Bat-Inspired Optimization Approach for the Brushless DC Wheel Motor Problem

This paper presents a metaheuristic algorithm inspired in evolutionary computation and swarm intelligence concepts and fundamentals of echolocation of micro bats. The aim is to optimize the mono and multiobjective optimization problems related to the brushless DC wheel motor problems, which has 5 design parameters and 6 constraints for the mono-objective problem and 2 objectives, 5 design parameters, and 5 constraints for multiobjective version. Furthermore, results are compared with other optimization approaches proposed in the recent literature, showing the feasibility of this newly introduced technique to high nonlinear problems in electromagnetics.

Determination of chlorine in food samples via the AlCl molecule using high-resolution continuum source molecular absorption spectrometry in a graphite furnace

Determination of chlorine using the molecular absorption of aluminum mono-chloride (AlCl) at the 261.418 nm wavelength was accomplished by high-resolution continuum source molecular absorption spectrometry using a transversely heated graphite tube furnace with an integrated platform. For the analysis. 10 mu L of the sample followed by 10 mu L of a solution containing Al-Ag-Sr modifier, (1 g L-1 each), were directly injected onto the platform. A spectral interference due to the use of Al-Ag-Sr as mixed modifier was easily corrected by the least-squares algorithm present in the spectrometer software. The pyrolysis and vaporization temperatures were 500 degrees C and 2200 degrees C, respectively. To evaluate the feasibility of a simple procedure for the determination of chlorine in food samples present in our daily lives, two different digestion methods were applied, namely (A) an acid digestion method using HNO3 only at room temperature, and (B) a digestion method with Ag, HNO3 and H2O2, where chlorine is precipitated as a low-solubility salt (AgCl), which is then dissolved with ammonia solution. The experimental results obtained with method B were in good agreement with the certified values and demonstrated that the proposed method is more accurate than method A. This is because the formation of silver chloride prevented analyte losses by volatilization. The limit of detection (LOD, 3 sigma/s) for Cl in methods A and B was 18 mu g g(-1) and 9 mu g g(-1), respectively, 1.7 and 3.3 times lower compared to published work using inductively coupled plasma optical emission spectrometry, and absolute LODs were 2.4 and 1.2 ng, respectively. (C) 2012 Elsevier B.V. All rights reserved.

Dieta e aspectos nutricionais no lúpus eritematoso sistêmico

Os autores revisaram a influência dos fatores nutricionais sobre o lúpus eritematoso sistêmico (LES) e abordaram uma alternativa complementar em seu tratamento. A autoimunidade e o processo inflamatório do LES estão relacionados à presença de dislipidemias, obesidade, hipertensão arterial sistêmica e síndrome metabólica, que devem ser adequadamente consideradas para diminuir o risco cardiovascular. Uma alimentação com moderado teor energético e proteico, mas rica em vitaminas, minerais (principalmente os antioxidantes) e ácidos graxos mono/poli-insaturados, pode promover ação benéfica protetora contra danos tissulares e supressão da atividade inflamatória, além de auxiliar no tratamento dessas comorbidades. A dietoterapia é uma abordagem promissora, e algumas recomendações podem oferecer melhor qualidade de vida aos pacientes com LES.

PVC orientado-avaliação de processo de orientação e das propriedades mecânicas em função da razão de estiramento

Este artigo avalia o efeito da "orientação molecular" nas propriedades mecânicas do PVC Rígido. Introduz-se o tema associando-o à aplicação do PVC Orientado em sistemas de tubulações, considerando a importância do nível de gelificação na qualidade desses produtos. É descrito e testado um método experimental de orientação mono-axial em um extrudado e materiais com diferentes razões de estiramento são produzidos para avaliação de propriedades mecânicas. Aumentando a razão de estiramento, há ganhos principalmente no limite de resistência à tração, além do módulo elástico sob tração e tenacidade. Por outro lado, a deformação na ruptura é reduzida.

Reaction intermediates of ethanol electro-oxidation on platinum investigated by SFG spectroscopy

Although electrochemical oxidation of simple organic molecules on metal catalysts is the basic ingredient of fuel cells, which have great technological potential as a renewable source of electrical energy, the detailed reaction mechanisms are in most cases not completely understood. Here, we investigate the ethanol-platinum interface in acidic aqueous solution using infrared-visible sum frequency generation (SFG) spectroscopy and theoretical calculations of vibrational spectra in order to identify the intermediates present during the electro-oxidation of ethanol. The complex vibrational spectrum in the fingerprint region imply on the coexistence of several adsorbates. Based on spectra in ultra-high-vacuum (UHV) and electrochemical environment from the literature and our density functional theory (DFT) calculations of vibrational spectra, new adsorbed intermediates, never before observed with conventional infrared (IR) spectroscopy, are proposed here: g2-acetaldehyde, g2-acetyl, ethylidyne, monodentate acetate, methoxy, tertiary methanol derivative, COH residue, g2-formaldehyde, mono and bidentate formate, CH3 and CH2 residues. In addition, we present new evidences for an ethoxy intermediate, a secondary ethanol derivative and an acetyl species, and we confirm the presence of previously observed adsorbates: a tertiary ethanol derivative, bidentate acetate, and COad. These results indicate that the platinum surface is much more reactive, and the reaction mechanism for ethanol electro-oxidation is considerably more complex than previously considered. This might be also true for many other molecule-catalyst systems.

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.

Metabolismo di oligosaccaridi prebiotici in Bifidobacterium per il potenziale sviluppo di nuovi prodotti alimentari funzionali

The growth and the metabolism of Bifidobacterium adolescentis MB 239 fermenting GOS, lactose, galactose, and glucose were investigated. An unstructerd unsegregated model for growth of B. adolescentis MB 239 in batch cultures was developed and kinetic parameters were calculated with a Matlab algorithm. Galactose was the best carbon source; lactose and GOS led to lower growth rate and cellular yield, but glucose was the poorest carbon source. Lactate, acetate and ethanol yields allowed calculation of the carbon fluxes toward fermentation products. Similar distribution between 3- and 2-carbon products was observed on all the carbohydrates (45 and 55%, respectively), but ethanol production was higher on glucose than on GOS, lactose and galactose, in decreasing order. Based on the stoichiometry of the fructose 6-phosphate shunt and on the carbon distribution among the products, ATP yield was calculated on the different carbohydrates. ATP yield was the highest on galactose, while it was 5, 8, and 25% lower on lactose, GOS, and glucose, respectively. Therefore, a correspondance among ethanol production, low ATP yields, and low biomass production was established demonstrating that carbohydrate preferences may result from different sorting of carbon fluxes through the fermentative pathway. During GOS fermentation, stringent selectivity based on the degree of polymerization was exhibited, since lactose and the trisaccharide were first to be consumed, and a delay was observed until longer oligosaccharides were utilized. Throughout the growth on both lactose and GOS, galactose accumulated in the cultural broth, suggesting that β-(1-4) galactosides can be hydrolysed before they are taken up. The physiology of Bifidobacterium adolescentis MB 239 toward xylooligosaccharides (XOS) was also studied and our attention was focused on an extracellular glycosyl-hydrolase (β-Xylosidase) expressed by a culture of B. adolescentis grown on XOS as sole carbon source. The extracellular enzyme was purified from the the supernatant, which was dialyzed and concentrated by ultrafiltration. A two steps purification protocol was developed: the sample was loaded on a Mono-Q anion exchange chromatography and then, the active fractions were pooled and β-Xylosidase was purified by gel filtration chromatography on a Superdex-75. The enzyme was characterized in many aspects. β- Xylosidase was an homo-tetramer of 160 kDa as native molecular mass; it was a termostable enzyme with an optimum of temperature at 53 °C and an optimum of pH of 6.0. The kinetics parameter were calculated: km = 4.36 mM, Vmax = 0.93 mM/min. The substrate specificity with different di-, oligo- and polysaccharides was tested. The reactions were carried out overnight at pH 7 and at the optimum of temperature and the carbohydrates hydrolysis were analyzed by thin layer chromatography (TLC). Only glycosyl-hydrolase activities on XOS and on xylan were detected, whereas sucrose, lactose, cellobiose, maltose and raffinose were not hydrolyzed. It’s clearly shown that β-Xylosidase activity was higher than the Xylanase one. These studies on the carbohydrate preference of a strain of Bifidobacterium underlined the importance of the affinity between probiotics and prebiotics. On the basis of this concept, together with Barilla G&R f.lli SpA, we studied the possibility to develop a functional food containing a synbiotic. Three probiotic strains Lactobacillus plantarum BAR 10, Streptococcus thermophilus BAR 20, and Bifidobacterium lactis BAR 30 were studied to assess their suitability for utilization in synbiotic products on the basis of antioxidative activity, glutathione production, acid and bile tolerance, carbohydrates fermentation and viability in food matrices. Bile and human gastric juice resistance was tested in vitro to estimate the transit tolerance in the upper gastrointestinal tract. B. lactis and L. plantarum were more acid tolerant than S. thermophilus. All the strains resisted to bile. The growth kinetics on 13 prebiotic carbohydrates were determined. Galactooligosaccharides and fructo-oligosaccharides were successfully utilized by all the strains and could be considered the most appropriate prebiotics to be used in effective synbiotic formulations. The vitality of the three strains inoculated in different food matrices and maintained at room temperature was studied. The best survival of Lactobacillus plantarum BAR 10, Streptococcus thermophilus BAR 20, and Bifidobacterium lactis BAR 30 was found in food chocolate matrices. Then an in vivo clinical trial was carried out for 20 healthy volunteers. The increase in faecal bifidobacteria and lactobacilli populations and the efficacy of the pre-prototype was promising for the future develop of potential commercial products.

Análisis, diseño y desarrollo de un videojuego en 2D con perspectiva top-down

[ES]En este proyecto la alumna ha desarrollado la demo jugable de un videojuego en 2D con perspectiva top-down. El juego transcurre en un zoológico, con un mono como protagonista, y el objetivo del mismo es lograr escapar al tiempo que se evita a los empleados del zoo. Para conseguir huir, el jugador tendrá que obtener algunos objetos y liberar a otros animales. En la propia demo se pueden consultar los controles y las distintas opciones disponibles. Para la creación del juego se ha utilizado el motor de juegos Unity 5 (edición personal) y recursos obtenidos de diversas fuentes de contenido gratuito.

Effetti del chitosano su composti polifenolici in colture cellulari di vite: aspetti molecolari e metabolici

Polyphenols, including flavonoids and stilbenes, are an essential part of human diet and constitute one of the most abundant and ubiquitous group of plant secondary metabolites. The level of these compounds is inducible by stress or fungal attack, so attempts are being made to identify likely biotic and abiotic elicitors and to better understand the underlying mechanism. Resveratrol (3,5,4’-trihydroxystilbene), which belongs to the stilbene family, is a naturally occurring polyphenol, found in several fruits, vegetables and beverages including red wine. It is one of the most important plant polyphenols with proved benefic activity on animal health. In the last two decades, the potential protective effects of resveratrol against cardiovascular and neurodegenerative diseases, as well as the chemopreventive properties against cancer, have been largely investigated. The most important source of polyphenols and in particular resveratrol for human diet is grape (Vitis vinifera). Since stilbenes and flavonoids play a very important role in plant defence responses and enviromental interactions, and their effects on human health seem promising, the aim of the research of this Thesis was to study at different levels the activation and the regulation of their biosynthetic pathways after chitosan treatment. Moreover, the polyphenol production in grape cells and the optimisation of cultural conditions bioreactor scale-up, were also investigated. Cell suspensions were obtained from cv. Barbera (Vitis vinifera L.) petioles and were treated with a biotic elicitor, chitosan (50 μg/mL, dissolved in acetic acid) to promote phenylpropanoid metabolism. Chitosan is a D-glucosamine polymer from fungi cell wall and therefore mimes fungal pathogen attack. Liquid cultures have been monitored for 15 days, measuring cell number, cell viability, pH and grams of fresh weight. The endogenous and released amounts of 7 stilbenes (trans and cis isomers of resveratrol, piceid and resveratroloside, and piceatannol), gallic acid, 6 hydroxycinnamic acids (trans-cinnamic, p-coumaric, caffeic, ferulic, sinapic and chlorogenic acids), 5 catechines (catechin, epicatechin, epigallocatechin-gallate (EGCG), epigallocatechin and epicatechin-gallate) and other 5 flavonoids (chalcon, naringenin, kaempferol, quercetin and rutin) in cells and cultural medium, were measured by HPLC-DAD analysis and total anthocyanins were quantified by spectrophotometric analysis. Chitosan was effective in stimulating trans-resveratrol endogenous accumulation with a sharp peak at day 4 (exceeding acetic acid and water controls by 36% and 63%, respectively), while it did not influence the production of the cis-isomer. Compared to both water and acetic acid controls, chitosan decreased the release of both trans- and cis-resveratrol respect to controls. No effect was shown on the accumulation of single resveratrol mono-glucoside isomers, but considering their total amount, normalized for the relative water control, it was possible to evidence an increase in both accumulation and release of those compounds, in chitosan-treated cells, throughout the culture period and particularly during the second week. Many of the analysed flavonoids and hydroxycinnamic acids were not present or detectable in trace amounts. Catechin, epicatechin and epigallocatechin-gallate (EGCG) were detectable both inside the cells and in the culture media, but chitosan did not affect their amounts. On the contrary, total anthocyanins have been stimulated by chitosan and their level, from day 4 to 14, was about 2-fold higher than in both controls, confirming macroscopic observations that treated suspensions showed an intense brown-red color, from day 3 onwards. These elicitation results suggest that chitosan selectively up-regulates specific biosynthetic pathways, without modifying the general accumulation pattern of other flavonoids. Proteins have been extracted from cells at day 4 of culture (corresponding to the production peak of trans-resveratrol) and separated by bidimensional electrophoresis. The 73 proteins that showed a consistently changed amount between untreated, chitosan and acetic acid (chitosan solvent) treated cells, have been identified by mass spectrometry. Chitosan induced an increase in stilbene synthase (STS, the resveratrol biosynthetic enzyme), chalcone-flavanone isomerase (CHI, that switches the pathway from chalcones to flavones and anthocyanins), pathogenesis-related proteins 10 (PRs10, a large family of defence proteins), and a decrease in many proteins belonging to primary metabolisms. A train of six distinct spots of STS encoded by the same gene and increased by chitosan, was detected on the 2-D gels, and related to the different phosphorylation degree of STS spots. Northern blot analyses have been performed on RNA extracted from cells treated with chitosan and relative controls, using probes for STS, PAL (phenylalanine ammonia lyase, the first enzyme of the biosynthetic pathway), CHS (chalcone synthase, that shares with STS the same precursors), CHI and PR-10. The up-regulation of PAL, CHS and CHI transcript expression levels correlated with the accumulation of anthocyanins. The strong increase of different molecular weight PR-10 mRNAs, correlated with the 11 PR-10 protein spots identified in proteomic analyses. The sudden decrease in trans-resveratrol endogenous accumulation after day 4 of culture, could be simply explained by the diminished resveratrol biosynthetic activity due to the lower amount of biosynthetic enzymes. This might be indirectly demonstrated by northern blot expression analyses, that showed lower levels of phenylalanine ammonia lyase (PAL) and stilbene synthase (STS) mRNAs starting from day 4. Other possible explanations could be a resveratrol oxidation process and/or the formation of other different mono-, di-glucosides and resveratrol oligomers such as viniferins. Immunolocalisation experiments performed on grape protoplasts and the subsequent analyses by confocal microscope, showed that STS, and therefore the resveratrol synthetic site, is mostly associated to intracellular membranes close to the cytosolic side of plasma membrane and in a smaller amount is localized in the cytosol. STS seemed not to be present inside vacuole and nucleus. There were no differences in the STS intracellular localisation between the different treatments. Since it was shown that stilbenes are largely released in the culture medium and that STS is a soluble protein, a possible interaction of STS with a plasma membrane transporter responsible for the extrusion of stilbenes in the culture medium, might be hypothesized. Proteomic analyses performed on subcellular fractions identified in the microsomial fraction 5 proteins taking part in channel complexes or associated with channels, that significantly changed their amount after chitosan treatment. In soluble and membrane fractions respectively 3 and 4 STS and 6 and 3 PR-10 have been identified. Proteomic results obtained from subcellular fractions substantially confirmed previous result obtained from total cell protein extracts and added more information about protein localisation and co-localisation. The interesting results obtained on Barbera cell cultures with the aim to increase polyphenol (especially stilbenes) production, have encouraged scale up tests in 1 litre bioreactors. The first trial fermentation was performed in parallel with a normal time-course in 20 mL flasks, showing that the scale-up (bigger volume and different conditions) process influenced in a very relevant way stilbenes production. In order to optimise culture parameters such as medium sucrose amount, fermentation length and inoculum cell concentration, few other fermentations were performed. Chitosan treatments were also performed. The modification of each parameter brought relevant variations in stilbenes and catechins levels, so that the production of a certain compound (or class of compounds) could be hypothetically promoted by modulating one or more culture parameters. For example the catechin yield could be improved by increasing sucrose content and the time of fermentation. The best results in stilbene yield were obtained in a 800 mL fermentation inoculated with 10.8 grams of cells and supplemented with chitosan. The culture was fed with MS medium added with 30 g/L sucrose, 25 μg/mL rifampicin and 50 μg/mL of chitosan, and was maintained at 24°C, stirred by marine impeller at 100 rpm and supplied of air at 0.16 L/min rate. Resveratroloside was the stilbene present in the larger amount, 3-5 times more than resveratrol. Because resveratrol glucosides are similarly active and more stable than free resveratrol, their production using a bioreactor could be a great advantage in an hypothetical industrial process. In my bioreactor tests, stilbenes were mainly released in the culture medium (60-80% of the total) and this fact could be another advantage for industrial applications, because it allows recovering the products directly from the culture medium without stopping the fermentation and/or killing the cells. In my best cultural conditions, it was possible to obtain 3.95 mg/L of stilbenes at day 4 (maximum resveratrol accumulation) and 5.13 mg/L at day 14 (maximum resveratroloside production). In conclusion, chitosan effect in inducing Vitis vinifera defense mechanisms can be related to its ability to increase the intracellular content of a large spectrum of antioxidants, and in particular of resveratrol, its derivates and anthocyanins. Its effect can be observed at transcriptional, proteomic (variation of soluble and membrane protein amounts) and metabolic (polyphenols production) level. The chitosan ability to elicit specific plant matabolisms can be useful to produce large quantities of antioxidant compounds from cell culture in bioreactor.

Studio di una copertura di grande luce a forma libera

L' argomento di questa tesi tratta l'analisi di una copertura reticolare a forma libera di grande luce. Partendo da una modellazione FEM della reticolare risolta al calcolatore si è cercato un metodo di analisi semplificato alternativo per l'individuazione approssimata delle sollecitazioni che nascono in seguito ai carichi. Ripercorrendo i passi sviluppati dal metodo americano per il calcolo dei solai a fungo, si individuano le sezioni portanti principali della forma strutturale, deducendo l'andamento del momento flettente dagli sforzi in corrispondenza dei correnti tesi e compressi. Sulle stesse sezioni sono stati costruiti dei modelli mono e bidimensionali semplificati che cercano di rappresentare, con diversa scala di precisione, l'andamento della sollecitazione flettente realmente presente nella struttura. Dall'analisi del momento flettente risultante dai modelli monodimensionali si individuano le modifiche effettuabili sulla geometria strutturale con lo scopo di migliorarne la risposta globale ed i parametri di progetto utili per il dimensionamento. Al termine si sono confrontati i risultati ottenuti dalle due strutture analizzate, ovvero con o senza le modifiche alla geometria, riportando alcuni parametri caratteristici del comportamento strutturale e traendo così conclusioni sulla soluzione migliore.

Risposta sismica torsionale di edifici multipiano irregolari in pianta

Le strutture caratterizzate da una non coincidenza tra il baricentro delle masse e quello delle rigidezze, chiamate strutture eccentriche, sviluppano degli effetti torsionali se soggette ad un’eccitazione dinamica. Un’accurata analisi delle equazioni del moto di sistemi lineari e non lineari di strutture ad un singolo piano ha portato allo sviluppo di un metodo, detto metodo ALPHA, che, attraverso un parametro, detto parametro “alpha”, permette di stimare gli spostamenti di rotazione in funzione dei soli spostamenti longitudinali. Il limite di questo metodo, tuttavia, è quello di essere riferito a strutture ad un singolo piano, non comuni nella pratica progettuale: si è reso quindi necessario uno studio per testarne la validità anche per strutture multi piano, partendo da strutture semplici a due e tre piani. Data la semplicità del metodo ALPHA, si è deciso di affrontare questo problema cercando di cogliere il comportamento dei diversi piani della struttura multipiano con delle strutture ad un singolo piano. Sono state svolte numerose analisi numeriche in cui sono stati fatti variare i parametri di rigidezza, massa, eccentricità e distribuzione delle rigidezze dei vari piani; come indice di validità della struttura mono piano scelta si è utilizzato il rapporto tra il parametro “psi” dell’i-esimo piano e quello della struttura mono piano scelta, dove “psi” rappresenta il rapporto tra “R” ed “alpha”; “R” è il rapporto tra la massima rotazione e il massimo spostamento longitudinale per una struttura eccentrica soggetta ad un’eccitazione dinamica. Dai risultati ottenuti si deduce che, nella maggioranza dei casi, la struttura mono piano che meglio rappresenta il comportamento di tutti i piani è caratterizzata da massa e rigidezza dell’intera struttura multipiano, da un’eccentricità pari alla minore tra quelle dei vari piani e presenta la peggiore distribuzione delle rigidezze tra quelle che si riscontrano nei vari piani.

Low-dimensional carbon allotropes: an electron microscopy investigation

The research reported in this manuscript concerns the structural characterization of graphene membranes and single-walled carbon nanotubes (SWCNTs). The experimental investigation was performed using a wide range of transmission electron microscopy (TEM) techniques, from conventional imaging and diffraction, to advanced interferometric methods, like electron holography and Geometric Phase Analysis (GPA), using a low-voltage optical set-up, to reduce radiation damage in the samples. Electron holography was used to successfully measure the mean electrostatic potential of an isolated SWCNT and that of a mono-atomically thin graphene crystal. The high accuracy achieved in the phase determination, made it possible to measure, for the first time, the valence-charge redistribution induced by the lattice curvature in an individual SWCNT. A novel methodology for the 3D reconstruction of the waviness of a 2D crystal membrane has been developed. Unlike other available TEM reconstruction techniques, like tomography, this new one requires processing of just a single HREM micrograph. The modulations of the inter-planar distances in the HREM image are measured using Geometric Phase Analysis, and used to recover the waviness of the crystal. The method was applied to the case of a folded FGC, and a height variation of 0.8 nm of the surface was successfully determined with nanometric lateral resolution. The adhesion of SWCNTs to the surface of graphene was studied, mixing shortened SWCNTs of different chiralities and FGC membranes. The spontaneous atomic match of the two lattices was directly imaged using HREM, and we found that graphene membranes act as tangential nano-sieves, preferentially grafting achiral tubes to their surface.

Gondor e Zarado: valutazione degli effetti di nuovi coadiuvanti antideriva sull'attività degli erbicidi

L’irrigidimento del contesto regolamentare europeo dovuto all’attuale condizione di contaminazione diffusa dell’ambiente, riscontrata in Italia e in molti altri paesi europei, ha visto l’esigenza sempre più pressante di razionalizzare le dosi dei fitofarmaci utilizzati in agricoltura. Lo sviluppo e l’utilizzo di nuovi prodotti coadiuvanti come specifici antideriva per erbicidi, rappresenta in questo senso, un’importante risorsa su cui si inizia a fare affidamento. In Francia, per esempio, già da alcuni anni ci sono normative che obbligano l’utilizzo in agricoltura di tali prodotti, mentre in Italia non si hanno ancora direttive precise a riguardo. In tal contesto l’obiettivo principale di questa ricerca, effettuata in collaborazione con la ditta Intrachem, è stato quello di studiare alcune caratteristiche funzionali relative a due prodotti, che verranno lanciati a breve sul mercato, come specifici antideriva per erbicidi. In particolar modo è stato fatto uno studio per verificare se ed eventualmente come, questi coadiuvanti (Gondor e Zarado) possono influenzare l’attività del principio attivo a cui vengono aggiunti, apportando variazioni relative alla sua efficacia. Lo schema di lavoro seguito ha previsto una prima fase di saggio dove venivano effettuati test dose-risposta, utilizzando diversi erbicidi a diverse concentrazioni. I test sono stati effettuati su alcune malerbe mono e dicotiledoni. In ciascuna di queste prove è stata valutata e confrontata la percentuale di sopravvivenza e il peso dei sopravvissuti tra le tesi trattate. Le tesi prevedevano trattamenti con erbicida e trattamenti con erbicida più uno dei due coadiuvanti. Nella seconda fase si è effettuato un approfondimento sulle tesi che hanno mostrato i risultati più interessanti, per capirne possibilmente le basi fisiologiche. In particolare si è verificato se l’aggiunta dei due antideriva potesse determinare cambiamenti durante la fase di assorbimento e di traslocazione del principio attivo all’interno della piantina, utilizzando molecole radiomarcate con C14. Dai risultati ottenuti si è potuto evidenziare come l’aggiunta dei coadiuvanti possa rendere più efficace l’azione dell’erbicida nei casi in cui le infestanti non vengono completamente controllate dagli stessi (stadio vegetativo troppo avanzato e resistenza all’erbicida). Non è stato sempre verificato che ad un miglioramento dell’efficacia coincida un aumento dell’assorbimento e della traslocazione del principio attivo, all’interno della pianta. In conclusione si è potuto constatare che Gondor e Zarado oltre a svolgere la loro funzione antideriva, non influenzano negativamente l’efficacia dell’erbicida, salvo poche eccezioni, ma al contrario possono potenziarne l’azione, nelle situazioni “border line”.

Geladene Kugeln, Oberflächen, elektrische Felder

Die vorliegende Arbeit widmet sich dem Einsatz geladener kolloidaler Partikel zur Präparation verschiedenartig geordneter Mono- und Multischichten. Dieses globale Ziel wird auf zwei, einander ergänzenden Wegen angesteuert. Einerseits werden neue Ansätze zur Charakterisierung kolloidaler Partikel mit elektrokinetischen Methoden verfolgt, andererseits werden die so untersuchten Partikel als Modellsysteme in Versuchen zur reproduzierbaren Präparation von Schichtsystemen eingesetzt, was in bisherigen Arbeiten, die sich praktisch ausschließlich mit den Volumeneigenschaften von suspendierten Partikeln beschäftigten, noch nicht untersucht wurde. Das aufgebaute Rasterkraftmikroskop und die teilweise neu entwickelten Präparationstechniken zur Erzeugung kolloidaler Adsorbate, ermöglichen systematische Untersuchungen auf Nanometerskala. Neben der Leistungsfähigkeit des Rasterkraftmikroskops im Bereich der kolloidalen Suspensionen, werden neue Präparationstechniken vorgestellt, mit denen die Erzeugung von langreichweitig geordneter Monolagen möglich ist. Auch die Erzeugung von geordneten Multilagen, sowie Untersuchungen von zweidimensionalen amorphen Schichten stehen im Fokus dieser Arbeit. Es werden insgesamt vier prinzipiell verschiedene Präparationstechniken angewendet. Besonderes Augenmerk wurde dabei auf die an der Trocknung beteiligten Kräfte und die Dynamik des Trocknungsprozesses gelegt.Die Arbeit stellt eine Basis für in der Kolloidphysik mögliche Untersuchung zusammen und bewertet die prinzipielle Machbarkeit und Analysemethoden der erzielbaren Topologien. Schwerpunkt wurde dabei auf die Herstellung von Monolagen in beschränkten Geometrien gelegt.

Progettazione e sintesi di nuovi derivati azetidinonici biologicamente attivi

In this PhD-thesis new synthetic approaches towards new azetidinone derivatives are described. In particular, 4-alkyliden-β-lactams were used as starting materials for the preparation of new biologically active compounds. The carbapenem Thienamycin has got a broad spectrum of activity as antibiotic. It has got 3 stereocenters and apart of one epimer, all isomers have been synthesized. Using the 4-alkyliden-β-lactam benzilyc ester as precursor, we developed a synthesis for this missing epimer, which is described in chapter II. Biological tests in order to establish its biological activity are under way. The Hunsdiecker-Borodine reaction was extensively studied for the preparation of the mono halogenated and – surprisingly – the dihalogenated derivative from the 4-alkyliden-azetidinone carboxylic acid. The herein described synthetic procedures allowed the preparation of chloro-, bromo- and iodo derivatives in good to excellent yield. Furthermore, the reaction mechanism was investigated by NMR-experiments and is described in detail in chapter III. In chapter IV, synthetic approaches towards new β-lactam derivatives for inhibition of the histone deacetylase enzymes (HDACs) are reported. In collaboration with the company Sigma-Tau (Rome), 14 new β-lactams were synthesized. The new β-lactams were evaluated for the activity showing a promising activityparticulary, 10 of the β-lactams synthesized were evaluated for the in vitro inhibitory activity against the 11 human HDACs isoforms and they showed a selective inhibition of HDAC6 or HDAC8 in micromolar range. Finally, preliminary studies were conducted for the employment of 4-alkyliden-β-lactams as precursors for the synthesis of chiral β-amino acids by an opening of the β-lactam ring. In chapter V is described the ring opening reaction catalyzed by the enzyme lipase Cal-B. Preliminary results have shown that the enzyme not only catalyzes the ring opening of the β-lactam precursor, moreover, it leads to the formation of a cyclic dimer by the reaction of two molecules of β-amino acid obtained.