DYNAMICAL EVOLUTION OF VISCOUS DISKS AROUND Be STARS. I. PHOTOMETRY

Be stars possess gaseous circumstellar disks that modify in many ways the spectrum of the central B star. Furthermore, they exhibit variability at several timescales and for a large number of observables. Putting the pieces together of this dynamical behavior is not an easy task and requires a detailed understanding of the physical processes that control the temporal evolution of the observables. There is an increasing body of evidence that suggests that Be disks are well described by standard alpha-disk theory. This paper is the first of a series that aims at studying the possibility of inferring several disk and stellar parameters through the follow-up of various observables. Here we study the temporal evolution of the disk density for different dynamical scenarios, including the disk buildup as a result of a long and steady mass injection from the star, the disk dissipation that occurs after mass injection is turned off, as well as scenarios in which active periods are followed by periods of quiescence. For those scenarios, we investigate the temporal evolution of continuum photometric observables using a three-dimensional non-LTE radiative transfer code. We show that light curves for different wavelengths are specific of a mass loss history, inclination angle, and alpha viscosity parameter. The diagnostic potential of those light curves is also discussed.

New activity in the large circumstellar disk of the Be-shell star 48 Librae

Aims. Spectroscopic, polarimetric, and high spectral resolution interferometric data covering the period 1995-2011 are analyzed to document the transition into a new phase of circumstellar disk activity in the classical Be-shell star 48 Lib. The objective is to use this broad data set to additionally test disk oscillations as the basic underlying dynamical process. Methods. The long-term disk evolution is described using the V/R ratio of the violet and red emission components of H alpha and Br gamma, radial velocities and profiles of He I and optical metal shell lines, as well as multi-band BVRI polarimetry. Single-epoch broad-band and high-resolution interferometric visibilities and phases are discussed with respect to a classical disk model and the given baseline orientations. Results. Spectroscopic signatures of disk asymmetries in 48 Lib vanished in the late nineties but recovered some time between 2004 and 2007, as shown by a new large-amplitude and long-duration V/R cycle. Variations in the radial velocity and line profile of conventional shell lines correlate with the V/R behavior. They are shared by narrow absorption cores superimposed on otherwise seemingly photospheric He I lines, which may form in high-density gas at the inner disk close to the photosphere. Large radial velocity variations continued also during the V/R-quiet years, suggesting that V/R may not always be a good indicator of global density waves in the disk. The comparison of the polarization after the recovery of the V/R activity shows a slight increase, while the polarization angle has been constant for more than 20 years, placing tight limits on any 3-D precession or warping of the disk. The broad H-band interferometry gives a disk diameter of (1.72 +/- 0.2) mas (equivalent to 15 stellar radii), position angle of the disk (50 +/- 9)degrees and a relatively low disk flattening of 1.66 +/- 0.3. Within the errors the same disk position angle is derived from polarimetric observations and from photocenter shifts across Br gamma. The high-resolution interferometric visibility and phase profiles show a double or even multiple-component structure. A preliminary estimate based on the size of the Br gamma emitting region indicates a large diameter for the disk (tens of stellar radii). Overall, no serious contradiction between the observations and the disk-oscillation model could be construed.

Manganese-enhanced magnetic resonance imaging detects mossy fiber sprouting in the pilocarpine model of epilepsy

Purpose: Mossy fiber sprouting (MFS) is a frequent finding following status epilepticus (SE). The present study aimed to test the feasibility of using manganese-enhanced magnetic resonance imaging (MEMRI) to detect MFS in the chronic phase of the well-established pilocarpine (Pilo) rat model of temporal lobe epilepsy (TLE). Methods: To modulate MFS, cycloheximide (CHX), a protein synthesis inhibitor, was coadministered with Pilo in a subgroup of animals. In vivo MEMRI was performed 3 months after induction of SE and compared to the neo-Timm histologic labeling of zinc mossy fiber terminals in the dentate gyrus (DG). Key Findings: Chronically epileptic rats displaying MFS as detected by neo-Timm histology had a hyperintense MEMRI signal in the DG, whereas chronically epileptic animals that did not display MFS had minimal MEMRI signal enhancement compared to nonepileptic control animals. A strong correlation (r = 0.81, p < 0.001) was found between MEMRI signal enhancement and MFS. Significance: This study shows that MEMRI is an attractive noninvasive method for detection of mossy fiber sprouting in vivo and can be used as an evaluation tool in testing therapeutic approaches to manage chronic epilepsy.

Experimental diabetes modulates collagen remodelling of joints in rats

The aim of this study was to evaluate extracellular matrix components in articular cartilage, ligaments and synovia in an experimental model of diabetes. Young Wistar rats were divided into a streptozotocin-induced (STZ; 35 mg/kg) diabetic group (DG; n=15) and a control group (CG; n=15). Weight, blood glucose and plasma anti-carboxymethyllysine were measured 70 days after STZ infusions. Knee joints, patellar ligaments, and lateral and medial collateral ligaments were isolated and stained with hematoxylineosin and Picrosirius. The total collagen content was determined by morphometry. Immunofluorescence was employed to evaluate types I, III, and V collagen in ligaments and synovial tissues and types II and XI collagen in cartilage. Results: Higher blood glucose levels and plasma anti-carboxymethyllysine were observed in DG rats when compared to those in CG rats. The final weight was significantly lower in the DG rats than in the CG rats. Histomorphometric evaluation depicted a small quantity of collagen fibers in ligaments and articular cartilage in DG rats, as well as increased collagen in synovial tissue. There was a decrease in cartilage proteoglycans in DG rats when compared with CG rats. Immunofluorescence staining revealed an increase of collagen III and V in ligaments, collagen XI in cartilage, and collagen I in synovial tissue of DG rats compared with CG rats. Conclusion: The ligaments, cartilage and synovia are highly affected following STZ-induced diabetes in rats, due the remodeling of collagen types in these tissues. This process may promote the degradation of the extracellular matrix, thus compromising joint function. Our data may help to better understand the pathogenesis of joint involvement related to diabetes.

Maximal exercise test is a useful method for physical capacity and oxygen consumption determination in streptozotocin-diabetic rats

Abstract Background The aim of the present study was to investigate the relationship between speed during maximum exercise test (ET) and oxygen consumption (VO2) in control and STZ-diabetic rats, in order to provide a useful method to determine exercise capacity and prescription in researches involving STZ-diabetic rats. Methods Male Wistar rats were divided into two groups: control (CG, n = 10) and diabetic (DG, n = 8). The animals were submitted to ET on treadmill with simultaneous gas analysis through open respirometry system. ET and VO2 were assessed 60 days after diabetes induction (STZ, 50 mg/Kg). Results VO2 maximum was reduced in STZ-diabetic rats (72.5 ± 1 mL/Kg/min-1) compared to CG rats (81.1 ± 1 mL/Kg/min-1). There were positive correlations between ET speed and VO2 (r = 0.87 for CG and r = 0.8 for DG), as well as between ET speed and VO2 reserve (r = 0.77 for CG and r = 0.7 for DG). Positive correlations were also obtained between measured VO2 and VO2 predicted values (r = 0.81 for CG and r = 0.75 for DG) by linear regression equations to CG (VO2 = 1.54 * ET speed + 52.34) and DG (VO2 = 1.16 * ET speed + 51.99). Moreover, we observed that 60% of ET speed corresponded to 72 and 75% of VO2 reserve for CG and DG, respectively. The maximum ET speed was also correlated with VO2 maximum for both groups (CG: r = 0.7 and DG: r = 0.7). Conclusion These results suggest that: a) VO2 and VO2 reserve can be estimated using linear regression equations obtained from correlations with ET speed for each studied group; b) exercise training can be prescribed based on ET in control and diabetic-STZ rats; c) physical capacity can be determined by ET. Therefore, ET, which involves a relatively simple methodology and low cost, can be used as an indicator of cardio-respiratory capacity in future studies that investigate the physiological effect of acute or chronic exercise in control and STZ-diabetic male rats.

Global gene expression profiling of oral cavity cancers suggests molecular heterogeneity within anatomic subsites

Abstract Background Oral squamous cell carcinoma (OSCC) is a frequent neoplasm, which is usually aggressive and has unpredictable biological behavior and unfavorable prognosis. The comprehension of the molecular basis of this variability should lead to the development of targeted therapies as well as to improvements in specificity and sensitivity of diagnosis. Results Samples of primary OSCCs and their corresponding surgical margins were obtained from male patients during surgery and their gene expression profiles were screened using whole-genome microarray technology. Hierarchical clustering and Principal Components Analysis were used for data visualization and One-way Analysis of Variance was used to identify differentially expressed genes. Samples clustered mostly according to disease subsite, suggesting molecular heterogeneity within tumor stages. In order to corroborate our results, two publicly available datasets of microarray experiments were assessed. We found significant molecular differences between OSCC anatomic subsites concerning groups of genes presently or potentially important for drug development, including mRNA processing, cytoskeleton organization and biogenesis, metabolic process, cell cycle and apoptosis. Conclusion Our results corroborate literature data on molecular heterogeneity of OSCCs. Differences between disease subsites and among samples belonging to the same TNM class highlight the importance of gene expression-based classification and challenge the development of targeted therapies.

Chemical composition and enzymatic digestibility of sugarcane clones selected for varied lignin content

Abstract Background The recalcitrance of lignocellulosic materials is a major limitation for their conversion into fermentable sugars. Lignin depletion in new cultivars or transgenic plants has been identified as a way to diminish this recalcitrance. In this study, we assessed the success of a sugarcane breeding program in selecting sugarcane plants with low lignin content, and report the chemical composition and agronomic characteristics of eleven experimental hybrids and two reference samples. The enzymatic digestion of untreated and chemically delignified samples was evaluated to advance the performance of the sugarcane residue (bagasse) in cellulosic-ethanol production processes. Results The ranges for the percentages of glucan, hemicellulose, lignin, and extractive (based on oven-dry biomass) of the experimental hybrids and reference samples were 38% to 43%, 25% to 32%, 17% to 24%, and 1.6% to 7.5%, respectively. The samples with the smallest amounts of lignin did not produce the largest amounts of total polysaccharides. Instead, a variable increase in the mass of a number of components, including extractives, seemed to compensate for the reduction in lignin content. Hydroxycinnamic acids accounted for a significant part of the aromatic compounds in the samples, with p-coumaric acid predominating, whereas ferulic acid was present only in low amounts. Hydroxycinnamic acids with ester linkage to the hemicelluloses varied from 2.3% to 3.6%. The percentage of total hydroxycinnamic acids (including the fraction linked to lignin through ether linkages) varied from 5.0% to 9.2%, and correlated to some extent with the lignin content. These clones released up to 31% of glucose after 72 hours of digestion with commercial cellulases, whereas chemically delignified samples led to cellulose conversion values of more than 80%. However, plants with lower lignin content required less delignification to reach higher efficiencies of cellulose conversion during the enzymatic treatment. Conclusion Some of the experimental sugarcane hybrids did have the combined characteristics of high biomass and high sucrose production with low lignin content. Conversion of glucan to glucose by commercial cellulases was increased in the samples with low lignin content. Chemical delignification further increased the cellulose conversion to values of more than 80%. Thus, plants with lower lignin content required less delignification to reach higher efficiencies of cellulose conversion during the enzymatic treatment.

Growth and fatty acid composition of Octopus vulgaris fed different diets based on bogue (Boops boops) in comparison to wild individuals

[EN] Octopus vulgaris is a suitable candidate to diversify marine aquaculture (Iglesias et al., 2000; Vaz Pires et al. 2004). Actually, wild sub-adults are on-growing in floating cages showing promising results (Chapela et al., 2006; Rodríguez et al., 2006). Even though octopus industrial development is still limited, mainly associated to the dependence of wild catch individuals for ongrowing (Iglesias et al., 2007) and a lack of an appropriate formulated diet (García García and Cerezo, 2006). In addition, essential macronutrient requirements for this species are still not well known. Used of discarded bogue as single food for Octopus on-growth results in similar growth than co-fed diets with the crab (Portunus pelagic). FA content of Muscle and DG showed important ARA content, suggesting the important functions of this FA in this specie.

Application of chromatographic and spectroscopic techniques in the evaluation of the lipid fraction of animal products

Lipolysis and oxidation of lipids in foods are the major biochemical and chemical processes that cause food quality deterioration, leading to the characteristic, unpalatable odour and flavour called rancidity. In addition to unpalatability, rancidity may give rise to toxic levels of certain compounds like aldehydes, hydroperoxides, epoxides and cholesterol oxidation products. In this PhD study chromatographic and spectroscopic techniques were employed to determine the degree of rancidity in different animal products and its relationship with technological parameters like feeding fat sources, packaging, processing and storage conditions. To achieve this goal capillary gas chromatography (CGC) was employed not only to determine the fatty acids profile but also, after solid phase extraction, the amount of free fatty acids (FFA), diglycerides (DG), sterols (cholesterol and phytosterols) and cholesterol oxidation products (COPs). To determine hydroperoxides, primary products of oxidation and quantify secondary products UV/VIS absorbance spectroscopy was applied. Most of the foods analysed in this study were meat products. In actual fact, lipid oxidation is a major deterioration reaction in meat and meat products and results in adverse changes in the colour, flavour and texture of meat. The development of rancidity has long recognized as a serious problem during meat handling, storage and processing. On a dairy product, a vegetal cream, a study of lipid fraction and development of rancidity during storage was carried out to evaluate its shelf-life and some nutritional features life saturated/unsaturated fatty acids ratio and phytosterols content. Then, according to the interest that has been growing around functional food in the last years, a new electrophoretic method was optimized and compared with HPLC to check the quality of a beehive product like royal jelly. This manuscript reports the main results obtained in the five activities briefly summarized as follows: 1) comparison between HPLC and a new electrophoretic method in the evaluation of authenticity of royal jelly; 2) study of the lipid fraction of a vegetal cream under different storage conditions; 3) study of lipid oxidation in minced beef during storage under a modified atmosphere packaging, before and after cooking; 4) evaluation of the influence of dietary fat and processing on the lipid fraction of chicken patties; 5) study of the lipid fraction of typical Italian and Spanish pork dry sausages and cured hams.

The effects of supplementation of decapod zoea to Artemia basal diet on the digestive gland histology and the fatty acid composition in common octopus (Octopus vulgaris) paralarvae.

[EN]The present study aimed to evaluate the effect of the supplementation of different crab zoeas to enriched Artemia basal diet for O. vulgaris paralarvae during the first month of life. Paralarvae were fed using: enriched Artemia nauplii alone and Artemia co-fed with either first zoea stages of Grapsus adscensionis or Plagusia depressa. The experiment was carried out over a period of 28 days, in 0.12 m3 tanks with a flow-through rearing system. Growth in dry weightas well as mantle length and width were assessed weekly. Additionally, prey and paralarvae fatty acid composition and digestive gland (DG) histology were evaluated.

Morphological and functional study of cerebral aging in rat

Aging is a physiological process characterized by a progressive decline of the “cellular homeostatic reserve”, refereed as the capability to respond suitably to exogenous and endogenous stressful stimuli. Due to their high energetic requests and post-mitotic nature, neurons are peculiarly susceptible to this phenomenon. However, the aged brain maintains a certain level of adaptive capacities and if properly stimulated may warrant a considerable functional recovery. Aim of the present research was to verify the plastic potentialities of the aging brain of rats subjected to two kind of exogenous stimuli: A) the replacement of the standard diet with a ketogenic regimen (the change forces the brain to use ketone bodies (KB) in alternative to glucose to satisfy the energetic needs) and B) a behavioural task able to induce the formation of inhibitory avoidance memory. A) Fifteen male Wistar rats of 19 months of age were divided into three groups (average body weight pair-matched), and fed for 8 weeks with different dietary regimens: i) diet containing 10% medium chain triglycerides (MCT); ii) diet containing 20% MCT; iii) standard commercial chow. Five young (5 months of age) and five old (26-27 months of age) animals fed with the standard diet were used as further controls. The following morphological parameters reflecting synaptic plasticity were evaluated in the stratum moleculare of the hippocampal CA1 region (SM CA1), in the outer molecular layer of the hippocampal dentate gyrus (OML DG), and in the granule cell layer of the cerebellar cortex (GCL-CCx): average area (S), numeric density (Nvs), and surface density (Sv) of synapses, and average volume (V), numeric density (Nvm), and volume density (Vv) of synaptic mitochondria. Moreover, succinic dehydrogenase (SDH) activity was cytochemically determined in Purkinje cells (PC) and V, Nvm, Vv, and cytochemical precipitate area/mitochondrial area (R) of SDH-positive mitochondria were evaluated. In SM CA1, MCT-KDs induced the early appearance of the morphological patterns typical of old animals: higher S and V, and lower Nvs and Nvm. On the contrary, in OML DG, Sv and Vv of MCT-KDs-fed rats were higher (as a result of higher Nvs and Nvm) vs. controls; these modifications are known to improve synaptic function and metabolic supply. The opposite effects of MCT-KDs might reflect the different susceptibility of these brain regions to the aging processes: OML DG is less vulnerable than SM CA1, and the reactivation of ketone bodies uptake and catabolism might occur more efficiently in this region, allowing the exploitation of their peculiar metabolic properties. In GCL-CCx, the results described a new scenario in comparison to that found in the hippocampal formation: 10%MCT-KD induced the early appearance of senescent patterns (decreased Nvs and Nvm; increased V), whereas 20%MCT-KD caused no changes. Since GCL-CCx is more vulnerable to age than DG, and less than CA1, these data further support the hypothesis that MCT-KDs effects in the aging brain critically depend on neuronal vulnerability to age, besides MCT percentage. Regarding PC, it was decided to evaluate only the metabolic effect of the dietetic regimen (20%MCT-KD) characterized by less side effects. KD counteracted age-related decrease in numeric density of SDH-positive mitochondria, and enhanced their energetic efficiency (R was significantly higher in MCT-KD-fed rats vs. all the controls). Since it is well known that Purkinje and dentate gyrus cells are less vulnerable to aging than CA1 neurons, these results corroborate our previous hypothesis. In conclusion, the A) experimental line provides the first evidence that morphological and functional parameters reflecting synaptic plasticity and mitochondrial metabolic competence may be modulated by MCT-KDs in the pre-senescent central nervous system, and that the effects may be heterogeneous in different brain regions. MCT-KDs seem to supply high energy metabolic intermediates and to be beneficial (“anti-aging”) for those neurons that maintain the capability to exploit them. This implies risks but also promising potentialities for the therapeutic use of these diets during aging B) Morphological parameters of synapses and synaptic mitochondria in SM CA1 were investigated in old (26-27 month-old) female Wistar rats following a single trial inhibitory avoidance task. In this memory protocol animals learn to avoid a dark compartment in which they received a mild, inescapable foot-shock. Rats were tested 3 and 6 or 9 hours after the training, divided into good and bad responders according to their performance (retention times above or below 100 s, respectively) and immediately sacrificed. Nvs, S, Sv, Nvm, V, and Vv were evaluated. In the good responder group, the numeric density of synapses and mitochondria was significantly higher and the average mitochondrial volume was significantly smaller 9 hours vs. 6 hours after the training. No significant differences were observed among bad responders. Thus, better performances in passive avoidance memory task are correlated with more efficient plastic remodeling of synaptic contacts and mitochondria in hippocampal CA1. These findings indicate that maintenance of synaptic plastic reactivity during aging is a critical requirement for preserving long-term memory consolidation.

Valutazione del danno da stress ossidativo come indicatore di effetto biologico dell'esposizione professionale a xenobiotici

Oxidative DNA damages determine the activation of cell repair processes. These processes originate repair products, including the most studied one, 8-hydroxy-2’-deoxyguanosine (8-OH-dG). Several analytical techniques have been applied to measure urinary 8-OH-dG, but a discrepancy in basal urinary 8-OH-dG levels has been noted when comparing chromatographic techniques with immunoenzymatic assays (ELISA). Our laboratory has developed a fully validated, liquid chromatography-tandem mass spectrometry method presenting high sensitivity and specificity, which has participated in an inter-laboratory validation of assays for the measurement of urinary 8-OH-dG (ESCULA project). Mass Spectrometric techniques showed more accuracy and specificity than immunoenzymatic methods. Human spot urine samples were analyzed in order to investigate the possibility to correct urinary lesion measurements for creatinine and to evaluate the intra- and inter-day variability of 8-OH-dG excretion in urine. Our results confirm the opportunity to delve into these issues. Finally, we measured urinary 8-OH-dG in workers exposed to antineoplastic drugs and in a group of unexposed subjects to evaluate the relationship between occupational exposure and oxidative damage related to the internal dose. We found higher levels of 8-OH-dG in exposed nurses, but, as compared to the non-exposed subjects, the difference was not statistically significant, probably do to the very low level of exposure. The scientific literature is rapidly developing on the topic of DNA damage and related repair capacity. Nevertheless, further studies are needed to achieve a better understanding of the sources of DNA lesions in urine and their significance, both in clinical and occupational medicine.

Sviluppo di nuovi catalizzatori per la reazione di water gas shift a media temperatura

L’idrogeno è un elemento di elevato interesse economico, con una produzione industriale che supera i 55 x 1010 m3/anno e notevoli prospettive di sviluppo delle sue applicazioni. Attualmente l’idrogeno è prodotto principalmente in impianti di larga scala (circa 1000 m3/h) da combustibili fossili attraverso processi di steam reforming ed ossidazione parziale catalitica. Per aumentare la produzione di idrogeno un ruolo fondamentale è svolto dalla reazione di water gas shift (WGS) che abbatte il contenuto di CO, massimizzando la produzione di idrogeno. La reazione è condotta industrialmente in due stadi, operanti ad alta temperatura (HTS, circa 350 °C) e bassa temperatura (LTS, circa 250 °C), utilizzando rispettivamente catalizzatori a base di ferro o rame. Tuttavia, è evidente l’interesse per nuove formulazioni in grado di operare in un unico stadio a temperatura intermedia (MTS), mantenendo le caratteristiche ottimali di attività e stabilità. In questo lavoro di tesi, condotto in collaborazione con AIR LIQUIDE (F), è stato affrontato uno studio della reazione di WGS finalizzato allo sviluppo di nuove formulazioni attive e stabili nell’MTS. In particolare, sono stati sintetizzati precursori idrotalcitici Cu/Zn/Al (contenenti carbonati o silicati), con bassi contenuti di rame (diversamente da quanto riportato in letteratura), modulandone le proprietà chimico-fisiche, l’attività catalitica e la stabilità con il tempo di reazione. Si è osservato come i catalizzatori con minori contenuti di rame ed ottenuti da precursori contenenti carbonati mostrassero un’elevata attività e selettività nell’MTS, raggiungendo valori di conversione del CO analoghi a quelli all’equilibrio termodinamico già a 300 °C, indipendentemente dai valori del rapporto S/DG e del tempo di contatto. Tutti i catalizzatori mostrano un’elevata stabilità con il tempo di reazione, con incrementi del quantitativo del CO in uscita dopo 100h di circa lo 0,7 % v/v. I catalizzatori scaricati dopo le prove catalitiche evidenziano gli effetti dei processi di sinterizzazione (diminuzione dell’area superficiale ed incremento delle dimensioni dei cristalliti), la cui entità diminuisce al diminuire del contenuto di rame. Infine, confrontando l’attività dei migliori catalizzatori preparati in questo lavoro di tesi con quella di uno dei più utilizzati catalizzatori commerciali per la reazione di WGS a bassa temperatura, si sono osservati valori di attività analoghi, raggiungendo quelli di equilibrio per temperature  300°C, ma con una attività significativamente superiore nelle condizioni LTS, soprattutto considerando il valore del tempo di contatto inferiore a quelli comunemente utilizzati negli impianti industriali.

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.

Valutazione del comportamento ad impatto di un aliante in materiali compositi

I fattori che, nei primi anni dell'aviazione, contribuivano al verificarsi o meno di una sciagura aerea erano principalmente di natura meccanica, mentre oggi la maggior parte degli incidenti è attribuibile all’errore umano. Nel corso del tempo sono stati sviluppati modelli per l’analisi del fattore umano ed ha assunto un ruolo fondamentale lo studio del crashworthiness allo scopo di sviluppare tecnologie che contribuiscano alla riduzione di incidenti aerei e del tasso di mortalità. In questo studio è stata analizzata la resistenza della fusoliera di un aliante DG-100G Elan nelle principali tipologie di impatto. Le statistiche evidenziano, come cause principali di incidente, la caduta in vite e lo stallo in prossimità del suolo. Dall’analisi dei risultati ottenuti con la configurazione di base dell’aliante è stata delineata una possibile modifica per migliorarne la resistenza ad impatto. Obiettivo dello studio è la verifica in prima approssimazione della bontà o meno dei risultati ottenuti attraverso l’introduzione delle modifiche, valutando la differenza di quest’ultimi fra le due configurazioni.