New materials for electrochemiluminescence

The study of electrochemiluminescence (ECL) involves photophysical and electrochemical aspects. Excited states are populated by an electrical stimulus. The most important applications are in the diagnostic field where a number of different biologically-relevant molecules (e.g. proteins and nucleic acids) can be recognized and quantified with a sensitivity and specificity previously not reachable. As a matter of fact the electrochemistry, differently to the classic techniques as fluorescence and chemiluminescence, allows to control the excited state generation spatially and temporally. The two research visits into A. J. Bard electrochemistry laboratories were priceless. Dr. Bard has been one of ECL pioneers, the first to introduce the technique and the one who discovered in 1972 the surprising emission of Ru(bpy)3 2+. I consider necessary to thank by now my supervisors Massimo and Francesco for their help and for giving me the great opportunity to know this unique science man that made me feel enthusiastic. I will never be grateful enough… Considering that the experimental techniques of ECL did not changed significantly in these last years the most convenient research direction has been the developing of materials with new or improved properties. In Chapter I the basics concepts and mechanisms of ECL are introduced so that the successive experiments can be easily understood. In the final paragraph the scopes of the thesis are briefly described. In Chapter II by starting from ECL experimental apparatus of Dr. Bard’s laboratories the design, assembly and preliminary tests of the new Bologna instrument are carefully described. The instrument assembly required to work hard but resulted in the introduction of the new technique in our labs by allowing the continuation of the ECL studies began in Texas. In Chapter III are described the results of electrochemical and ECL studies performed on new synthesized Ru(II) complexes containing tetrazolate based ligands. ECL emission has been investigated in solution and in solid thin films. The effect of the chemical protonation of the tetrazolate ring on ECL emission has been also investigated evidencing the possibility of a catalytic effect (generation of molecular hydrogen) of one of the complexes in organic media. Finally, after a series of preliminary studies on ECL emission in acqueous buffers, the direct interaction with calf thymus DNA of some complexes has been tested by ECL and photoluminescence (PL) titration. In Chapter IV different Ir(III) complexes have been characterized electrochemically and photophysically (ECL and PL). Some complexes were already well-known in literature for their high quantum efficiency whereas the remaining were new synthesized compounds containing tetrazolate based ligands analogous to those investigated in Chapt. III. During the tests on a halogenated complex was unexpectedly evidenced the possibility to follow the kinetics of an electro-induced chemical reaction by using ECL signal. In the last chapter (V) the possibility to use mono-use silicon chips electrodes as ECL analitycal devices is under investigation. The chapter begins by describing the chip structure and materials then a signal reproducibility study and geometry optimization is carried on by using two different complexes. In the following paragraphs is reported in detail the synthesis of an ECL label based on Ru(bpy)3 2+ and the chip functionalization by using a lipoic acid SAM and the same label. After some preliminary characterizations (mass spectroscopy TOF) has been demonstrated that by mean of a simple and fast ECL measurement it’s possible to confirm the presence of the coupling product SAM-label into the chip with a very high sensitivity. No signal was detected from the same system by using photoluminescence.

"Narrativa di frontiera". Fenomenologia di una forma aperta.

«Fiction of frontier». Phenomenology of an open form/voice. Francesco Giustini’s PhD dissertation fits into a genre of research usually neglected by the literary criticism which nevertheless is arousing much interest in recent years: the relationship between Literature and Space. In this context, the specific issue of his work consists in the category of the Frontier including its several implications for the XX century fiction. The preliminary step, at the beginning of the first section of the dissertation, is a semantic analysis: with precision, Giustini describes the meaning of the word “frontier” here declined in a multiplicity of cultural, political and geographical contexts, starting from the American frontier of the pioneers who headed for the West, to the exotic frontiers of the world, with whose the imperialistic colonization has come into contact; from the semi-uninhabited areas like deserts, highlands and virgin forests, to the ethnic frontiers between Indian and white people in South America, since the internal frontiers of the Countries like those ones between the District and the Capital City, the Centre and the Outskirts. In the next step, Giustini wants to focus on a real “ myth of the frontier”, able to nourish cultural and literary imagination. Indeed, the literature has told and chosen the frontier as the scenery for many stories; especially in the 20th Century it made the frontier a problematic space in the light of events and changes that have transformed the perception of space and our relationship with it. Therefore, the dissertation proposes a critical category, it traces the hallmarks of a specific literary phenomenon defined “ Fiction of the frontier” ,present in many literary traditions during the 20th Century. The term “Fiction” (not “Literature” or “Poetics”) does not define a genre but rather a “procedure”, focusing on a constant issue pointed out from the texts examined in this work : the strong call to the act of narration and to its oral traditions. The “Fiction of the Frontier” is perceived as an approach to the world, a way of watching and feeling the objects, an emotion that is lived and told through the story- a story where the narrator ,through his body and his voice, takes the rule of the witness. The following parts, that have an analytic style, are constructed on the basis of this theoretical and methodological reflection. The second section gives a wide range of examples into we can find the figure and the myth of the frontier through the textual analysis which range over several literary traditions. Starting from monographic chapters (Garcia Marquez, Callado, McCarthy), to the comparative reading of couples of texts (Calvino and Verga Llosa, Buzzati and Coetzee, Arguedas and Rulfo). The selection of texts is introduced so as to underline a particular aspect or a form of the frontier at every reading. This section is articulated into thematic voices which recall some actions that can be taken into the ambiguous and liminal space of the frontier (to communicate, to wait, to “trans-culturate”, to imagine, to live in, to not-live in). In this phenomenology, the frontier comes to the light as a physical and concrete element or as a cultural, imaginary, linguistic, ethnic and existential category. In the end, the third section is centered on a more defined and elaborated analysis of two authors, considered as fundamental for the comprehension of the “Fiction of the frontier”: Joseph Conrad and João Guimarães Rosa. Even if they are very different, being part of unlike literary traditions, these two authors show many connections which are pointed by the comparative analysis. Maybe Conrad is the first author that understand the feeling of the frontier , freeing himself from the adventure romance and from the exotic nineteenthcentury tradition. João Guimarães Rosa, in his turn, is the great narrator of Brazilian and South American frontier, he is the man of sertão and of endless spaces of the Centre of Brazil. His production is strongly linked to that one belonged to the author of Heart of Darkness.

Investigation on the Navigation Anomaly of Pioneer 10 and 11 probes

The present work consists of the investigation of the navigation of Pioneer 10 and 11 probes becoming known as the “Pioneer Anomaly”: the trajectories followed by the spacecrafts did not match the ones retrieved with standard navigation software. Mismatching appeared as a linear drift in the Doppler data received by the spacecrafts, which has been ascribed to a constant sunward acceleration of about 8.5×10-10 m/s2. The study presented hereafter tries to find a convincing explanation to this discrepancy. The research is based on the analysis of Doppler tracking data through the ODP (Orbit Determination Program), developed by NASA/JPL. The method can be summarized as: seek for any kind of physics affecting the dynamics of the spacecraft or the propagation of radiometric data, which may have not been properly taken into account previously, and check whether or not these might rule out the anomaly. A major effort has been put to build a thermal model of the spacecrafts for predicting the force due to anisotropic thermal radiation, since this is a model not natively included in the ODP. Tracking data encompassing more than twenty years of Pioneer 10 interplanetary cruise, plus twelve years of Pioneer 11 have been analyzed in light of the results of the thermal model. Different strategies of orbit determination have been implemented, including single arc, multi arc and stochastic filters, and their performance compared. Orbital solutions have been obtained without the needing of any acceleration other than the thermal recoil one indicating it as the responsible for the observed linear drift in the Doppler residuals. As a further support to this we checked that inclusion of additional constant acceleration as does not improve the quality of orbital solutions. All the tests performed lead to the conclusion that no anomalous acceleration is acting on Pioneers spacecrafts.