806 resultados para Internet of things, Mqtt, domotica, Raspberry Pi
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Pós-graduação em Geografia - IGCE
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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
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This Article reports a combined experimental and theoretical analysis on the one and two-photon absorption properties of a novel class of organic molecules with a pi-conjugated backbone based on phenylacetylene (JCM874, FD43, and FD48) and azoaromatic (YB3p2S) moieties. Linear optical properties show that the phenylacetylene-based compounds exhibit strong molar absorptivity in the UV and high fluorescence quantum yield with lifetimes of approximately 2.0 ns, while the azoaromatic-compound has a strong absorption in the visible region with very low fluorescence quantum yield. The two-photon absorption was investigated employing nonlinear optical techniques and quantum chemical calculations based on the response functions formalism within the density functional theory framework. The experimental data revealed well-defined 2PA spectra with reasonable cross-section values in the visible and IR. Along the nonlinear spectra we observed two 2PA allowed bands, as well as the resonance enhancement effect due to the presence of one intermediate one-photon allowed state. Quantum chemical calculations revealed that the 2PA allowed bands correspond to transitions to states that are also one-photon allowed, indicating the relaxation of the electric-dipole selection rules. Moreover, using the theoretical results, we were able to interpret the experimental trends of the 2PA spectra. Finally, using a few-energy-level diagram, within the sum-over-essential states approach, we observed strong qualitative and quantitative correlation between experimental and theoretical results.
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«In altri termini mi sfuggiva e ancora oggi mi sfugge gran parte del significato dell’evoluzione del tempo; come se il tempo fosse una materia che osservo dall’esterno. Questa mancanza di evoluzione è fonte di alcune mie sventure ma anche mi appartiene con gioia.» Aldo Rossi, Autobiografia scientifica. The temporal dimension underpinning the draft of Autobiografia scientifica by Aldo Rossi may be referred to what Lucien Lévy-Bruhl, the well-known French anthropologist, defines as “primitive mentality” and “prelogical” conscience : the book of life has lost its page numbers, even punctuation. For Lévy-Bruhl, but certainly for Rossi, life or its summing up becomes a continuous account of ellipses, gaps, repetitions that may be read from left to right or viceversa, from head to foot or viceversa without distinction. Rossi’s autobiographical writing seems to accept and support the confusion with which memories have been collected, recording them after the order memory gives them in the mental distillation or simply according to the chronological order in which they have happened. For Rossi, the confusion reflects the melting of memory elements into a composite image which is the result of a fusion. He is aware that the same sap pervades all memories he is going to put in order: each of them has got a common denominator. Differences have diminished, almost faded; the quick glance is prevalent over the distinction of each episode. Rossi’s writing is beyond the categories dependent on time: past and present, before and now. For Rossi, the only repetition – the repetition the text will make possible for an indefinite number of times – gives peculiarity to the event. As Gilles Deleuze knows, “things” may only last as “singleness”: more frequent the repetition is, more singular is the memory phenomenon that recurs, because only what is singular magnifies itself and happens endlessly forever. Rossi understands that “to raise the first time to nth forever”, repetition becomes glorification . It may be an autobiography that, celebrating the originality, enhances the memory event in the repetition; in fact it greatly differs from the biographical reproduction, in which each repetition is but a weaker echo, a duller copy, provided with a smaller an smaller power in comparison with the original. Paradoxically, for Deleuze the repetition asserts the originality and singularity of what is repeated. Rossi seems to share the thought expressed by Kierkegaard in the essay Repetition: «The hope is a graceful maiden slipping through your fingers; the memory of an elderly woman, indeed pretty, but never satisfactory if necessary; the repetition is a loved friend you are never tired of, as it is only the new to make you bored. The old never bores you and its presence makes you happy [...] life is but a repetition [...] here is the beauty of life» . Rossi knows well that repetition hints at the lasting stability of cosmic time. Kierkegaard goes on: «The world exists, and it exists as a repetition» . Rossi devotes himself, on purpose and in all conscience, to collect, to inventory and «to review life», his own life, according to a recovery not from the past but of the past: a search work, the «recherche du temps perdu», as Proust entitled his masterpiece on memory. If you want the past time to be not wasted, you must give it presence. «Memoria e specifico come caratteristiche per riconoscere se stesso e ciò che è estraneo mi sembravano le più chiare condizioni e spiegazioni della realtà. Non esiste uno specifico senza memoria, e una memoria che non provenga da un momento specifico; e solo questa unione permette la conoscenza della propria individualità e del contrario (self e non-self)» . Rossi wants to understand himself, his own character; it is really his own character that requires to be understood, to increase its own introspective ability and intelligence. «Può sembrare strano che Planck e Dante associno la loro ricerca scientifica e autobiografica con la morte; una morte che è in qualche modo continuazione di energia. In realtà, in ogni artista o tecnico, il principio della continuazione dell’energia si mescola con la ricerca della felicità e della morte» . The eschatological incipit of Rossi’s autobiography refers to Freud’s thought in the exact circularity of Dante’s framework and in as much exact circularity of the statement of the principle of the conservation of energy: in fact it was Freud to connect repetition to death. For Freud, the desire of repetition is an instinct rooted in biology. The primary aim of such an instinct would be to restore a previous condition, so that the repeated history represents a part of the past (even if concealed) and, relieving the removal, reduces anguish and tension. So, Freud ask himself, what is the most remote state to which the instinct, through the repetition, wants to go back? It is a pre-vital condition, inorganic of the pure entropy, a not-to-be condition in which doesn’t exist any tension; in other words, Death. Rossi, with the theme of death, introduces the theme of circularity which further on refers to the sense of continuity in transformation or, in the opposite way, the transformation in continuity. «[...] la descrizione e il rilievo delle forme antiche permettevano una continuità altrimenti irripetibile, permettevano anche una trasformazione, una volta che la vita fosse fermata in forme precise» . Rossi’s attitude seems to hint at the reflection on time and – in a broad sense – at the thought on life and things expressed by T.S. Eliot in Four Quartets: «Time present and time past / Are both perhaps present in time future, / And time future is contained in time past. / I all time is eternally present / All time is unredeemable. / What might have been is an abstraction / Remaining perpetual possibility / Only in a word of speculation. / What might have been and what has been / Point to one end, which is always present. [...]» . Aldo Rossi’s autobiographical story coincides with the description of “things” and the description of himself through the things in the exact parallel with craft or art. He seems to get all things made by man to coincide with the personal or artistic story, with the consequent immediate necessity of formulating a new interpretation: the flow of things has never met a total stop; all that exists nowadays is but a repetition or a variant of something existing some time ago and so on, without any interruption until the early dawnings of human life. Nevertheless, Rossi must operate specific subdivisions inside the continuous connection in time – of his time – even if limited by a present beginning and end of his own existence. This artist, as an “historian” of himself and his own life – as an auto-biographer – enjoys the privilege to be able to decide if and how to operate the cutting in a certain point rather than in another one, without being compelled to justify his choice. In this sense, his story is a matter very ductile and flexible: a good story-teller can choose any moment to start a certain sequence of events. Yet, Rossi is aware that, beyond the mere narration, there is the problem to identify in history - his own personal story – those flakings where a clean cut enables the separation of events of different nature. In order to do it, he has to make not only an inventory of his own “things”, but also to appeal to authority of the Divina Commedia started by Dante when he was 30. «A trent’anni si deve compiere o iniziare qualcosa di definitivo e fare i conti con la propria formazione» . For Rossi, the poet performs his authority not only in the text, but also in his will of setting out on a mystical journey and handing it down through an exact descriptive will. Rossi turns not only to the authority of poetry, but also evokes the authority of science with Max Plank and his Scientific Autobiography, published, in Italian translation, by Einaudi, 1956. Concerning Planck, Rossi resumes an element seemingly secondary in hit account where the German physicist «[...] risale alle scoperte della fisica moderna ritrovando l’impressione che gli fece l’enunciazione del principio di conservazione dell’energia; [...]» . It is again the act of describing that links Rossi to Planck, it is the description of a circularity, the one of conservation of energy, which endorses Rossi’s autobiographical speech looking for both happiness and death. Rossi seems to agree perfectly to the thought of Planck at the opening of his own autobiography: «The decision to devote myself to science was a direct consequence of a discovery which was never ceased to arouse my enthusiasm since my early youth: the laws of human thought coincide with the ones governing the sequences of the impressions we receive from the world surrounding us, so that the mere logic can enable us to penetrate into the latter one’s mechanism. It is essential that the outer world is something independent of man, something absolute. The search of the laws dealing with this absolute seems to me the highest scientific aim in life» . For Rossi the survey of his own life represents a way to change the events into experiences, to concentrate the emotion and group them in meaningful plots: «It seems, as one becomes older. / That the past has another pattern, and ceases to be a mere sequence [...]» Eliot wrote in Four Quartet, which are a meditation on time, old age and memory . And he goes on: «We had the experience but missed the meaning, / And approach to the meaning restores the experience / In a different form, beyond any meaning [...]» . Rossi restores in his autobiography – but not only in it – the most ancient sense of memory, aware that for at least 15 centuries the Latin word memoria was used to show the activity of bringing back images to mind: the psychology of memory, which starts with Aristotele (De Anima), used to consider such a faculty totally essential to mind. Keith Basso writes: «The thought materializes in the form of “images”» . Rossi knows well – as Aristotele said – that if you do not have a collection of mental images to remember – imagination – there is no thought at all. According to this psychological tradition, what today we conventionally call “memory” is but a way of imagining created by time. Rossi, entering consciously this stream of thought, passing through the Renaissance ars memoriae to reach us gives a great importance to the word and assumes it as a real place, much more than a recollection, even more than a production and an emotional elaboration of images.
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Con il termine Smart Grid si intende una rete urbana capillare che trasporta energia, informazione e controllo, composta da dispositivi e sistemi altamente distribuiti e cooperanti. Essa deve essere in grado di orchestrare in modo intelligente le azioni di tutti gli utenti e dispositivi connessi al fine di distribuire energia in modo sicuro, efficiente e sostenibile. Questo connubio fra ICT ed Energia viene comunemente identificato anche con il termine Smart Metering, o Internet of Energy. La crescente domanda di energia e l’assoluta necessità di ridurre gli impatti ambientali (pacchetto clima energia 20-20-20 [9]), ha creato una convergenza di interessi scientifici, industriali e politici sul tema di come le tecnologie ICT possano abilitare un processo di trasformazione strutturale di ogni fase del ciclo energetico: dalla generazione fino all’accumulo, al trasporto, alla distribuzione, alla vendita e, non ultimo, il consumo intelligente di energia. Tutti i dispositivi connessi, diventeranno parte attiva di un ciclo di controllo esteso alle grandi centrali di generazione così come ai comportamenti dei singoli utenti, agli elettrodomestici di casa, alle auto elettriche e ai sistemi di micro-generazione diffusa. La Smart Grid dovrà quindi appoggiarsi su una rete capillare di comunicazione che fornisca non solo la connettività fra i dispositivi, ma anche l’abilitazione di nuovi servizi energetici a valore aggiunto. In questo scenario, la strategia di comunicazione sviluppata per lo Smart Metering dell’energia elettrica, può essere estesa anche a tutte le applicazioni di telerilevamento e gestione, come nuovi contatori dell’acqua e del gas intelligenti, gestione dei rifiuti, monitoraggio dell’inquinamento dell’aria, monitoraggio del rumore acustico stradale, controllo continuo del sistema di illuminazione pubblico, sistemi di gestione dei parcheggi cittadini, monitoraggio del servizio di noleggio delle biciclette, ecc. Tutto ciò si prevede possa contribuire alla progettazione di un unico sistema connesso, dove differenti dispositivi eterogenei saranno collegati per mettere a disposizione un’adeguata struttura a basso costo e bassa potenza, chiamata Metropolitan Mesh Machine Network (M3N) o ancora meglio Smart City. Le Smart Cities dovranno a loro volta diventare reti attive, in grado di reagire agli eventi esterni e perseguire obiettivi di efficienza in modo autonomo e in tempo reale. Anche per esse è richiesta l’introduzione di smart meter, connessi ad una rete di comunicazione broadband e in grado di gestire un flusso di monitoraggio e controllo bi-direzionale esteso a tutti gli apparati connessi alla rete elettrica (ma anche del gas, acqua, ecc). La M3N, è un’estensione delle wireless mesh network (WMN). Esse rappresentano una tecnologia fortemente attesa che giocherà un ruolo molto importante nelle futura generazione di reti wireless. Una WMN è una rete di telecomunicazione basata su nodi radio in cui ci sono minimo due percorsi che mettono in comunicazione due nodi. E’ un tipo di rete robusta e che offre ridondanza. Quando un nodo non è più attivo, tutti i rimanenti possono ancora comunicare tra di loro, direttamente o passando da uno o più nodi intermedi. Le WMN rappresentano una tipologia di rete fondamentale nel continuo sviluppo delle reti radio che denota la divergenza dalle tradizionali reti wireless basate su un sistema centralizzato come le reti cellulari e le WLAN (Wireless Local Area Network). Analogamente a quanto successo per le reti di telecomunicazione fisse, in cui si è passati, dalla fine degli anni ’60 ai primi anni ’70, ad introdurre schemi di rete distribuite che si sono evolute e man mano preso campo come Internet, le M3N promettono di essere il futuro delle reti wireless “smart”. Il primo vantaggio che una WMN presenta è inerente alla tolleranza alla caduta di nodi della rete stessa. Diversamente da quanto accade per una rete cellulare, in cui la caduta di una Base Station significa la perdita di servizio per una vasta area geografica, le WMN sono provviste di un’alta tolleranza alle cadute, anche quando i nodi a cadere sono più di uno. L'obbiettivo di questa tesi è quello di valutare le prestazioni, in termini di connettività e throughput, di una M3N al variare di alcuni parametri, quali l’architettura di rete, le tecnologie utilizzabili (quindi al variare della potenza, frequenza, Building Penetration Loss…ecc) e per diverse condizioni di connettività (cioè per diversi casi di propagazione e densità abitativa). Attraverso l’uso di Matlab, è stato quindi progettato e sviluppato un simulatore, che riproduce le caratteristiche di una generica M3N e funge da strumento di valutazione delle performance della stessa. Il lavoro è stato svolto presso i laboratori del DEIS di Villa Grifone in collaborazione con la FUB (Fondazione Ugo Bordoni).
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Streptococcus pneumoniae is an important life threatening human pathogen causing agent of invasive diseases such as otitis media, pneumonia, sepsis and meningitis, but is also a common inhabitant of the respiratory tract of children and healthy adults. Likewise most streptococci, S. pneumoniae decorates its surface with adhesive pili, composed of covalently linked subunits and involved in the attachment to epithelial cells and virulence. The pneumococcal pili are encoded by two genomic regions, pilus islet 1 (PI-1), and pilus islet-2 (PI-2), which are present in about 30% and 16% of the pneumococcal strains, respectively. PI-1 exists in three clonally related variants, whereas PI-2 is highly conserved. The presence of the islets does not correlate with the serotype of the strains, but with the genotype (as determined by Multi Locus Sequence Typing). The prevalence of PI-1 and PI-2 positive strains is similar in isolates from invasive disease and carriage. To better dissect a possible association between PIs presence and disease we evaluated the distribution of the two PIs in a panel of 113 acute otitis media (AOM) clinical isolates from Israel. PI-1 was present in 30.1% (N=34) of the isolates tested, and PI-2 in 7% (N=8). We found that 50% of the PI-1 positive isolates belonged to the international clones Spain9V-3 (ST156) and Taiwan19F-14 (ST236), and that PI-2 was not present in the absence of Pl-1. In conclusion, there was no correlation between PIs presence and AOM, and, in general, the observed differences in PIs prevalence are strictly dependent upon regional differences in the distribution of the clones. Finally, in the AOM collection the prevalence of PI-1 was higher among antibiotic resistant isolates, confirming previous indications obtained by the in silico analysis of the MLST database collection. Since the pilus-1 subunits were shown to confer protection in mouse models of infection both in active and passive immunization studies, and were regarded as potential candidates for a new generation of protein-based vaccines, the functional characterization was mainly focused on S. pneumoniae pilus -1 components. The pneumococcal pilus-1 is composed of three subunits, RrgA, RrgB and RrgC, each stabilized by intra-molecular isopeptide bonds and covalently polymerized by means of inter-molecular isopeptide bonds to form an extended fibre. The pilus shaft is a multimeric structure mainly composed by the RrgB backbone subunit. The minor ancillary proteins are located at the tip and at the base of the pilus, where they have been proposed to act as the major adhesin (RrgA) and as the pilus anchor (RrgC), respectively. RrgA is protective in in vivo mouse models, and exists in two variants (clades I and II). Mapping of the sequence variability onto the RrgA structure predicted from X-ray data showed that the diversity was restricted to the “head” of the protein, which contains the putative binding domains, whereas the elongated “stalk” was mostly conserved. To investigate whether this variability could influence the adhesive capacity of RrgA and to map the regions important for binding, two full-length protein variants and three recombinant RrgA portions were tested for adhesion to lung epithelial cells and to purified extracellular matrix (ECM) components. The two RrgA variants displayed similar binding abilities, whereas none of the recombinant fragments adhered at levels comparable to those of the full-length protein, suggesting that proper folding and structural arrangement are crucial to retain protein functionality. Furthermore, the two RrgA variants were shown to be cross-reactive in vitro and cross-protective in vivo in a murine model of passive immunization. Taken together, these data indicate that the region implicated in adhesion and the functional epitopes responsible for the protective ability of RrgA may be conserved and that the considerable level of variation found within the “head” domain of RrgA may have been generated by immunologic pressure without impairing the functional integrity of the pilus.
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In this work, solid-state NMR methods suitable for the investigation of supramolecular systems were developed and improved. In this context, special interest was focussed on non-covalent interactions responsible for the formation of supramolecular structures, such as pi-pi interacions and hydrogen-bonds. In the first part of this work, solid-state NMR methods were presented that provide information on molecular structure and motion via the investigation of anisotropic interactions, namely quadrupole and dipole-dipole couplings, under magic-angle spinning conditions. A two-dimensional 2H double quantum experiment was developed, which is performed under off magic-angle conditions and correlates 2H isotropic chemical shifts with quasistatic DQ-filtered line shapes. From the latter, the quadrupole coupling parameters of samples deuterated at multiple sites can be extracted in a site-selective fashion. Furthermore, 7Li quadrupole parameters of lithium intercalated into TiO2 were determined by NMR experiments performed under static and MAS conditions, and could provide information on the crystal geometry. For the determination of 7Li-7Li dipole-dipole couplings, multiple-quantum NMR experiments were performed. The 1H-13C REREDOR experiment was found to be capable of determining strong proton-carbon dipole-dipole couplings with an accuracy of 500~Hz, corresponding to a determination of proton-carbon chemical-bond lengths with picometer accuracy In the second part of this work, solid-state NMR experiments were combined with quantum-chemical calculations in order to aid and optimise the interpretation of experimental results. The investigations on Calix[4]hydroquinone nanotubes have shown that this combined approach can provide information on the presence of disordered and/or mobile species in supramolecular structures. As a second example, C3-symmetric discs arranging in helical columnar stacks were investigated. In these systems, 1H chemical shifts experience large pi-shifts due to packing effects, which were found to be long-ranged. Moreover, quantum-chemical calculations revealed that helicity in these systems is induced by the propeller-like conformation of the core of the molecules.
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Internet of Energy è un progetto di ricerca europeo nato con lo scopo di sviluppare infrastrutture hardware e software volte a introdurre la mobilità elettrica veicolare nei moderni contesti urbani. È stato oggetto di tesi di Federco Montori il quale ha sviluppato un primo prototipo di piattaforma comprendente un servizio cittadino di gestione delle ricariche, un’applicazione mobile che vi interagiva e infine un simulatore necessario al test della piattaforma. Nel corso di oltre un anno di sviluppo ho riscritto tutte le componenti software che costituivano il progetto ampliandone notevolmente le funzionalità, rendendole modulari e ben ingegnerizzate. Del progetto originario è stata ereditata l’architettura ontology-based basata sullo scambio di informazioni tramite il Semantic Information Broker (SIB). Il mio contributo è iniziato nel 2012 con la riscrittura dell’applicazione mobile che inizialmente funzionava solo in presenza del simulatore. Attualmente permette di interfacciarsi a un veicolo reale tramite la tecnologia Blue&Me di Fiat. Questo approccio è stato reso possibile grazie all’opportunità offerta dal Centro Ricerche Fiat, che ci ha permesso di testare presso loro sede l’applicazione mobile su un prototipo di Daily elettrico. Ho inoltre introdotto lo studio del profilo altimetrico e consumo energetico che separa il possessore dello smartphone da una determinata destinazione. Nel 2013 ho deciso di riscrivere il Servizio Cittadino per renderlo conforme a un nuovo protocollo di prenotazione. Ho colto l’occasione per rendere il servizio altamente performante grazie a tecniche quali: pool di thread, pool di oggetti e caching. Infine a cavallo tra il 2013 e il 2014 ho riscritto il simulatore al fine di ottimizzare il consumo di risorse, velocizzare il setup delle simulazioni e sopratutto renderlo più conforme alla realtà. Questo lavoro ha permesso di avere una piattaforma software che permette di valutare realisticamente gli scenari di mobilità elettrica veicolare.
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Internet of Energy for Electric Mobility è un progetto di ricerca europeo il cui scopo consiste nello sviluppo di infrastrutture di comunicazione, siano esse sia hardware che software, volte alla facilitazione, supporto e miglioramento di tutte quelle operazioni legate al processo di ricarica di auto elettriche. A tale progetto vi ha aderito anche l’Università di Bologna ed è stato oggetto di studio di Federico Montori e Simone Rondelli. Il primo ha dato il là allo sviluppo del progetto realizzandovi, in una fase embrionale, una piattaforma legata alla gestione di un servizio cittadino (bolognese) per la gestione di ricariche elettriche, un’applicazione mobile in grado di interagire con tale servizio ed un simulatore per la piattaforma. In un lavoro durato oltre un anno, Simone Rondelli ha ripreso il progetto di Federico Montori riscrivendone le componenti in maniera tale da migliorarne le funzionalità ed aggiungerne anche di nuove; in particolare ha realizzato in maniera efficiente un’applicazione mobile la quale si occupa di gestire la prenotazione di colonnine elettriche di ricarica e di monitorare lo stato attuale di un’auto peso, livello batteria, ecc... ). Nel marzo del 2014 è cominciato il mio contributo nel contesto di Internet of Energy di cui ne ho ereditato tutta l’architettura derivante dai due sviluppi precedenti. Il mio compito è stato quello di realizzare (cioè emulare) una colonnina di ricarica auto elettrica, tramite la piattaforma elettronica Arduino, la quale al suo primo avvio informa il database semantico del sistema (SIB) della sua presenza in maniera tale che il simulatore sia in grado di poter far ricaricare un’auto anche a questa nuova colonnina. Di conseguenza ho fatto in modo di instaurare (tramite socket) una comunicazione tra il simulatore e la colonnina così che il simulatore informi la colonnina che è stata raggiunta da un’auto e, viceversa, la colonnina informi il simulatore sullo stato di ricarica dell’auto in modo che quest’ultima possa ripartire al termine della ricarica. Ho anche realizzato un’applicazione mobile in grado di comunicare con la colonnina, il cui scopo è quello di ottenere un codice di ricarica che poi l’utente deve digitare per autenticarsi presso di essa. Realizzando tale tipo di contributo si è data dunque la possibilità di integrare una componente ”reale” con componenti simulate quali le auto del simulatore di Internet of Energy e si sono poste le basi per estensioni future, le quali permettano di integrare anche più componenti che si registrano nel sistema e danno dunque la possibilità di essere utilizzate dalle auto elettriche.
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La sempre minore disponibilità di combustibili fossili e il crescente inquinamento ambientale, hanno incentivato non solo la ricerca di fonti alternative di energia, ma anche lo sviluppo di nuove tecnologie che ci permettessero di sfruttarle. Non solo sono stati sviluppati pannelli solari e paleoliche, che ci permettono di ottenere energia rinnovabile; ma anche i "comuni" strumenti sono stati modificati per far fronte a queste esigenze. Tra le più importanti innovazioni, lo sviluppo delle auto elettriche è quella che ha riscosso più interesse. Nonostante gli ingenti investimenti iniziali però, l'immissione nel mercato non sta riscuotendo il successo sperato. Uno dei maggiori limiti riscontrati è quello che viene definito Range Anxiety, ovvero la paura che il veicolo elettrico (EV) non abbia abbastanza autonomia per garantire al conducente il raggiungimento della meta. Inoltre il tutto viene amplificato dai lunghi tempi di ricarica delle batterie e l'elevato costo degli EV. Per arginare questi problemi, in questo documento viene descritto lo sviluppo di un applicazione Android (WhatIfApp - WIA) per la valutazione della sostenibilità di un viaggio, facendo visualizzare all'utente i tempi di percorrenza (ottimizzati) e i consumi, che un EV dovrebbe affrontare in determinati percorsi. In particolare, ne viene spiegato l'utilizzo, le funzionalità, le scelte implementative e le future estensioni.
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Opera di recente pubblicazione, "The Story of Kullervo" è il racconto che più di tutti mostra l'esistenza di un profondo legame tra J. R. R. Tolkien e la lingua e cultura finlandese. Scopo di questo elaborato è quello di analizzare soprattutto il rapporto tra l'autore e il poema epico finlandese, il Kalevala, proponendo la traduzione della storia. L'elaborato è strutturato nel seguente modo: nel primo paragrafo viene trattato il Kalevala come opera letteraria e come fonte di ispirazione per Tolkien. Nel secondo paragrafo viene analizzato il testo del racconto in quanto testo letterario e nel terzo vengono commentate le scelte traduttive effettuate.
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We report the analysis of the SI So rotational band contours of jet-cooled 5-methyl-2-hydroxypyrimidine (5M2HP), the enol form of deoxythymine. Unlike thymine, which exhibits a structureless spectrum, the vibronic spectrum of 5M2HP is well structured, allowing us to determine the rotational constants and the methyl group torsional barriers in the S-0 and S-1 states. The 0(0)(0), 6a(0)(1), 6b(0)(1), and 14(0)(1) band contours were measured at 900 MHz (0.03 cm(-1)) resolution using mass-specific two-color resonant two-photon ionization (2C-R2PI) spectroscopy. All four bands are polarized perpendicular to the pyrimidine plane (>90% c type), identifying the S-1 <- S-0 excitation of 5M2HP as a 1n pi* transition. All contours exhibit two methyl rotor subbands that arise from the lowest 5-methyl torsional states 0A '' and 1E ''. The S-0 and S-1 state torsional barriers were extracted from fits to the torsional subbands. The 3-fold barriers are V-3 '' = 13 cm(-1) and V3' = SI cm(-1); the 6-fold barrier contributions V-6 '' and V-6' are in the range of 2-3 cm(-1) and are positive in both states. The changes of A, B, and C rotational constants upon S-1 <- S-0 excitation were extracted from the contours and reflect an "anti-quinoidal" distortion. The 0(0)(0) contour can only be simulated if a 3 GHz Lorentzian line shape is included, which implies that the S-1(1n pi*) lifetime is similar to 55 ps. For the 6a(0)(1) and 6b(0)(1) bands, the Lorentzian component increases to 5.5 GHz, reflecting a lifetime decrease to similar to 30 ps. The short lifetimes are consistent with the absence of fluorescence from the 1n pi* state. Combining these measurements with the previous observation of efficient intersystem crossing (ISC) from the Si state to a long-lived T-1((3)n pi*) state that lies similar to 2200 cm(-1) below [S. Lobsiger, S. et al. Phys. Chem. Chem. Phys. 2010, 12, 5032] implies that the broadening arises from fast intersystem crossing with k(ISC) approximate to 2 x 10(10) s(-1). In comparison to 5-methylpyrimidine, the ISC rate is enhanced by at least 10 000 by the additional hydroxy group in position 2.
Resumo:
For understanding the major- and minor-groove hydration patterns of DNAs and RNAs, it is important to understand the local solvation of individual nucleobases at the molecular level. We have investigated the 2-aminopurine center dot H2O. monohydrate by two-color resonant two-photon ionization and UV/UV hole-burning spectroscopies, which reveal two isomers, denoted A and B. The electronic spectral shift delta nu of the S-1 <- S-0 transition relative to bare 9H-2-aminopurine (9H-2AP) is small for isomer A (-70 cm(-1)), while that of isomer B is much larger (delta nu = 889 cm(-1)). B3LYP geometry optimizations with the TZVP basis set predict four cluster isomers, of which three are doubly H-bonded, with H2O acting as an acceptor to a N-H or -NH2 group and as a donor to either of the pyrimidine N sites. The "sugar-edge" isomer A is calculated to be the most stable form with binding energy D-e = 56.4 kJ/mol. Isomers B and C are H-bonded between the -NH2 group and pyrimidine moieties and are 2.5 and 6.9 kJ/mol less stable, respectively. Time-dependent (TD) B3LYP/TZVP calculations predict the adiabatic energies of the lowest (1)pi pi* states of A and B in excellent agreement with the observed 0(0)(0) bands; also, the relative intensities of the A and B origin bands agree well with the calculated S-0 state relative energies. This allows unequivocal identification of the isomers. The R2PI spectra of 9H-2AP and of isomer A exhibit intense low-frequency out-of-plane overtone and combination bands, which is interpreted as a coupling of the optically excited (1)pi pi* state to the lower-lying (1)n pi* dark state. In contrast, these overtone and combination bands are much weaker for isomer B, implying that the (1)pi pi* state of B is planar and decoupled from the (1)n pi* state. These observations agree with the calculations, which predict the (1)n pi* above the (1)pi pi* state for isomer B but below the (1)pi pi* for both 9H-2AP and isomer A.
Resumo:
INTRODUCTION Erectile dysfunction (ED) is an increasing health problem that demands effective treatment. There is evidence that phosphodiesterase-5 inhibitors (PDE5-Is) and psychological intervention (PI) are effective treatment options; however, little is known about their comparative efficacy and the efficacy of combined treatments. AIM The aim of this systematic review and meta-analysis is to evaluate the comparative efficacy of PI, PDE5-Is, and their combination in the treatment of ED. MAIN OUTCOME MEASURES Primary outcome was ED symptoms, and secondary outcome was sexual satisfaction of the patient. METHODS A systematic literature search was conducted in order to identify relevant articles published between 1998 and 2012. We included randomized controlled trials and controlled trials comparing PI with PDE5-I treatment or one of them against a combination of both. RESULTS Eight studies with a total number of 562 patients were included in the meta-analysis. The results of the included studies are inconclusive, though they show a trend towards a larger effect of combined treatment compared with PI or PDE5-I treatment alone. The meta-analysis found that, overall, combined treatment was more efficacious for ED symptoms than PDE5-I treatment or PI alone. Combined treatment was more efficacious than PDE5-I use alone on sexual satisfaction. No differences were found between PDE5-Is and PI as stand-alone treatments. None of the moderators (treatment duration, methodological quality, or researcher allegiance) altered the effects. CONCLUSIONS The combination of PI and PDE5-Is is a promising strategy for a favorable outcome in ED and can be considered as a first-choice option for ED patients. Stronger RCTs are required to confirm this initial finding. Schmidt HM, Munder T, Gerger H, Frühauf S, and Barth J. Combination of psychological intervention and phosphodiesterase-5 inhibitors for erectile dysfunction: A narrative review and meta-analysis. J Sex Med **;**:**-**.