The Effects of Airbags and Seatbelts on Occupant Injury in Longitudinal Barrier Crashes

Introduction: Longitudinal barriers, such as guardrails, are designed to prevent a vehicle that leaves the roadway from impacting a more dangerous object while minimizing the risk of injury to the vehicle occupants. Current full-scale test procedures for these devices do not consider the effect of occupant restraints such as seatbelts and airbags. The purpose of this study was to determine the extent to which restraints are used or deployed in longitudinal barrier collisions and their subsequent effect on occupant injury. Methods: Binary logistic regression models were generated to predict occupant injury risk using data from the National Automotive Sampling System / Crashworthiness Data System from 1997 through 2007. Results: In tow-away longitudinal barrier crashes, airbag deployment rates were 70% for airbag-equipped vehicles. Compared with unbelted occupants without an airbag available, seat belt restrained occupants with an airbag available had a dramatically decreased risk of receiving a serious (MAIS 3+) injury (odds-ratio (OR)=0.03; 95% CI: 0.004- 0.24). A similar decrease was observed among those restrained by seat belts, but without an airbag available (OR=0.03; 95% CI: 0.001- 0.79). No significant differences in risk of serious injuries were observed between unbelted occupants with an airbag available compared with unbelted occupants without an airbag available (OR=0.53; 95% CI=0.10-2.68). Impact on Industry: This study refutes the perception in the roadside safety community that airbags rarely deploy in frontal barrier crashes, and suggests that current longitudinal barrier occupant risk criteria may over-estimate injury potential for restrained occupants involved in a longitudinal barrier crash.

Secondary collisions revisited: real-world crash data and relationship to crash test criteria

Objectives: Previous research conducted in the late 1980s suggested that vehicle impacts following an initial barrier collision increase severe occupant injury risk. Now over 25years old, the data are no longer representative of the currently installed barriers or the present US vehicle fleet. The purpose of this study is to provide a present-day assessment of secondary collisions and to determine if current full-scale barrier crash testing criteria provide an indication of secondary collision risk for real-world barrier crashes. Methods: To characterize secondary collisions, 1,363 (596,331 weighted) real-world barrier midsection impacts selected from 13years (1997-2009) of in-depth crash data available through the National Automotive Sampling System (NASS) / Crashworthiness Data System (CDS) were analyzed. Scene diagram and available scene photographs were used to determine roadside and barrier specific variables unavailable in NASS/CDS. Binary logistic regression models were developed for second event occurrence and resulting driver injury. To investigate current secondary collision crash test criteria, 24 full-scale crash test reports were obtained for common non-proprietary US barriers, and the risk of secondary collisions was determined using recommended evaluation criteria from National Cooperative Highway Research Program (NCHRP) Report 350. Results: Secondary collisions were found to occur in approximately two thirds of crashes where a barrier is the first object struck. Barrier lateral stiffness, post-impact vehicle trajectory, vehicle type, and pre-impact tracking conditions were found to be statistically significant contributors to secondary event occurrence. The presence of a second event was found to increase the likelihood of a serious driver injury by a factor of 7 compared to cases with no second event present. The NCHRP Report 350 exit angle criterion was found to underestimate the risk of secondary collisions in real-world barrier crashes. Conclusions: Consistent with previous research, collisions following a barrier impact are not an infrequent event and substantially increase driver injury risk. The results suggest that using exit-angle based crash test criteria alone to assess secondary collision risk is not sufficient to predict second collision occurrence for real-world barrier crashes.

Secondary Collisions Revisited: Real-World Crash Characteristics and Relationship to Crash Test Criteria

Previous research conducted in the late 1980’s suggested that vehicle impacts following an initial barrier collision increase severe occupant injury risk. Now over twenty-five years old, the data used in the previous research is no longer representative of the currently installed barriers or US vehicle fleet. The purpose of this study is to provide a present-day assessment of secondary collisions and to determine if full-scale barrier crash testing criteria provide an indication of secondary collision risk for real-world barrier crashes. The analysis included 1,383 (596,331 weighted) real-world barrier midsection impacts selected from thirteen years (1997-2009) of in-depth crash data available through the National Automotive Sampling System (NASS) / Crashworthiness Data System (CDS). For each suitable case, the scene diagram and available scene photographs were used to determine roadside and barrier specific variables not available in NASS/CDS. Binary logistic regression models were developed for second event occurrence and resulting driver injury. Barrier lateral stiffness, post-impact vehicle trajectory, vehicle type, and pre-impact tracking conditions were found to be statistically significant contributors toward secondary event occurrence. The presence of a second event was found to increase the likelihood of a serious driver injury by a factor of seven compared to cases with no second event present. Twenty-four full-scale crash test reports were obtained for common non-proprietary US barriers, and the risk of secondary collisions was determined using recommended evaluation criteria from NCHRP Report 350. It was found that the NCHRP Report 350 exit angle criterion alone was not sufficient to predict second collision occurrence for real-world barrier crashes.

“Una Casa Entre el Greco y el Siroco” Crítica de la Malaparte

El título de esta tesis, utiliza primero una expresión periodística muy conocida sobre esta obra, que expresa muy bien su característica contradictoria, paradójica, siempre entre opuestos, frecuentemente utilizadas por los textos que sobre esta obra se han escrito. La segunda expresión define a esta tesis, incluida en el grupo de investigación sobre el objetivo común de la Crítica Arquitectónica. La casa Malaparte, olvidada durante largo tiempo y venerada en otros momentos, fue elegida por referéndum en 1979 por la revista “Modo (Cien proyectos para recordar)” como la obra más representativa de la arquitectura italiana del siglo XX. Un icono de modernidad en 1979 y paradójicamente no en su momento, ya que difícilmente se podría encuadrar en las tipologías de vivienda moderna de los años treinta. El objetivo de esta tesis es la racionalización del valor de esta obra, admitida de alguna manera en los “manuales de arquitectura moderna”, proponiendo para ello el reconocimiento de sus singularidades y regularidades como elementos de investigación del valor sustantivo de la arquitectura, el polinomio indisociable: contexto, forma, función, construcción. Tenemos datos, textos, hermenéutica. Nuestro método no puede ser otro que la crítica de los datos y texto y la crítica poética. Nuestra tesis, se inserta en este conjunto de crítica arquitectónica, vinculada al método llamado por el Catedrático Dr. Antonio Miranda Regojo “Mírregan-Todorov” que emplearemos como referencia y método para mostrar lo que más nos interesa, la calidad de la arquitectura, su ser, que paradójicamente, difiere de su descripción, de su momento histórico, en fin de todo aquello que en realidad solo la describe, la analiza y la interpreta. Nuestra variación propuesta al modelo de referencia, consta del siguiente desarrollo: 1. Crítica de “La Crítica”. 2. Crítica poética. 3. Conclusiones El primer capítulo, propone “La Crítica”, entendida como ese valor colectivo depositado por los textos escritos sobre la obra contrastado con nuestras observaciones personales respecto de cada uno de ellos. Las críticas seleccionadas muestran una nube de alternativas relativas a la descripción, análisis e interpretación que sobre la obra se han producido. Este capítulo, constituye una compilación de textos ordenada cronológicamente, que introduce al conocimiento de la obra. Recoge las primeras referencias, los artículos, los libros, las películas y anuncios así como alguno de los textos académicos que se han escrito sobre esta obra. 15 Los artículos seleccionados son los siguientes: Aldo Morbelli 1942. A. Alieri M.Clerici F.Palpacelli y G.Vaccaro 1966. Francesco Venezia con G.Petrusch 1973 Vieri Quilici.1977/1981 G.K.Koenig, 1979 John Hejduk 1980 Audrey Batey 1980. Manfredo Tafuri 1981. Francesco Venezia 1983. Joe Bostik 1989. Vittorio Savi, 1989. Marida Talamona 1989. W. Arets, W. Van der Bergh. 1989. Franco Purinni 1991. Marida Talamona 1997. Bruce Chatwin 1997. Los libros seleccionados han sido: Marida Talamona. Casa Malaparte, Milano 1990. Sergio Attanasio. Curzio Malaparte “Casa come me” Punta del Massullo, tel. 160 Capri. Nápoles 1990 Gianni Petenna. CasaMalaparte, Capri, 1999 Michael McDonough. A house like me. Edit.Clarkson Potter,New York 1999 Mario Ferrari. Adalberto Libera “Casa Malaparte en Capri1938-1942” 2008 Las películas seleccionadas: Il Cristo proibito, 1956 Le Mèpris, 1963 La Pelle, 1981 Anuncio de Hugo Boss 2010 16 Los textos académicos recogidos son: Angela delGaudio. Casa Malaparte. Interventi e restauri. 2003 Nicoletta Setola. Casa Malaparte. Il cantiere le tecnologie i materiali. 2004 Gloria Paz Saravia Ortiz. La casa Malaparte de A.libera. 2007 En el capítulo segundo “Crítica poética” se circunscribe, según la definición utilizada, a lo que en particular tiene como nivel de verdad, por la idoneidad de su construcción, tipología e iconología en relación al lugar (entidad propia, identidad auténtica). Existen algunos estudios que proponen a la casa Malaparte comprendida en la poética común de la obra de su arquitecto, Adalberto Libera. Nuestra posición nada tiene que ver con “la manera de hacer de un autor” se inclina a investigar obras enlazadas por estructuras comunes, reflejo y consecuencia especialmente de la propia arquitectura, nos interesa la poética de la arquitectura, no la de un autor. Realizamos tres ensayos, el primero trata de investigar el “Lugar” contexto de la obra, proponiendo el reconocimiento de un sistema lugar-arquitectura, (Conjunto de reglas o principios sobre una materia racionalmente enlazados entre sí) del que formulamos una serie de definiciones como características de esta relación: la analogía, la simpatía, la emulación, la signatura, la nematología y la sinexión. Concluyendo que la relación encontrada en la Malaparte podría explicarse de esta manera: ninguna mimesis, admite cierta analogía, un camuflaje solo geométrico, sin emulación de “tipismo” alguno, con emulación del modelo continuo de la “caja” desde el ataúd a la humilde vivienda , con “simpatía” como una obra contemporánea, con una fuerte signatura sobre el lugar, en correspondencia a lugar señalado por la historia y a la indeterminación iconológica que propone su arquitectura, (fetiche, simulacro) con una relación “nematológica” a través de su implantación y con una vinculación especial de “sinexión” entre la superficie del lugar y el acomodo de esta arquitectura. Continuamos con la relación propia de la obra y el lugar, concluyendo como la casa Malaparte propone el espacio sobre su cubierta, a modo de patio, de recinto. La obra demuestra que no es únicamente la sustancia material quien protagoniza la acción de “recintar”. El vértigo constituye la materia infranqueable del perímetro. En la Malaparte es el plano arquitectónico, (elevado) el recinto descubierto, el plano que posibilita la máxima relación con el exterior en esta arquitectura. En su interior el paisaje deja de ser fondo y el habitante se incorpora al escenario, se incorpora al paisaje. Te encuentras midiendo, relacionando distancias desde las espículas de pino, rocas, acantilados, barcos, islas, mar hasta la costa de Amalfi. Esta posición sobre el paisaje, es comparada con la casa Kaufman de F.L.Wrigth. El segundo ensayo investiga el proyecto de la obra. Distinguimos entre proyecto-forma, proyecto-origen, proyecto programa, proyecto-acción y proyectos-signo. Encontramos que no existe proyecto-forma que explique la casa Malaparte, tenemos proyectoorigen, proyecto-programa y proyectos-signo suficientes para racionalizar esta obra. Nos encontramos con un proyecto-acción, en permanente discusión, debatido hasta la saciedad, con la finalidad de habitar aquella roca, cuyas proposiciones se contrastan en la obra, ampliando el proceso de proyecto a la propia acción de construir, proyecto y construcción no estan disociados. Los proyectos “signo” de esta obra, nos permiten relacionar la permanencia de un programa, una organización, una comunicación y distribución que entendemos continua y conducida por Malaparte. Lo realmente importante previsto y controlable por aquel: programa y distribución. Nos permitimos afirmar que lo significante continuo es un proyecto–programa limitado a una forma necesaria iniciada por Libera, como una semilla. Su forma es el resultado de un procedimiento, arraigado y condicionado a un terreno. Un proceso que consiste en establecer unas alturas tipo sobre un programa distribuido en planta, y limitado con una construcción racional, tipológica sobre muros de carga, capaz de soportar cualquier programa habitacional, que proporciona inevitablemente un resultado seguro. El tercer ensayo propone una “novela” sobre la manera de construcción de la obra, que nos permite explicar la gran escalera de la Malaparte. Encontramos que la construcción de la Malaparte, también forma parte de un sistema. Este sistema es capaz de generar forma, sin recurrir a las mascaras fijadas por la tradición o las modas, manteniendo su libertad de expresión sin concesiones. Consideramos que en el camino de acceso a la obra que hubo que ejecutarse para tal fin están las claves para la comprensión de su escalera. La escalera de la Malaparte la comprendemos desde la propia accesibilidad a la obra. Su trazado abocinado, su forma “strombata”, es consecuencia para nosotros de sus límites físicos, su elevación, resultado de las cotas que responden a los niveles de los planos de trabajo, incluida la terraza –patio. Su expresión geométrica sería visible desde la ejecución de las obras; no es posterior al paralelepípedo inicial, sino previa. Su función de acceso a la terraza no es la principal, excluida desde el proyecto administrativo de Libera, al texto escrito de Malaparte sobre su casa (ninguna escalera exterior). Sus funciones principales subyacentes que quedan envueltas son primeramente abastecer la obra, en segundo lugar como cubierta de la escalera interior que tuvo que salir de su posición centrada en el paralelepípedo inicial, al extremo exterior de este. La solución a estas necesidades acuciantes, mostrarían su función paradigmática en un tercer lugar, su solución como cubierta peldañeada, como fachada remontable, que se produce desde nuestra visión del exterior, la gran escalera de acceso al lugar principal y el hecho único y genial de la Malaparte. Las conclusiones finales de esta tesis están referidas en primer lugar al Texto escrito sobre la obra y en segundo lugar a la obra misma: La Casa es entendida en los textos analizados, como objeto que soporta simultáneamente la idea romántica de emoción-inspiración y la contemporánea de invitación a su conocimiento. Producto de su singular abstracción explicamos su transformación en lo que constatamos dos vías extremas: una como artefacto, trasto inútil y pretencioso que explica las críticas extremas de Koening y Durante. Habría que demoler la Malaparte, y por la otra se produce su transformación en “objeto artístico” (inspiraciónemoción– conocimiento) que hay que venerar. Este trinomio deviene en interpretación y de aquí su provocación hacia la literatura, el cine y la imagen sobre la obra. Ambos extremos podrían originarse por no comprender, por no llegar a explicar cómo este objeto es también casa, casa con patio, habitación, refugio, arquitectura con toda su contingencia que con coherencia, razón y libertad de expresión produce aquel objeto, con la única intencionalidad acuciante de ser construido y habitado. El gran valor “literario-artístico” de la Malaparte recogido en sus textos, debemos admitir pues que tiene su origen en la interpretación de lo arquitectónico, que no es evidente, que entendemos no puede deducirse de su mera imagen, del mismo modo que la escultura asociada a un capitel corintio, que algunos pretenden disociar del apoyo constructivo de un pie derecho, como la solución del tímpano- escultura de una portada barroca, que pretendemos separar de la eficacia del dintel, como la cúpula solución a la cubierta del Panteón de Agripa, que estudiamos aparte como un problema de ingeniería, estos aspectos múltiples, complejos y no evidentes producen la fragmentación de lo arquitectónico, y permiten sus interpretaciones independientes, desguazando la arquitectura en trozos muy visibles que algunos llamaron “arte” y sistemas mas ocultos que otros llamaron “ingeniería y técnica”. Contemplar lo humano con fantasía es también nuestra conclusión deductiva de lo que nos permite la Malaparte, su identidad propia y peculiar deducida del Texto. Una arquitectura que permite examinar lo humano con fantasía, también un gran valor común, literario y arquitectónico que no queremos disociar. Si nos afirmamos en la autonomía de la arquitectura, sin renunciar al Texto, su identidad no es más que materialidad, ni menos que la metáfora del habitar diverso del hombre en la tierra. Ambos discursos permanecerán siempre abiertos para poetas y arquitectos. La Malaparte puede explicarse desde el lugar, de su proyecto y su construcción. Podríamos limitarnos aun más, solamente de su realidad congelada actual lograríamos inferir su valor como arquitectura que ha resuelto el problema; cubriendo, superponiendo con rigurosa limpieza, orden y geometría, al caos de accidentalidad y esfuerzo, un resultado despejado, de la materialidad y la técnica, esto es en definitiva el poder de lo arquitectónico, realizado no como máscara superpuesta, sino como resultado coherente, piel viva sobre huesos y músculos necesarios.

Synthesis of new calixarene-based lubricant additives

The lubricants are normally composed by base oils and a number of additives which are added to improve the performances of the final product. In this work, which is due to the collaboration between ENI S.p.A. and Prof. Casnati’s group, significant results in the application of calixarene structures to two classes of lubricant additives (viscosity index improvers and detergents) were shown. In particular, several calix[8]arene derivatives were synthesized to use as core precursors in the “arm-first" synthetic processes of star polymers for viscosity index improver applications. The use of calixarene derivatives enable the production of star polymers with a high and well-defined number of branches and endowed with a very low dispersivity of molecular weight which can originate better performances than the current commercially available viscosity index improvers of the major competitor. Several functional groups were considered to prepare reactive p-tert-butylcalix[8]arene cores to be used in living anionic polymerization. n-butyllithium was used as model of the living anionic polymer to test the outcome of the reaction of polymer insertion on the calixarene core, facilitating the analyses of the products. The calixarene derivative, which easier reacts with n-BuLi, was selected for the preparation of star polymers by using a isoprene/styrene living anionic polymer. Finally, the lubricant formulations, which include the calixarene-based star polymers or commercially available products as viscosity index improvers, were prepared and comparatively tested. In the last part of Thesis, the use of calixarenes as polycarboxylic acids to synthetize new sulfur-free detergents as lubricant additives was carried out. In this way, these calcium-based detergents can be used for the formulation of new automotive lubricants with low content of ash, phosphorus and sulfur (low SAPS). To increase the low deprotonation degree of OH groups and their capacity to complex calcium ions, a complete functionalization of the calixarene mixtures with acetic acid groups was required. Futhermore, the “one-step” synthesis of new calixarenes with alkyl chains in para positions longer than the ones already known was necessary to improve the oil solubility and stability of reverse micelles formed by the detergents. Moreover, the separation and characterization of the calixarenes were carried out to optimize their synthetic process, also on pilot scale. For our purpose, the use of p-tert-octylcalixarenes for the preparation of detergents was carried out to compare the properties of the final detergents respect to the use of the p-dodecyl calixarenes. Once achieved the functionalization of both calixarene mixtures with carboxylic acid groups, the syntheses of new calixarene-based detergents were carried out to identify the best calixarene derivative for our research goals. The synthetic process for the preparation of calixarene-based detergent having very high basicity (TBN 400) was also investigated for applications in lubricants for marine engines. In addition, with the aim of testing the calixarene-based detergents in automotive lubricants, several additive packages (concentrated mixture of additives) containing our detergents were prepared. Using these packages the corresponding automotive lubricants can be formulated. Besides, a lubricant containing commercial calcium alkylbenzene-sulfonates detergents was prepared to compare its detergency properties with those of the calixarene-based oils.

Efficacy of Stanozolol on bone regeneration: in vitro and in vivo study

La ricerca di nuove strategie per la rigenerazione ossea rappresenta un focus di interesse centrale per migliorare la gestione di casi clinici complessi nell’ambito della chirurgia orale e maxillo-facciale. Uno degli approcci più utilizzati in tale contesto si basa sull’utilizzo di molecole con proprietà osteoinduttive e molte sostanze sono state fino ad oggi sperimentate. E’ noto in letteratura che gli androgeni svolgono un ruolo chiave nella regolazione della morfogenesi ossea e nel mantenimento della sua omeostasi durante il corso della vita. Questo lavoro di tesi nasce dall’ipotesi che la somministrazione locale di tali ormoni, eventualmente combinata a materiali da innesto, possa favorire la guarigione di difetti ossei. Stando a questa premessa, sono stati valutati gli effetti dello steroide sintetico Stanozololo sulla rigenerazione ossea in diversi settings sperimentali. La tesi è strutturata secondo un percorso che segue le fasi della ricerca, attraverso sperimentazioni in vitro e in vivo; ogni capitolo può essere approcciato come uno studio a sé stante, corrispondente ad una determinata tappa dell’iter sperimentale. Sulla base di questi intenti, viene fornito inizialmente un quadro d’insieme circa gli effetti degli androgeni sull’osso. A seguire, è presentata una sperimentazione in vitro nella linea cellulare SaOS-2. Infine, è proposta un’innovativa metodologia di analisi per lo studio della rigenerazione ossea nel modello di ratto, ove viene testata la somministrazione locale di Stanozololo combinato a materiale da innesto.

Heterogeneous catalysts for environmentally sustainable reactions

This PhD work deals with problems of synthetic organic chemistry with particular attention to the development of environmentally friendly processes. In particular, new synthetic strategies have been studied based on the use of low cost heterogeneous catalysts, non-toxic reagents and mild operating conditions that do not involve, when possible, the use of solvents. The catalysts examined are both basic and acids, commercial or prepared by hetereogenization of homogeneous catalysts synthesized by tethering or impregnation. In particular it will be discussed the catalytic activity of oxides (Al2O3 and TiO2), supported sulphonic acids and hydrotalcites for the reactions of selective monoesterificazion of dicarboxylic acids, dehydrogenation of butane in gas phase, esterification of levulinic acid, Friedel-Craft acylations, C-C and C-P coupling. The use of these materials has allowed the development of simple processes with low environmental impact. The operating conditions are in fact mild and reaction times short. The selectivity for the desired products is in all reported cases very high and the catalysts can be recycled maintaining their optimum performances.

Modulation of Sarco/Endoplasmic Reticulum Ca2+-ATPase 2 (SERCA2) function by acetylation following the treatment with histone deacetylase inhibitor suberoylanilide hydroxamic acid (SAHA)

Background: Acetylation and deacetylation at specific lysine (K) residues is mediated by histone acetylases (HATs) and deacetylases (HDACs), respectively. HATs and HDACs act on both histone and non-histone proteins, regulating various processes, including cardiac impulse propagation. Aim of the present work was to establish whether the function of the Ca2+ ATPase SERCA2, one of the major players in Ca2+ reuptake during excitation-contraction coupling in cardiac myocytes (CMs), could be modulated by direct K acetylation. Materials and methods: HL-1 atrial mouse cells (donated by Prof. Claycomb), zebrafish and Streptozotocin-induced diabetic rat CMs were treated with the pan-inhibitor of class I and II HDACs suberanilohydroxamic acid (SAHA) for 1.5 hour. Evaluation of SERCA2 acetylation was analyzed by co-immunoprecipitation. SERCA2 activity was measured on microsomes by pyruvate/NADH coupled reaction assay. SERCA2 mutants were obtained after cloning wild-type and mutated sequences into the pCDNA3 vector and transfected into HEK cells. Ca2+ transients in CMs (loading with Fluo3-AM, field stimulation, 0.5 Hz) and in transfected HEK cells (loading with FLUO-4, caffeine pulse) were recorded. Results: Co-Immunoprecipitation experiments performed on HL-1 cells demonstrated a significant increase in the acetylation of SERCA2 after SAHA-treatment (2.5 µM, n=3). This was associated with an increase in SERCA2 activity in microsomes obtained from HL-1 cells, after SAHA exposure (n=5). Accordingly, SAHA-treatment significantly shortened the Ca2+ reuptake time of adult zebrafish CMs. Further, SAHA 2.5 nM restored to control values the recovery time of Ca2+ transients decay in diabetic rat CMs. HDAC inhibition also improved contraction parameters, such as fraction of shortening, and increased pump activity in microsomes isolated from diabetic CMs (n=4). Notably, the K464, identified by bioinformatic tools as the most probable acetylation site on human SERCA2a, was mutated into Glutamine (Q) or Arginine (R) mimicking acetylation and deacetylation respectively. Measurements of Ca2+ transients in HEK cells revealed that the substitution of K464 with R significantly delayed the transient recovery time, thus indicating that deacetylation has a negative impact on SERCA2 function. Conclusions: Our results indicate that SERCA2 function can be improved by pro-acetylation interventions and that this mechanism of regulation is conserved among species. Therefore, the present work provides the basis to open the search for novel pharmacological tools able to specifically improve SERCA2 activity in diseases where its expression and/or function is impaired, such as diabetic cardiomyopathy.

Tuning the functional properties of Silicon Carbide Thin Film and Nanowires

The present thesis has been devoted to the synthesis and investigation of functional properties of silicon carbide thin films and nanowires. The work took profit from the experience of the research group in the synthesis of 3C-SiC from vapour phase. 3C-SiC thin films Thin films heteroepitaxy on silicon substrates was carried out in a vapour phase epitaxy reactor. The initial efforts were committed to the process development in order to enhance the crystal quality of the epi-layer. The carbonization process and a buffer layer procedure were optimized in order to obtain good quality monocrystalline 3C-SiC layers. The films characterization was used not only to improve the entire process, but also to assess the crystalline quality and to identify the defects. Methyltrichlorosilane (MTS) was introduced during the synthesis to increase the growth rate and enhance crystalline quality. The effect of synthesis parameters such as MTS flow and process temperature was studied in order to promote defect density reduction and the release of the strain due to lattice mismatch between 3C-SiC and silicon substrate. In-growth n-type doping was implemented using a nitrogen gas line and the effect of different synthesis parameters on doping level was studied. Raman measurements allowed a contactless characterization and evaluation of electrically active dopant. The effect of MTS on nitrogen incorporation was investigated and a promotion of dopant concentration together with a higher growth rate were demonstrated. This result allows to obtain higher doping concentrations without deteriorating crystal quality in 3C-SiC and, to the best of our knowledge, it has never been demonstrated before. 3C-SiC nanowires Core-shell SiC-SiO2 nanowires were synthesized using a chemical vapour deposition technique in an open tube configuration reactor on silicon substrates. Metal catalyst were used to promote a uniaxial growth and a dense bundle of nanowires 100 µm long and 60 nm thick was obtained. Substrate preparation was found to be fundamental in order to obtain a uniform nanowire density. Morphological characterization was carried out using scanning electron microscopy and the analysis of structural, compositional, optical properties is reported.

Intermolecular and Intramolecular Charge Transfer in Functional Molecular Materials

This thesis is devoted to the investigation of inter and intramolecular charge transfer (CT) in molecular functional materials and specifically organic dyes and CT crystals. An integrated approach encompassing quantum-chemical calculations, semiempirical tools, theoretical models and spectroscopic measurements is applied to understand structure-property relationships governing the low-energy physics of these materials. Four main topics were addressed: 1) Spectral properties of organic dyes. Charge-transfer dyes are constituted by electron donor (D) and electron acceptor (A) units linked through bridge(s) to form molecules with different symmetry and dimensionality. Their low-energy physics is governed by the charge resonance between D and A groups and is effectively described by a family of parametric Hamiltonians known as essential-state models. These models account for few electronic states, corresponding to the main resonance structures of the relevant dye, leading to a simple picture that is completed introducing the coupling of the electronic system to molecular vibrations, treated in a non-adiabatic way, and an effective classical coordinate, describing polar solvation. In this work a specific essential-state model was proposed and parametrized for the dye Brilliant Green. The central issue in this work has been the definition of the diabatic states, a not trivial task for a multi-branched chromophore. In a second effort, we have used essential-state models for the description of the early-stage dynamics of excited states after ultrafast excitation. Crucial to this work is the fully non-adiabatic treatment of the coupled electronic and vibrational motion, allowing for a reliable description of the dynamics of systems showing a multistable, broken-symmetry excited state. 2) Mixed-stack CT salts. Mixed-stack (MS) CT crystals are an interesting class of multifunctional molecular materials, where D and A molecules arrange themselves to form stacks, leading to delocalized electrons in one dimension. The interplay between the intermolecular CT, electrostatic interactions, lattice phonons and molecular vibrations leads to intriguing physical properties that include (photoinduced) phase transitions, multistability, antiferromagnetism, ferroelectricity and potential multiferroicity. The standard microscopic model to describe this family of materials is the Modified Hubbard model accounting for electron-phonon coupling (Peierls coupling), electron-molecular vibrations coupling (Holstein coupling) and electrostatic interactions. We adopt and validate a method, based on DFT calculations on dimeric DA structures, to extract relevant model parameters. The approach offers a powerful tool to shed light on the complex physics of MS-CT salts. 3) Charge transfer in organic radical dipolar dyes. In collaboration with the group of Prof. Jaume Veciana (ICMAB- Barcellona), we have studied spectral properties of a special class of CT dyes with D-bridge-A structure where the acceptor group is a stable radical (of the perchlorotriphenylmethyl, PTM, family), leading to an open-shell CT dyes. These materials are of interest since they associate the electronic and optical properties of CT dyes with magnetic properties from the unpaired electron. The first effort was devoted to the parametrization of the relevant essential-state model. Two strategies were adopted, one based on the calculation of the low-energy spectral properties, the other based on the variation of ground state properties with an applied electric field. 4) The spectral properties of organic nanoparticles based on radical species are investigated in collaboration with Dr. I. Ratera (ICMAB- Barcellona). Intriguing spectroscopic behavior was observed pointing to the presence of excimer states. In an attempt to rationalize these findings, extensive calculations (TD-DFT and ZINDO) were performed. The results for the isolated dyes are validated against experimental spectra in solution. To address intermolecular interactions we studied dimeric structures in the gas phase, but the preliminary results obtained do not support excimer formation.

Molecular approaches to smart materials via interface recognition and conformationally switchable cavitands

In this thesis the molecular level design of functional materials and systems is reported. In the first part, tetraphosphonate cavitand (Tiiii) recognition properties towards amino acids are studied both in the solid state, through single crystal X-ray diffraction, and in solution, via NMR and ITC experiments. The complexation ability of these supramolecular receptors is then applied to the detection of biologically remarkable N-methylated amino acids and peptides using complex dynamic emulsions-based sensing platforms. In the second part, a general supramolecular approach for surface decoration with single-molecule magnets (SMMs) is presented. The self-assembly of SMMs is achieved through the formation of a multiple hydrogen bonds architecture (UPy-NaPy complexation). Finally we explore the possibility to impart auxetic behavior to polymeric material through the introduction of conformationally switchable monomers, namely tetraquinoxaline cavitands (QxCav). Their interconversion from a closed vase conformation to an extended kite form is studied first in solution, then in polymeric matrixes via pH and tensile stimuli by UV-Vis spectroscopy.

Synthesis and Characterisation of Functional Magnetic and Plasmonic Nanomaterials

The main aim of this thesis is the controlled and reproducible synthesis of functional materials at the nanoscale. In the first chapter, a tuning of morphology and magnetic properties of magnetite nanoparticles is presented. It was achieved by an innovative approach, which involves the use of an organic macrocycle (calixarene) to induce the oriented aggregation of NPs during the synthesis. This method is potentially applicable to the preparation of other metal oxide NPs by thermal decomposition of the respective precursors. Products obtained, in particular the multi-core nanoparticles, show remarkable magnetic and colloidal properties, making them very interesting for biomedical applications. The synthesis and functionalisation of plasmonic Au and Ag nanoparticles is presented in the second chapter. Here, a supramolecular approach was exploited to achieve a controlled and potentially reversible aggregation between Au and Ag NPs. This aggregation phenomena was followed by UV - visible spectroscopy and dynamic light scattering. In the final chapters, the conjugation of plasmonic and magnetic functionalities was tackled through the preparation of dimeric nanostructures. Au - Fe oxide heterodimeric nanoparticles were prepared and their magnetic properties thoroughly characterised. The results demonstrate the formation of FeO (wustite), together with magnetite, during the thermal decomposition of the iron precursor. By an oxidation process that preserves Au in the dimeric structures, wustite completely disappeared, with the formation of either magnetite and / or maghemite, much better from the magnetic point of view. The plasmon resonance of Au results damped by the presence of the iron oxide, a material with high refractive index, but it is still present if the Au domain of the nanoparticles is exposed towards the bulk. Finally, remarkable hyperthermia, also in vitro, was found for these structures.

Self-standing curved crystals for X and Gamma rays focusing

The efficiency of a Laue lens for X and Gamma ray focusing in the energy range 60 ÷ 600 keV is closely linked to the diffraction efficiency of the single crystals composing the lens. A powerful focusing system is crucial for applications like medical imaging and X ray astronomy where wide beams must be focused. Mosaic crystals with a high density, such as Cu or Au, and bent crystals with curved diffracting planes (CDP) are considered for the realization of a focusing system for X rays, owing to their high diffraction efficiency. In this work, a comparison of the efficiency of CDP crystals and mosaic crystals was performed on the basis of the theory of X-ray diffraction. Si, GaAs and Ge CDP crystals with optimized thicknesses and moderate radii of curvature of several tens of metres demonstrate comparable or superior performance with respect to the higher atomic number mosaic crystals generally used. A simplified approach for calculating the integrated reflectivity of the crystals is applied. A bending technique used during this work to realize CDP crystals consists in a controlled surface damaging induced by a mechanical lapping process. A compressive strained layer of few micrometres in thickness is generated and causes the convex curvature of the damaged side of the crystal. Another new bending technique is developed and the main results are shown. The process consists on a film deposition of a selected bi-component epoxy resin on one side of crystal, made uniform in thickness by mean of a spin-coater. Choosing the speed of spin-coating, so changing the thickness of the film, a control of radius of curvature can be obtained. Moreover the possibility to combine the two bending technique to obtain CDP crystal with a stronger curvature in rather thick crystals was demonstrated. Detailed characterization of Si, and GaAs CDP crystals at low and high x-ray energies are performed on flat and bent crystals obtained with the damaging and the resin deposition technique. As expected an increase of diffraction efficiency in asymmetrical diffraction geometry in CDP crystals with respect to the flat ones is observed. On the other hand an unexpected increase of the integrated intensity in symmetrical geometry, not predicted by the theory, is observed in all the measurements performed with different set up. The experimental trend of the integrated reflectivity as a function of the radius of curvature is in a good agreement with that predicted by the theory of bent perfect crystals, so it is possible to conclude that the surface damage has a limited effect on the crystal reflectivity. A study of the integrated reflectivity in the energy range of interest (100÷350 keV) in CDP crystals realized with damaging and resin deposition technique at symmetrical and asymmetrical geometries was performed at ILL Institute. Also at these energies the diffraction efficiency of bent crystals was much larger (a 12 time increase is observed for bent crystals in asymmetrical 111 geometry) than that measured in flat crystals. The diffraction efficiency of CDP crystals realized with both techniques tends to coincide with that of flat crystals at very high energies (> 200 keV). This suggesting that also real flat perfect crystals can be considered as strongly bent or mosaic crystals at very high X ray energies.

La memoria della pubblicità. Il ruolo dell'archivio. Il fondo Art Directors Club Italiano conservato al Centro Studi e Archivio della Comunicazione dell'Università di Parma.

La ricerca ha scelto di affrontare una serie di problemi connessi alla valorizzazione e alla conservazione del materiale pubblicitario rispetto a un caso studio selezionato, l’archivio dell’Art Directors Club Italiano conservato presso il Centro Studi e Archivio della Comunicazione dell’Università di Parma. Questo archivio è costituito principalmente da materiali della comunicazione pubblicitaria - suddivisi in categorie corrispondenti a media e tecniche - iscritti dal 1998 al 2003 agli ADCI Awards, il premio italiano di riferimento dedicato alla pubblicità e organizzato dall’Art Directors Club Italiano - ADCI a partire dall’anno della sua fondazione, il 1985. La sua storia è quindi connessa strettamente con quella dell’associazione, che rappresenta e riunisce professionisti della pubblicità che condividono obiettivi comuni, e in particolare il riconoscimento e la valorizzazione della creatività come elemento fondante della comunicazione d’impresa e istituzionale. Lo CSAC in parallelo, il contesto archivistico all’interno del quale questi fondi sono venuti a trovarsi in seguito alla donazione da parte dell’ADCI nel 2002-2003, è un centro di ricerca dell’Università di Parma dedicato alla conservazione e allo studio di archivi provenienti da diversi ambiti culturali. A partire da una mappatura dell’archivio e dalla ricostruzione di contesti e dibattiti fondamentali per studiare e organizzare i fondi, questa tesi si propone di individuare, in particolare attraverso gli strumenti digitali, possibili modalità di analisi, esposizione e accesso ai materiali, che possano aprire una rete di connessioni verso altri ambiti di ricerca e nuove prospettive in funzione delle storie della pubblicità.