contexts.

Copper(I) phenanthroline complexes and supramolecular systems containing fullerenes: Photophysics, photochemistry and potential applications in sustainable energy technologies.

Chemistry can contribute, in many different ways to solve the challenges we are facing to modify our inefficient and fossil-fuel based energy system. The present work was motivated by the search for efficient photoactive materials to be employed in the context of the energy problem: materials to be utilized in energy efficient devices and in the production of renewable electricity and fuels. We presented a new class of copper complexes, that could find application in lighting techhnologies, by serving as luminescent materials in LEC, OLED, WOLED devices. These technologies may provide substantial energy savings in the lighting sector. Moreover, recently, copper complexes have been used as light harvesting compounds in dye sensitized photoelectrochemical solar cells, which offer a viable alternative to silicon-based photovoltaic technologies. We presented also a few supramolecular systems containing fullerene, e.g. dendrimers, dyads and triads.The most complex among these arrays, which contain porphyrin moieties, are presented in the final chapter. They undergo photoinduced energy- and electron transfer processes also with long-lived charge separated states, i.e. the fundamental processes to power artificial photosynthetic systems.

X-Ray studies of the physics of matter around super-massive black-holes in nearby Seyfert galaxies

Seyfert galaxies are the closest active galactic nuclei. As such, we can use them to test the physical properties of the entire class of objects. To investigate their general properties, I took advantage of different methods of data analysis. In particular I used three different samples of objects, that, despite frequent overlaps, have been chosen to best tackle different topics: the heterogeneous BeppoS AX sample was thought to be optimized to test the average hard X-ray (E above 10 keV) properties of nearby Seyfert galaxies; the X-CfA was thought the be optimized to compare the properties of low-luminosity sources to the ones of higher luminosity and, thus, it was also used to test the emission mechanism models; finally, the XMM–Newton sample was extracted from the X-CfA sample so as to ensure a truly unbiased and well defined sample of objects to define the average properties of Seyfert galaxies. Taking advantage of the broad-band coverage of the BeppoS AX MECS and PDS instruments (between ~2-100 keV), I infer the average X-ray spectral propertiesof nearby Seyfert galaxies and in particular the photon index (~1.8), the high-energy cut-off (~290 keV), and the relative amount of cold reflection (~1.0). Moreover the unified scheme for active galactic nuclei was positively tested. The distribution of isotropic indicators used here (photon index, relative amount of reflection, high-energy cut-off and narrow FeK energy centroid) are similar in type I and type II objects while the absorbing column and the iron line equivalent width significantly differ between the two classes of sources with type II objects displaying larger absorbing columns. Taking advantage of the XMM–Newton and X–CfA samples I also deduced from measurements that 30 to 50% of type II Seyfert galaxies are Compton thick. Confirming previous results, the narrow FeK line is consistent, in Seyfert 2 galaxies, with being produced in the same matter responsible for the observed obscuration. These results support the basic picture of the unified model. Moreover, the presence of a X-ray Baldwin effect in type I sources has been measured using for the first time the 20-100 keV luminosity (EW proportional to L(20-100)^(−0.22±0.05)). This finding suggests that the torus covering factor may be a function of source luminosity, thereby suggesting a refinement of the baseline version of the unifed model itself. Using the BeppoSAX sample, it has been also recorded a possible correlation between the photon index and the amount of cold reflection in both type I and II sources. At a first glance this confirms the thermal Comptonization as the most likely origin of the high energy emission for the active galactic nuclei. This relation, in fact, naturally emerges supposing that the accretion disk penetrates, depending to the accretion rate, the central corona at different depths (Merloni et al. 2006): the higher accreting systems hosting disks down to the last stable orbit while the lower accreting systems hosting truncated disks. On the contrary, the study of the well defined X–C f A sample of Seyfert galaxies has proved that the intrinsic X-ray luminosity of nearby Seyfert galaxies can span values between 10^(38−43) erg s^−1, i.e. covering a huge range of accretion rates. The less efficient systems have been supposed to host ADAF systems without accretion disk. However, the study of the X–CfA sample has also proved the existence of correlations between optical emission lines and X-ray luminosity in the entire range of L_(X) covered by the sample. These relations are similar to the ones obtained if high-L objects are considered. Thus the emission mechanism must be similar in luminous and weak systems. A possible scenario to reconcile these somehow opposite indications is assuming that the ADAF and the two phase mechanism co-exist with different relative importance moving from low-to-high accretion systems (as suggested by the Gamma vs. R relation). The present data require that no abrupt transition between the two regimes is present. As mentioned above, the possible presence of an accretion disk has been tested using samples of nearby Seyfert galaxies. Here, to deeply investigate the flow patterns close to super-massive black-holes, three case study objects for which enough counts statistics is available have been analysed using deep X-ray observations taken with XMM–Newton. The obtained results have shown that the accretion flow can significantly differ between the objects when it is analyzed with the appropriate detail. For instance the accretion disk is well established down to the last stable orbit in a Kerr system for IRAS 13197-1627 where strong light bending effect have been measured. The accretion disk seems to be formed spiraling in the inner ~10-30 gravitational radii in NGC 3783 where time dependent and recursive modulation have been measured both in the continuum emission and in the broad emission line component. Finally, the accretion disk seems to be only weakly detectable in rk 509, with its weak broad emission line component. Finally, blueshifted resonant absorption lines have been detected in all three objects. This seems to demonstrate that, around super-massive black-holes, there is matter which is not confined in the accretion disk and moves along the line of sight with velocities as large as v~0.01-0.4c (whre c is the speed of light). Wether this matter forms winds or blobs is still matter of debate together with the assessment of the real statistical significance of the measured absorption lines. Nonetheless, if confirmed, these phenomena are of outstanding interest because they offer new potential probes for the dynamics of the innermost regions of accretion flows, to tackle the formation of ejecta/jets and to place constraints on the rate of kinetic energy injected by AGNs into the ISM and IGM. Future high energy missions (such as the planned Simbol-X and IXO) will likely allow an exciting step forward in our understanding of the flow dynamics around black holes and the formation of the highest velocity outflows.

Interessi finanziari e diritto sanzionatorio comunitario

L’oggetto della presente tesi di ricerca è l’analisi della situazione attuale della protezione degli interessi finanziari delle Comunità Europee, oltre che le sue prospettive di futuro. Il lavoro è suddiviso in due grandi parti. La prima studia il regime giuridico del Diritto sanzionatorio comunitario, cioè, la competenza sanzionatoria dell’Unione Europea. Questa sezione è stata ricostruita prendendo in considerazione i precetti normativi del Diritto originario e derivato, oltre che le principali sentenze della Corte di Giustizia, tra cui assumono particolare rilievo le sentenze di 27 ottobre 1992, Germania c. Commissione, affare C-240/90 e di 13 settembre 2005 e di 23 ottobre 2007, Commissione c. Consiglio, affari C-176/03 e C-440/05. A questo segue l’analisi del ruolo dei diritti fondamentali nell’ordinamento comunitario, così come la rilevanza della Convenzione Europea dei Diritti dell’Uomo e la Corte Europea dei Diritti dell’Uomo. Il secondo capitolo si sofferma particolarmente sullo studio delle sanzioni comunitarie, classificandole in ragione della loro natura giuridica alla luce anche dei principi generali di legalità, di proporzionalità, di colpevolezza e del non bis in idem. La seconda sezione sviluppa un’analisi dettagliata del regime giuridico della protezione degli interessi finanziari comunitari. Questa parte viene costruita indagando tutta l’evoluzione normativa e istituzionale, in considerazione anche delle novità più recenti (ad esempio, l’istituzione del Pubblico Ministero Europeo). In questo contesto si definisce il contenuto del concetto di interessi finanziari comunitari, dato che non esiste un’analoga definizione comunitaria della fattispecie. L’attenzione del dottorando si concentra poi sulla Convenzione avente ad oggetto la tutela degli interessi finanziari delle Comunità Europee e i regolamenti del Consiglio n. 2988/95 e 2185/96, che costituiscono la parte generale del Diritto sanzionatorio comunitario. Alla fine si esamina la ricezione della Convenzione PIF nel Codice Penale spagnolo e i principali problemi di cui derivano. L’originalità dell’approccio proposto deriva dell’assenza di un lavoro recente che, in modo esclusivo e concreto, analizzi la protezione amministrativa e penale degli interessi finanziari della Comunità. Inoltre, la Carta Europea di Diritti Fondamentali e il Trattato di Lisbona sono due grandi novità che diventeranno una realtà tra poco tempo.

Transformations of bridging ligands in diiron complexes: unconventional routes to new functionalized multisite bound organic frames

The main scope of this Ph.D. thesis has concerned the possible transformations of bridging ligands in diiron complexes, in order to explore unconventional routes to the synthesis of new functionalized multisite bound organic frames. The results achieved during the Ph.D. can be summarized in the following points: 1) We have extended the assembling between small unsaturated molecules and bridging carbyne ligands in diiron complexes to other species. In particular, we have investigated the coupling between olefins and thiocarbyne, leading to the synthesis of thioallylidene bridging diiron complexes. Then, we have extended the study to the coupling between olefins and aminocarbyne. This result shows that the coupling between activated olefins and heteroatom substituted bridging carbynes has a general character. 2) As we have shown, the coupling of bridging alkylidyne ligands with alkynes and alkenes provides excellent routes to the synthesis of bridging C3 hydrocarbyl ligands. As a possible extension of these results we have examined the synthesis of C4 bridging frames through the combination of bridging alkylidynes with allenes. Also in this case the reaction has a general character. 3) Diiron complexes bearing bridging functionalized C3 organic frames display the presence of donor atoms, such as N and S, potentially able to coordinate unsaturated metal fragments. Thus, we have studied the possibility for these systems to act as ‘organometallic ligands’, in particular towards Pd and Rh. 4) The possibility of releasing the organic frame from the bridging coordination appears particularly appealing in the direction of a metal-assisted organic synthesis. Within this field, we have investigated the possibility of involving the C3 bridging ligand in cycloaddition reactions with alkynes, with the aim of generating variously functionalized five-membered cycles. The [3+2] cyclization does not lead to the complete release of the organic fragment but rather it produces its transformation into a cyclopentadienyl ring, which remains coordinated to one Fe atom. This result introduces a new approach to the formation of polyfunctionalised ferrocenes. 5) Furthermore, I have spent a research period of about six months at the Department of Inorganic Chemistry of the Barcelona University, under the supervision of Prof. Concepción López, with the aim of studying the chemistry of polydentate ferrocenyl ligands and their use in organometallic synthesis.