Studies of pure rotational spectra of isolated molecules and molecular adducts using pulsed jet Fourier transform microwave (PJ-FTM) spectroscopy

This thesis focuses on studying molecular structure and internal dynamics by using pulsed jet Fourier transform microwave (PJ-FTMW) spectroscopy combined with theoretical calculations. Several kinds of interesting chemical problems are investigated by analyzing the MW spectra of the corresponding molecular systems. First, the general aspects of rotational spectroscopy are summarized, and then the basic theory on molecular rotation and experimental method are described briefly. ab initio and density function theory (DFT) calculations that used in this thesis to assist the assignment of rotational spectrum are also included. From chapter 3 to chapter 8, several molecular systems concerning different kind of general chemical problems are presented. In chapter 3, the conformation and internal motions of dimethyl sulfate are reported. The internal rotations of the two methyl groups split each rotational transition into several components line, allowing for the determination of accurate values of the V3 barrier height to internal rotation and of the orientation of the methyl groups with respect to the principal axis system. In chapter 4 and 5, the results concerning two kinds of carboxylic acid bi-molecules, formed via two strong hydrogen bonds, are presented. This kind of adduct is interesting also because a double proton transfer can easily take place, connecting either two equivalent or two non-equivalent molecular conformations. Chapter 6 concerns a medium strong hydrogen bonded molecular complex of alcohol with ether. The dimer of ethanol-dimethylether was chosen as the model system for this purpose. Chapter 7 focuses on weak halogen…H hydrogen bond interaction. The nature of O-H…F and C-H…Cl interaction has been discussed through analyzing the rotational spectra of CH3CHClF/H2O. In chapter 8, two molecular complexes concerning the halogen bond interaction are presented.

La filosofia di Hans-Georg Gadamer e il problema del disagio della modernità. Ermeneutica, estetica, etica e politica

L’ermeneutica filosofica di Hans-Georg Gadamer – indubbiamente uno dei capisaldi del pensiero novecentesco – rappresenta una filosofia molto composita, sfaccettata e articolata, per così dire formata da una molteplicità di dimensioni diverse che si intrecciano l’una con l’altra. Ciò risulta evidente già da un semplice sguardo alla composizione interna della sua opera principale, Wahrheit und Methode (1960), nella quale si presenta una teoria del comprendere che prende in esame tre differenti dimensioni dell’esperienza umana – arte, storia e linguaggio – ovviamente concepite come fondamentalmente correlate tra loro. Ma questo quadro d’insieme si complica notevolmente non appena si prendano in esame perlomeno alcuni dei numerosi contributi che Gadamer ha scritto e pubblicato prima e dopo il suo opus magnum: contributi che testimoniano l’importante presenza nel suo pensiero di altre tematiche. Di tale complessità, però, non sempre gli interpreti di Gadamer hanno tenuto pienamente conto, visto che una gran parte dei contributi esegetici sul suo pensiero risultano essenzialmente incentrati sul capolavoro del 1960 (ed in particolare sui problemi della legittimazione delle Geisteswissenschaften), dedicando invece minore attenzione agli altri percorsi che egli ha seguito e, in particolare, alla dimensione propriamente etica e politica della sua filosofia ermeneutica. Inoltre, mi sembra che non sempre si sia prestata la giusta attenzione alla fondamentale unitarietà – da non confondere con una presunta “sistematicità”, da Gadamer esplicitamente respinta – che a dispetto dell’indubbia molteplicità ed eterogeneità del pensiero gadameriano comunque vige al suo interno. La mia tesi, dunque, è che estetica e scienze umane, filosofia del linguaggio e filosofia morale, dialogo con i Greci e confronto critico col pensiero moderno, considerazioni su problematiche antropologiche e riflessioni sulla nostra attualità sociopolitica e tecnoscientifica, rappresentino le diverse dimensioni di un solo pensiero, le quali in qualche modo vengono a convergere verso un unico centro. Un centro “unificante” che, a mio avviso, va individuato in quello che potremmo chiamare il disagio della modernità. In altre parole, mi sembra cioè che tutta la riflessione filosofica di Gadamer, in fondo, scaturisca dalla presa d’atto di una situazione di crisi o disagio nella quale si troverebbero oggi il nostro mondo e la nostra civiltà. Una crisi che, data la sua profondità e complessità, si è per così dire “ramificata” in molteplici direzioni, andando ad investire svariati ambiti dell’esistenza umana. Ambiti che pertanto vengono analizzati e indagati da Gadamer con occhio critico, cercando di far emergere i principali nodi problematici e, alla luce di ciò, di avanzare proposte alternative, rimedi, “correttivi” e possibili soluzioni. A partire da una tale comprensione di fondo, la mia ricerca si articola allora in tre grandi sezioni dedicate rispettivamente alla pars destruens dell’ermeneutica gadameriana (prima e seconda sezione) ed alla sua pars costruens (terza sezione). Nella prima sezione – intitolata Una fenomenologia della modernità: i molteplici sintomi della crisi – dopo aver evidenziato come buona parte della filosofia del Novecento sia stata dominata dall’idea di una crisi in cui verserebbe attualmente la civiltà occidentale, e come anche l’ermeneutica di Gadamer possa essere fatta rientrare in questo discorso filosofico di fondo, cerco di illustrare uno per volta quelli che, agli occhi del filosofo di Verità e metodo, rappresentano i principali sintomi della crisi attuale. Tali sintomi includono: le patologie socioeconomiche del nostro mondo “amministrato” e burocratizzato; l’indiscriminata espansione planetaria dello stile di vita occidentale a danno di altre culture; la crisi dei valori e delle certezze, con la concomitante diffusione di relativismo, scetticismo e nichilismo; la crescente incapacità a relazionarsi in maniera adeguata e significativa all’arte, alla poesia e alla cultura, sempre più degradate a mero entertainment; infine, le problematiche legate alla diffusione di armi di distruzione di massa, alla concreta possibilità di una catastrofe ecologica ed alle inquietanti prospettive dischiuse da alcune recenti scoperte scientifiche (soprattutto nell’ambito della genetica). Una volta delineato il profilo generale che Gadamer fornisce della nostra epoca, nella seconda sezione – intitolata Una diagnosi del disagio della modernità: il dilagare della razionalità strumentale tecnico-scientifica – cerco di mostrare come alla base di tutti questi fenomeni egli scorga fondamentalmente un’unica radice, coincidente peraltro a suo giudizio con l’origine stessa della modernità. Ossia, la nascita della scienza moderna ed il suo intrinseco legame con la tecnica e con una specifica forma di razionalità che Gadamer – facendo evidentemente riferimento a categorie interpretative elaborate da Max Weber, Martin Heidegger e dalla Scuola di Francoforte – definisce anche «razionalità strumentale» o «pensiero calcolante». A partire da una tale visione di fondo, cerco quindi di fornire un’analisi della concezione gadameriana della tecnoscienza, evidenziando al contempo alcuni aspetti, e cioè: primo, come l’ermeneutica filosofica di Gadamer non vada interpretata come una filosofia unilateralmente antiscientifica, bensì piuttosto come una filosofia antiscientista (il che naturalmente è qualcosa di ben diverso); secondo, come la sua ricostruzione della crisi della modernità non sfoci mai in una critica “totalizzante” della ragione, né in una filosofia della storia pessimistico-negativa incentrata sull’idea di un corso ineluttabile degli eventi guidato da una razionalità “irrazionale” e contaminata dalla brama di potere e di dominio; terzo, infine, come la filosofia di Gadamer – a dispetto delle inveterate interpretazioni che sono solite scorgervi un pensiero tradizionalista, autoritario e radicalmente anti-illuminista – non intenda affatto respingere l’illuminismo scientifico moderno tout court, né rinnegarne le più importanti conquiste, ma più semplicemente “correggerne” alcune tendenze e recuperare una nozione più ampia e comprensiva di ragione, in grado di render conto anche di quegli aspetti dell’esperienza umana che, agli occhi di una razionalità “limitata” come quella scientista, non possono che apparire come meri residui di irrazionalità. Dopo aver così esaminato nelle prime due sezioni quella che possiamo definire la pars destruens della filosofia di Gadamer, nella terza ed ultima sezione – intitolata Una terapia per la crisi della modernità: la riscoperta dell’esperienza e del sapere pratico – passo quindi ad esaminare la sua pars costruens, consistente a mio giudizio in un recupero critico di quello che egli chiama «un altro tipo di sapere». Ossia, in un tentativo di riabilitazione di tutte quelle forme pre- ed extra-scientifiche di sapere e di esperienza che Gadamer considera costitutive della «dimensione ermeneutica» dell’esistenza umana. La mia analisi della concezione gadameriana del Verstehen e dell’Erfahrung – in quanto forme di un «sapere pratico (praktisches Wissen)» differente in linea di principio da quello teorico e tecnico – conduce quindi ad un’interpretazione complessiva dell’ermeneutica filosofica come vera e propria filosofia pratica. Cioè, come uno sforzo di chiarificazione filosofica di quel sapere prescientifico, intersoggettivo e “di senso comune” effettivamente vigente nella sfera della nostra Lebenswelt e della nostra esistenza pratica. Ciò, infine, conduce anche inevitabilmente ad un’accentuazione dei risvolti etico-politici dell’ermeneutica di Gadamer. In particolare, cerco di esaminare la concezione gadameriana dell’etica – tenendo conto dei suoi rapporti con le dottrine morali di Platone, Aristotele, Kant e Hegel – e di delineare alla fine un profilo della sua ermeneutica filosofica come filosofia del dialogo, della solidarietà e della libertà.

Second law analysis and simulation techniques for the energy optimization of buildings

The research activity described in this thesis is focused mainly on the study of finite-element techniques applied to thermo-fluid dynamic problems of plant components and on the study of dynamic simulation techniques applied to integrated building design in order to enhance the energy performance of the building. The first part of this doctorate thesis is a broad dissertation on second law analysis of thermodynamic processes with the purpose of including the issue of the energy efficiency of buildings within a wider cultural context which is usually not considered by professionals in the energy sector. In particular, the first chapter includes, a rigorous scheme for the deduction of the expressions for molar exergy and molar flow exergy of pure chemical fuels. The study shows that molar exergy and molar flow exergy coincide when the temperature and pressure of the fuel are equal to those of the environment in which the combustion reaction takes place. A simple method to determine the Gibbs free energy for non-standard values of the temperature and pressure of the environment is then clarified. For hydrogen, carbon dioxide, and several hydrocarbons, the dependence of the molar exergy on the temperature and relative humidity of the environment is reported, together with an evaluation of molar exergy and molar flow exergy when the temperature and pressure of the fuel are different from those of the environment. As an application of second law analysis, a comparison of the thermodynamic efficiency of a condensing boiler and of a heat pump is also reported. The second chapter presents a study of borehole heat exchangers, that is, a polyethylene piping network buried in the soil which allows a ground-coupled heat pump to exchange heat with the ground. After a brief overview of low-enthalpy geothermal plants, an apparatus designed and assembled by the author to carry out thermal response tests is presented. Data obtained by means of in situ thermal response tests are reported and evaluated by means of a finite-element simulation method, implemented through the software package COMSOL Multyphysics. The simulation method allows the determination of the precise value of the effective thermal properties of the ground and of the grout, which are essential for the design of borehole heat exchangers. In addition to the study of a single plant component, namely the borehole heat exchanger, in the third chapter is presented a thorough process for the plant design of a zero carbon building complex. The plant is composed of: 1) a ground-coupled heat pump system for space heating and cooling, with electricity supplied by photovoltaic solar collectors; 2) air dehumidifiers; 3) thermal solar collectors to match 70% of domestic hot water energy use, and a wood pellet boiler for the remaining domestic hot water energy use and for exceptional winter peaks. This chapter includes the design methodology adopted: 1) dynamic simulation of the building complex with the software package TRNSYS for evaluating the energy requirements of the building complex; 2) ground-coupled heat pumps modelled by means of TRNSYS; and 3) evaluation of the total length of the borehole heat exchanger by an iterative method developed by the author. An economic feasibility and an exergy analysis of the proposed plant, compared with two other plants, are reported. The exergy analysis was performed by considering the embodied energy of the components of each plant and the exergy loss during the functioning of the plants.

Stereoselective synthesis of heterocycles as intermediates of biologically active compounds

The aim of this thesis was to investigate the synthesis of enantiomerically enriched heterocycles and dehydro-β-amino acid derivatives which can be used as scaffolds or intermediates of biologically active compounds, in particular as novel αvβ3 and α5β1 integrin ligands. The starting materials of all the compounds here synthesized are alkylideneacetoacetates. Alkylidene derivates are very usefull compounds, they are usually used as unsaturated electrophiles and they have the advantage of introducing different kind of functionality that may be further elaborated. In chapter 1, regio- and stereoselective allylic amination of pure carbonates is presented. The reaction proceeds via uncatalyzed or palladium-catalyzed conditions and affords enantiopure dehydro-β-amino esters that are useful precursor of biologically active compounds. Chapter 2 illustrates the synthesis of substituted isoxazolidines and isoxazolines via Michael addition followed by intramolecular hemiketalisation. The investigation on the effect of the Lewis acid catalysis on the regioselectivity of the addition it also reported. Isoxazolidines and isoxazolines are interesting heterocyclic compounds that may be regarded as unusual constrained -amino acids or as furanose mimetics. The synthesis of unusual cyclic amino acids precursors, that may be envisaged as proline analogues, as scaffolds for the design of bioactive peptidomimetics is presented in chapter 3. The synthesis of 2-substituted-3,4-dehydropyrrole derivatives starting from allylic carbonates via a two step allylic amination/ring closing metathesis (RCM) protocol is carried out. The reaction was optimized by testing different Grubbs’ catalysts and carbamate nitrogen protecting groups. Moreover, in view of a future application of these dehydro-β-amino acids as central core of peptidomimetics , the malonate chain was also used to protect nitrogen prior to RCM. Finally, chapter 4 presents the synthesis of two novel different classes of integrin antagonists, one derived from dehydro-β-amino acid prepared as described in chapter 1 and the other one has isoxazolidines synthesized in chapter 2 as rigid constrained core. Since that these compounds are promising RGD mimetics for αvβ3 and α5β1 integrins, they have been submitted to biological assay. and to interpret on a molecular basis their different affinities for the αvβ3 receptor, docking studies were performed using Glide program.

The potential of the 3-UPU translational parallel manipulator and a procedure to select the best architecture

The 3-UPU three degrees of freedom fully parallel manipulator, where U and P are for universal and prismatic pair respectively, is a very well known manipulator that can provide the platform with three degrees of freedom of pure translation, pure rotation or mixed translation and rotation with respect to the base, according to the relative directions of the revolute pair axes (each universal pair comprises two revolute pairs with intersecting and perpendicular axes). In particular, pure translational parallel 3-UPU manipulators (3-UPU TPMs) received great attention. Many studies have been reported in the literature on singularities, workspace, and joint clearance influence on the platform accuracy of this manipulator. However, much work has still to be done to reveal all the features this topology can offer to the designer when different architecture, i.e. different geometry are considered. Therefore, this dissertation will focus on this type of the 3-UPU manipulators. The first part of the dissertation presents six new architectures of the 3-UPU TPMs which offer interesting features to the designer. In the second part, a procedure is presented which is based on some indexes, in order to allows the designer to select the best architecture of the 3-UPU TPMs for a given task. Four indexes are proposed as stiffness, clearance, singularity and size of the manipulator in order to apply the procedure.

InSAR deformation measurements of the earthquake cycle in transcurrent tectonic domains, analytical and analog modeling

I applied the SBAS-DInSAR method to the Mattinata Fault (MF) (Southern Italy) and to the Doruneh Fault System (DFS) (Central Iran). In the first case, I observed limited internal deformation and determined the right lateral kinematic pattern with a compressional pattern in the northern sector of the fault. Using the Okada model I inverted the observed velocities defining a right lateral strike slip solution for the MF. Even if it fits the data within the uncertainties, the modeled slip rate of 13-15 mm yr-1 seems too high with respect to the geological record. Concerning the Western termination of DFS, SAR data confirms the main left lateral transcurrent kinematics of this fault segment, but reveal a compressional component. My analytical model fits successfully the observed data and quantifies the slip in ~4 mm yr-1 and ~2.5 mm yr-1 of pure horizontal and vertical displacement respectively. The horizontal velocity is compatible with geological record. I applied classic SAR interferometry to the October–December 2008 Balochistan (Central Pakistan) seismic swarm; I discerned the different contributions of the three Mw > 5.7 earthquakes determining fault positions, lengths, widths, depths and slip distributions, constraining the other source parameters using different Global CMT solutions. A well constrained solution has been obtained for the 09/12/2008 aftershock, whereas I tested two possible fault solutions for the 28-29/10/08 mainshocks. It is not possible to favor one of the solutions without independent constraints derived from geological data. Finally I approached the study of the earthquake-cycle in transcurrent tectonic domains using analog modeling, with alimentary gelatins like crust analog material. I successfully joined the study of finite deformation with the earthquake cycle study and sudden dislocation. A lot of seismic cycles were reproduced in which a characteristic earthquake is recognizable in terms of displacement, coseismic velocity and recurrence time.

Analysis of the memory B cell response against glycoconjugate vaccines

The development of vaccines directed against polysaccharide capsules of S. pneumoniae, H. influenzae and N. meningitidis have been of great importance in preventing potentially fatal infections. Bacterial capsular polysaccharides are T-cell-independent antigens that induce specific antibody response characterized by IgM immunoglobulins, with a very low IgG class switched response and lack of capability of inducing a booster response. The inability of pure polysaccharides to induce sustained immune responses has required the development of vaccines containing polysaccharides conjugated to a carrier protein, with the aim to generate T cell help. It is clear that the immunogenicity of glycoconjugate vaccines can vary depending on different factors, e.g. chemical nature of the linked polysaccharide, carrier protein, age of the target population, adjuvant used. The present study analyzes the memory B cell (MBC) response to the polysaccharide and to the carrier protein following vaccination with a glycoconjugate vaccine for the prevention of Group B streptococcus (GBS) infection. Not much is known about the role of adjuvants in the development of immunological memory raised against GBS polysaccharides, as well as about the influence of having a pre-existing immunity against the carrier protein on the B cell response raised against the polysaccharide component of the vaccine. We demonstrate in the mouse model that adjuvants can increase the antibody and memory B cell response to the carrier protein and to the conjugated polysaccharide. We also demonstrate that a pre-existing immunity to the carrier protein favors the development of the antibody and memory B cell response to subsequent vaccinations with a glycoconjugate, even in absence of adjuvants. These data provide a useful insight for a better understanding of the mechanism of action of this class of vaccines and for designing the best vaccine that could result in a productive and long lasting memory response.

Comparison of affinity chromatography supports for separation of protein

Chromatography is the most widely used technique for high-resolution separation and analysis of proteins. This technique is very useful for the purification of delicate compounds, e.g. pharmaceuticals, because it is usually performed at milder conditions than separation processes typically used by chemical industry. This thesis focuses on affinity chromatography. Chromatographic processes are traditionally performed using columns packed with porous resin. However, these supports have several limitations, including the dependence on intra-particle diffusion, a slow mass transfer mechanism, for the transport of solute molecules to the binding sites within the pores and high pressure drop through the packed bed. These limitations can be overcome by using chromatographic supports like membranes or monoliths. Dye-ligands are considered important alternatives to natural ligands. Several reactive dyes, particularly Cibacron Blue F3GA, are used as affinity ligand for protein purification. Cibacron Blue F3GA is a triazine dye that interacts specifically and reversibly with albumin. The aim of this study is to prepare dye-affinity membranes and monoliths for efficient removal of albumin and to compare the three different affinity supports: membranes and monoliths and a commercial column HiTrapTM Blue HP, produced by GE Healthcare. A comparison among the three supports was performed in terms of binding capacity at saturation (DBC100%) and dynamic binding capacity at 10% breakthrough (DBC10%) using solutions of pure BSA. The results obtained show that the CB-RC membranes and CB-Epoxy monoliths can be compared to commercial support, column HiTrapTM Blue HP, for the separation of albumin. These results encourage a further characterization of the new supports examined.

Solubility, diffusivity and permeability of gases in glassy polymers

Gas separation membranes of high CO2 permeability and selectivity have great potential in both natural gas sweetening and carbon dioxide capture. Many modified PIM membranes results permselectivity above Robinson upper bound. The big problem that should be solved for these polymers to be commercialized is their aging through time. In high glassy polymeric membrane such as PIM-1 and its modifications, solubility selectivity has more contribution towards permselectivity than diffusivity selectivity. So in this thesis work pure and mixed gas sorption behavior of carbon dioxide and methane in three PIM-based membranes (PIM-1, TZPIM-1 and AO-PIM-1) and Polynonene membrane is rigorously studied. Sorption experiment is performed at different temperatures and molar fraction. Sorption isotherms found from the experiment shows that there is a decrease of solubility as the temperature of the experiment increases for both gases in all polymers. There is also a decrease of solubility due to the presence of the other gas in the system in the mixed gas experiments due to competitive sorption effect. Variation of solubility is more visible in methane sorption than carbon dioxide, which will make the mixed gas solubility selectivity higher than that of pure gas solubility selectivity. Modeling of the system using NELF and Dual mode sorption model estimates the experimental results correctly Sorption of gases in heat treated and untreated membranes show that the sorption isotherms don’t vary due to the application of heat treatment for both carbon dioxide and methane. But there is decrease in the diffusivity coefficient and permeability of pure gases due to heat treatment. Both diffusivity coefficient and permeability decreases with increasing of heat treatment temperature. Diffusivity coefficient calculated from transient sorption experiment and steady state permeability experiment is also compared in this thesis work. The results reveal that transient diffusivity coefficient is higher than steady state diffusivity selectivity.

Kinematics and statics of cable-driven parallel robots by interval-analysis-based methods

In the past two decades the work of a growing portion of researchers in robotics focused on a particular group of machines, belonging to the family of parallel manipulators: the cable robots. Although these robots share several theoretical elements with the better known parallel robots, they still present completely (or partly) unsolved issues. In particular, the study of their kinematic, already a difficult subject for conventional parallel manipulators, is further complicated by the non-linear nature of cables, which can exert only efforts of pure traction. The work presented in this thesis therefore focuses on the study of the kinematics of these robots and on the development of numerical techniques able to address some of the problems related to it. Most of the work is focused on the development of an interval-analysis based procedure for the solution of the direct geometric problem of a generic cable manipulator. This technique, as well as allowing for a rapid solution of the problem, also guarantees the results obtained against rounding and elimination errors and can take into account any uncertainties in the model of the problem. The developed code has been tested with the help of a small manipulator whose realization is described in this dissertation together with the auxiliary work done during its design and simulation phases.

Study and experimental characterization of the laser welding process for the manufacturing of electric powertrain components in the automotive industry

The PhD project that will be presented in this thesis is focused on the study and optimization of the production process for the manufacturing of electrical powertrain components in the automotive field using the laser beam welding process (LBW). The objective is to define, through experimental activities, an optimized process condition for applications in the electrical field that can be generalized, that is, which guarantees its reproducibility as the types of connections vary and which represents the basis for extending the method to future applications in e-mobility sector. The work developed along two lines of research, the convergence of which made it possible to create prototypes of battery modules based on different types of lithium-ion cells and stator windings for electric motors. On the one hand, the different welding configurations involving the production of batteries based on pouch cells and therefore the welding of aluminum and copper in dissimilar configuration were studied, while for the prismatic cells only one configuration was analyzed. On the other hand, the welding of pure copper hairpins with rectangular shape in edge joint configuration was studied for the production of stator windings. The experimental tests carried out have demonstrated the feasibility of using the LBW process for the production of electric powertrain components entirely designed and developed internally as the types of materials and welding configurations vary; the methodologies required for the characterization methods, necessary for the end-of-line tests, for the evaluation of the properties of the different joint configurations and components (battery and electric motor) were also defined with the aim of obtaining the best performance. The entire doctorate program was conducted in collaboration with Ferrari Auto S.p.A. and the direct industrial application of the issues addressed has been faced.