Cordas cósmicas e gravitação planar de ordem superior

The possibility of generalizing gravity in 2+1 dimensions to include higher-derivative terms, thereby allowing for a dynamical theory, opens up a variety of new interesting questions. This is in great contrast with pure Einstein gravity which is a generally covariant theory that has no degrees of freedom - a peculiarity that, in a sense, renders it a little insipid and odorless. The research on gravity of particles moving in a plane, that is, living in flatland, within the context of higher-derivative gravity, leads to novel and interesting effects. For instance, the generation of gravity, antigravity, and gravitational shielding by the interaction of massive scalar bosons via a graviton exchange. In addition, the gravitational deffection angle of a photon, unlike that of Einstein gravity, is dependent of the impact parameter. On the other hand, the great drawback to using linearized general relativity for describing a gravitating string is that this description leads to some unphysical results such as: (i) lack of a gravity force in the nonrelativistic limit; (ii) gravitational deffection independent of the impact parameter. Interesting enough, the effective cure for these pathologies is the replacement of linearized gravity by linearized higher-derivative gravity. We address these issues here

Bach-Busoni Chaconne: A Piano Transcription Analysis

In 1893 Ferruccio Busoni transcribed, for the piano, the famous Bach Chaconne for violin solo from the Partita No.2 in D minor. Numerous transcriptions of this piece for different various instruments exist; however Busoni's transcription stands above all others. The purpose of this study was to analyze what the famous, twentieth-century pianist did when he transcribed Bach's Chaconne. What information exists on the topic comes primarily from pianists who dared to learn this exceptionally difficult, beautiful composition. Busoni's accomplishments lie in the new concept, a conceptual transcription, which has two roots: understanding how, historically, we are connected to the music, and how once genres have a special meaning in the twentieth-century. Every generation of musicians brings their own specific point of view and interpretation. Busoni lived on the border of the two centuries and, in his transcription, reveled in several issues overlooked by the previous generation. With his keen understanding of the piece, Busoni highlighted many different genres present in the music, thus allowing recognition of the last movement of the Partita No. 2 in D minor as a Requiem for Bach's wife. By underscoring the genres, Busoni used them as strata. The idea of strata comes from the aesthetics of “play,” and from a different approach to the quality of sound on piano originally intended for a high string instrument. Busoni's arrangement of the texture added both orchestral quality and stereophonic perception. The strata add to a certain reading of Bach's original. Busoni promoted a dramatic approach opening the possibility of reading the chaconne as a multi-layered form. Through Busoni', we see the possibility not only of a tripartite, variation form, but also a composition, with the elements of a concerto, and a sonata. Who could imagine, that a composition written by a young composer at the fin de siecle, intended for practical use by pianists, would subtly influence so many contemporaries and generations, that they will find his findings and music inspiring. Adviser: Dr. Mark K. Clinton

Means to an end: Neotropical parrots manage to pull strings to meet their goals

Although parrots share with corvids and primates many of the traits believed to be associated with advanced cognitive processing, knowledge of parrot cognition is still limited to a few species, none of which are Neotropical. Here we examine the ability of three Neotropical parrot species (Blue-Fronted Amazons, Hyacinth and Lear`s macaws) to spontaneously solve a novel physical problem: the string-pulling test. The ability to pull up a string to obtain out-of-reach food has been often considered a cognitively complex task, as it requires the use of a sequence of actions never previously assembled, along with the ability to continuously monitor string, food and certain body movements. We presented subjects with pulling tasks where we varied the spatial relationship between the strings, the presence of a reward and the physical contact between the string and reward to determine whether (1) string-pulling is goal-oriented in these parrots, (2) whether the string is recognized as a means to obtain the reward and (3) whether subjects can visually determine the continuity between the string and the reward, selecting only those strings for which no physical gaps between string and reward were present. Our results show that some individuals of all species were able to use the string as a means to reach a specific goal, in this case, the retrieval of the food treat. Also, subjects from both macaw species were able to visually determine the presence of physical continuity between the string and reward, making their choices consistently with the recognition that no gaps should be present between the string and the reward. Our findings highlight the potential of this taxonomic group for the understanding of the underpinnings of cognition in evolutionarily distant groups such as birds and primates.

Compact groups of galaxies selected by stellar mass: the 2MASS compact group catalogue

We present a photometric catalogue of compact groups of galaxies (p2MCGs) automatically extracted from the Two-Micron All Sky Survey (2MASS) extended source catalogue. A total of 262 p2MCGs are identified, following the criteria defined by Hickson, of which 230 survive visual inspection (given occasional galaxy fragmentation and blends in the 2MASS parent catalogue). Only one quarter of these 230 groups were previously known compact groups (CGs). Among the 144 p2MCGs that have all their galaxies with known redshifts, 85 (59?per cent) have four or more accordant galaxies. This v2MCG sample of velocity-filtered p2MCGs constitutes the largest sample of CGs (with N = 4) catalogued to date, with both well-defined selection criteria and velocity filtering, and is the first CG sample selected by stellar mass. It is fairly complete up to Kgroup similar to 9 and radial velocity of similar to 6000?km?s-1. We compared the properties of the 78 v2MCGs with median velocities greater than 3000?km?s-1 with the properties of other CG samples, as well as those (mvCGs) extracted from the semi-analytical model (SAM) of Guo et al. run on the high-resolution Millennium-II simulation. This mvCG sample is similar (i.e. with 2/3 of physically dense CGs) to those we had previously extracted on three other SAMs run on the Millennium simulation with 125 times worse spatial and mass resolutions. The space density of v2MCGs within 6000?km?s-1 is 8.0 X 10-5?h3?Mpc-3, i.e. four times that of the Hickson sample [Hickson Compact Group (HCG)] up to the same distance and with the same criteria used in this work, but still 40?per cent less than that of mvCGs. The v2MCG constitutes the first group catalogue to show a statistically large firstsecond ranked galaxy magnitude gap according to TremaineRichstone statistics, as expected if the first ranked group members tend to be the products of galaxy mergers, and as confirmed in the mvCGs. The v2MCG is also the first observed sample to show that first-ranked galaxies tend to be centrally located, again consistent with the predictions obtained from mvCGs. We found no significant correlation of group apparent elongation and velocity dispersion in the quartets among the v2MCGs, and the velocity dispersions of apparently round quartets are not significantly larger than those of chain-like ones, in contrast to what has been previously reported in HCGs. By virtue of its automatic selection with the popular Hickson criteria, its size, its selection on stellar mass, and its statistical signs of mergers and centrally located brightest galaxies, the v2MCG catalogue appears to be the laboratory of choice to study physically dense groups of four or more galaxies of comparable luminosity.

A Simple Artificial Life Model Explains Irrational Behavior in Human Decision-Making

Although praised for their rationality, humans often make poor decisions, even in simple situations. In the repeated binary choice experiment, an individual has to choose repeatedly between the same two alternatives, where a reward is assigned to one of them with fixed probability. The optimal strategy is to perseverate with choosing the alternative with the best expected return. Whereas many species perseverate, humans tend to match the frequencies of their choices to the frequencies of the alternatives, a sub-optimal strategy known as probability matching. Our goal was to find the primary cognitive constraints under which a set of simple evolutionary rules can lead to such contrasting behaviors. We simulated the evolution of artificial populations, wherein the fitness of each animat (artificial animal) depended on its ability to predict the next element of a sequence made up of a repeating binary string of varying size. When the string was short relative to the animats' neural capacity, they could learn it and correctly predict the next element of the sequence. When it was long, they could not learn it, turning to the next best option: to perseverate. Animats from the last generation then performed the task of predicting the next element of a non-periodical binary sequence. We found that, whereas animats with smaller neural capacity kept perseverating with the best alternative as before, animats with larger neural capacity, which had previously been able to learn the pattern of repeating strings, adopted probability matching, being outperformed by the perseverating animats. Our results demonstrate how the ability to make predictions in an environment endowed with regular patterns may lead to probability matching under less structured conditions. They point to probability matching as a likely by-product of adaptive cognitive strategies that were crucial in human evolution, but may lead to sub-optimal performances in other environments.

Coupled Boltzmann calculation of mixed axion/neutralino cold dark matter production in the early universe

We calculate the relic abundance of mixed axion/neutralino cold dark matter which arises in R-parity conserving supersymmetric (SUSY) models wherein the strong CP problem is solved by the Peccei-Quinn (PQ) mechanism with a concommitant axion/saxion/axino supermultiplet. By numerically solving the coupled Boltzmann equations, we include the combined effects of 1. thermal axino production with cascade decays to a neutralino LSP, 2. thermal saxion production and production via coherent oscillations along with cascade decays and entropy injection, 3. thermal neutralino production and re-annihilation after both axino and saxion decays, 4. gravitino production and decay and 5. axion production both thermally and via oscillations. For SUSY models with too high a standard neutralino thermal abundance, we find the combined effect of SUSY PQ particles is not enough to lower the neutralino abundance down to its measured value, while at the same time respecting bounds on late-decaying neutral particles from BBN. However, models with a standard neutralino underabundance can now be allowed with either neutralino or axion domination of dark matter, and furthermore, these models can allow the PQ breaking scale f(a) to be pushed up into the 10(14) - 10(15) GeV range, which is where it is typically expected to be in string theory models.

Constraints on enhanced dark matter annihilation from IceCube results

Excesses on positron and electron fluxes-measured by ATIC and the PAMELA and Fermi-LAT telescopes-can be explained by dark matter annihilation in the Galaxy, however, it requires large boosts on the dark matter annihilation rate. There are many possible enhancement mechanisms such as the Sommerfeld effect or the existence of dark matter clumps in our halo. If enhancements on the dark matter annihilation cross section are taking place, the dark matter annihilation in the core of the Earth will be enhanced. Here we use recent results from the IceCube 40-string configuration to probe generic enhancement scenarios. We present results as a function of the dark matter-proton interaction cross section, sigma(chi p) weighted by the branching fraction into neutrinos f(nu(nu) over bar) as a function of a generic boost factor B-F, which parametrizes the expected enhancement of the annihilation rate. We find that dark matter models that require annihilation enhancements of O(100) or more and that annihilate significantly into neutrinos are excluded as an explanation for these excesses. We also determine the boost range that can be probed by the full IceCube telescope.

Induction of Psychosis by Delta 9-Tetrahydrocannabinol Reflects Modulation of Prefrontal and Striatal Function During Attentional Salience Processing

Context: The aberrant processing of salience is thought to be a fundamental factor underlying psychosis. Cannabis can induce acute psychotic symptoms, and its chronic use may increase the risk of schizophrenia. We investigated whether its psychotic effects are mediated through an influence on attentional salience processing. Objective: To examine the effects of Delta 9-tetrahydrocannabinol (Delta 9-THC) and cannabidiol (CBD) on regional brain function during salience processing. Design: Volunteers were studied using event-related functional magnetic resonance imaging on 3 occasions after administration of Delta 9-THC, CBD, or placebo while performing a visual oddball detection paradigm that involved allocation of attention to infrequent (oddball) stimuli within a string of frequent (standard) stimuli. Setting: University center. Participants: Fifteen healthy men with minimal previous cannabis use. Main Outcome Measures: Symptom ratings, task performance, and regional brain activation. Results: During the processing of oddball stimuli, relative to placebo, Delta 9-THC attenuated activation in the right caudate but augmented it in the right prefrontal cortex. Delta 9-Tetrahydrocannabinol also reduced the response latency to standard relative to oddball stimuli. The effect of Delta 9-THC in the right caudate was negatively correlated with the severity of the psychotic symptoms it induced and its effect on response latency. The effects of CBD on task-related activation were in the opposite direction of those of Delta 9-THC; relative to placebo, CBD augmented left caudate and hippocampal activation but attenuated right prefrontal activation. Conclusions: Delta 9-Tetrahydrocannabinol and CBD differentially modulate prefrontal, striatal, and hippocampal function during attentional salience processing. These effects may contribute to the effects of cannabis on psychotic symptoms and on the risk of psychotic disorders.

Multibrane solutions in cubic superstring field theory

Using the elements of the so-called KBc gamma subalgebra, we study a class of analytic solutions depending on a single function F(K) in the modified cubic superstring field theory. We compute the energy associated to these solutions and show that the result can be expressed in terms of a contour integral. For a particular choice of the function F(K), we show that the energy is given by integer multiples of a single D-brane tension.

Haydn, segundo Villa-Lobos: uma análise do 1º movimento do Quarteto de cordas nº 7 de Villa-Lobos

Este estudo analisa o 1º movimento do Quarteto de Cordas nº 7 de Villa-Lobos e investiga possíveis referências aos quartetos de cordas compostos por Franz Haydn, como Villa-Lobos sugeriu a Arnaldo Estrella.

Usable work of macro-scale cavities in liquids

It is shown that the generation of cavities in a liquid can produce usable work, which is illustrated by the stretching of a string. This work is done during the expansion of the cavity, and not with its collapse. Basic equations are presented for the movement of a device moved by the so called cavity events. A theoretical solution is also proposed, which uses polynomial functions relating the so called "excess of pressure" in the cavity and time. Evaluations of the force generated during the expansion of the cavity showed a mean peak value of about 58 N for the moving container, while measurements with the container fixed to a support showed a peak value of 476 N, considered somewhat overestimated, because high frequency oscillations seem to superpose the mean behavior. Simultaneous phenomena occurring during the cavity events are also described. Series of pictures of the experiments are presented.

MWRegEx : monitor web de expresiones regulares

[ES] El Trabajo de Fin de Grado, Monitor Web de Expresiones Regulares (MWRegEx), es una herramienta basada en tecnologías web, desarrollada usando el entorno Visual Studio. El objetivo principal de la aplicación es dar apoyo a la docencia de expresiones regulares, en el marco de la enseñanza del manejo de ristras de caracteres en las asignaturas de programación del Grado en Ingeniería Informática.  La aplicación permite obtener el dibujo de un autómata de una expresión regular, facilitando su comprensión; además, permite aplicar la expresión a diferentes ristras de caracteres, mostrando las coincidencias encontradas, y ofrece una versión de la expresión adaptada a su uso en literales string de lenguajes como Java y otros. La herramienta se ha implementado en dos partes: un servicio web, escrito en C#, donde se realizan todos los análisis de las expresiones regulares y las ristras a contrastar; y un cliente web, implementado usando tecnología asp.net, con JavaScript y JQuery, que gestiona la interfaz de usuario y muestra los resultados. Esta separación permite que el servicio web pueda ser reutilizado con otras aplicaciones cliente. El autómata que representa una expresión regular esta dibujado usando la librería Raphaël JavaScript que permite manejar los elementos SVG. Cada elemento de la expresión regular tiene un dibujo diferente y único para así diferenciarlo. Toda la interfaz gráfica de usuario está internacionalizada de manera tal que pueda adaptarse a diferentes idiomas y regiones sin la necesidad de realizar cambios de ingeniería ni en el código. Tanto el servicio web como la parte cliente están estructurados para que se puedan agregar nuevas modificaciones sin que esto genere una onda expansiva a lo largo de las diversas clases existentes.

Diseño e implementación de un convertidor numérico como aplicación Android

[ES] El Trabajo de Fin de Grado, Diseño e Implementación de un Convertidor Numérico como Aplicación Android es una aplicación desarrollada para terminales móviles con SO Android. Esta desarrollada en el entorno de desarrollo Eclipse, sobre el lenguaje de programación Java y hace uso de diferentes herramientas, las más importante de ellas el SDK TOOLS para Android. El objetivo o principal motivación por el cual he creado dicha aplicación es facilitarle al usuario final una forma más fácil y amena de acceder a toda la información proporcionada por el Servicio Web Números TIP. Esta aplicación podría tener gran uso en el campo de las enseñanzas primarias para enseñar a los niños a escribir números con letras y también podría ser de gran utilidad para las personas que no tengan un dominio extenso de nuestro idioma. La principal funcionalidad de la aplicación es realizar una consulta al Servicio Web Números TIP y luego mostrar por pantalla todos los datos devueltos. Todo el proceso de dibujo de la interfaz de usuario se realiza de manera dinámica y en tiempo de ejecución, logrando de esta manera adaptarnos a los datos que devuelva el servicio web. Para realizar la consulta al Servicio Web Números TIP el usuario introduce una ristra de caracteres sobre la cual se realizan determinadas comprobaciones en el servidor y se dibuja en la interfaz de usuario la respuesta devuelta. Esta ristra de caracteres puede contener cualquier signo, letra o número y el servicio web se encarga de devolver un error o reconocer un número, ya sea en su forma entera, fraccionaria, decimal o romana. La aplicación esta estandarizada para los cuatro tamaños generales reconocidos por Android y para sus densidades. Además se podría decir que la aplicación reconoce el idioma pre configurado en el teléfono y en base a ello solicita al servicio web las respuestas en español o en inglés.

Aldo Rossi, autobiografia scientifica: scrittura come progetto. Indagine critica tra scrittura e progetto di architettura

«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.

Supramolecular functional assemblies with photo or chemical addressability

Supramolecular self-assembly represents a key technology for the spontaneous construction of nanoarchitectures and for the fabrication of materials with enhanced physical and chemical properties. In addition, a significant asset of supramolecular self-assemblies rests on their reversible formation, thanks to the kinetic lability of their non-covalent interactions. This dynamic nature can be exploited for the development of “self-healing” and “smart” materials towards the tuning of their functional properties upon various external factors. One particular intriguing objective in the field is to reach a high level of control over the shape and size of the supramolecular architectures, in order to produce well-defined functional nanostructures by rational design. In this direction, many investigations have been pursued toward the construction of self-assembled objects from numerous low-molecular weight scaffolds, for instance by exploiting multiple directional hydrogen-bonding interactions. In particular, nucleobases have been used as supramolecular synthons as a result of their efficiency to code for non-covalent interaction motifs. Among nucleobases, guanine represents the most versatile one, because of its different H-bond donor and acceptor sites which display self-complementary patterns of interactions. Interestingly, and depending on the environmental conditions, guanosine derivatives can form various types of structures. Most of the supramolecular architectures reported in this Thesis from guanosine derivatives require the presence of a cation which stabilizes, via dipole-ion interactions, the macrocyclic G-quartet that can, in turn, stack in columnar G-quadruplex arrangements. In addition, in absence of cations, guanosine can polymerize via hydrogen bonding to give a variety of supramolecular networks including linear ribbons. This complex supramolecular behavior confers to the guanine-guanine interactions their upper interest among all the homonucleobases studied. They have been subjected to intense investigations in various areas ranging from structural biology and medicinal chemistry – guanine-rich sequences are abundant in telomeric ends of chromosomes and promoter regions of DNA, and are capable of forming G-quartet based structures– to material science and nanotechnology. This Thesis, organized into five Chapters, describes mainly some recent advances in the form and function provided by self-assembly of guanine based systems. More generally, Chapter 4 will focus on the construction of supramolecular self-assemblies whose self-assembling process and self-assembled architectures can be controlled by light as external stimulus. Chapter 1 will describe some of the many recent studies of G-quartets in the general area of nanoscience. Natural G- quadruplexes can be useful motifs to build new structures and biomaterials such as self-assembled nanomachines, biosensors, therapeutic aptamer and catalysts. In Chapters 2-4 it is pointed out the core concept held in this PhD Thesis, i.e. the supramolecular organization of lipophilic guanosine derivatives with photo or chemical addressability. Chapter 2 will mainly focus on the use of cation-templated guanosine derivatives as a potential scaffold for designing functional materials with tailored physical properties, showing a new way to control the bottom-up realization of well-defined nanoarchitectures. In section 2.6.7, the self-assembly properties of compound 28a may be considered an example of open-shell moieties ordered by a supramolecular guanosine architecture showing a new (magnetic) property. Chapter 3 will report on ribbon-like structures, supramolecular architectures formed by guanosine derivatives that may be of interest for the fabrication of molecular nanowires within the framework of future molecular electronic applications. In section 3.4 we investigate the supramolecular polymerizations of derivatives dG 1 and G 30 by light scattering technique and TEM experiments. The obtained data reveal the presence of several levels of organization due to the hierarchical self-assembly of the guanosine units in ribbons that in turn aggregate in fibrillar or lamellar soft structures. The elucidation of these structures furnishes an explanation to the physical behaviour of guanosine units which display organogelator properties. Chapter 4 will describe photoresponsive self-assembling systems. Numerous research examples have demonstrated that the use of photochromic molecules in supramolecular self-assemblies is the most reasonable method to noninvasively manipulate their degree of aggregation and supramolecular architectures. In section 4.4 we report on the photocontrolled self-assembly of modified guanosine nucleobase E-42: by the introduction of a photoactive moiety at C8 it is possible to operate a photocontrol over the self-assembly of the molecule, where the existence of G-quartets can be alternately switched on and off. In section 4.5 we focus on the use of cyclodextrins as photoresponsive host-guest assemblies: αCD–azobenzene conjugates 47-48 (section 4.5.3) are synthesized in order to obtain a photoresponsive system exhibiting a fine photocontrollable degree of aggregation and self-assembled architecture. Finally, Chapter 5 contains the experimental protocols used for the research described in Chapters 2-4.