6 resultados para rotational isomerism

em AMS Tesi di Laurea - Alm@DL - Università di Bologna


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Our solar system contains an impressive amount of celestial bodies. For example Saturn posses a huge variety of natural satellites, the diversity in size and physical proprieties of which might amaze imagination. The observational data gathered in 30 years range of deep space missions revealed, that some of these bodies can hide subsurface oceans under their crust. The water, as we know, serves as a fundamental base for a possible appearance of life. This statement is quite exited for the scientific society and serves as a reason for studying so called ”ocean worlds”. In order to detect the celestial bodies with the hidden subsurface ocean, one of the key aspects is the study of their rotational state, which is strongly coupled with the body internal structure. It can be done through the various techniques mentioned in Chapter 1. The main goal of the thesis is the study of rotational state of Titan, whose interior structure expectedly contains liquid ocean layer under its icy crust. Titan is the largest moon of Saturn and it is the second largest moon in the solar system in general. This natural satellite is of particular scientific interest, because it is one of a kind which has substantial atmosphere. The present work was done using radio tracking data of the Dragonfly mission which is one of the next NASA’s missions destined for Titan selected as a part of the New Frontiers Program in 2019. The detailed characteristic of the Dragonfly regarding the landing site and mission lifetime was reported in Chapter 2. The radio-tracking communication link from Titan side was performed using Dragonfly X band transponder according to the schedule tracking opportunity. From Earth side according to the mission, Deep Space Station 25 which is a part of NASA’s Deep Space Network was considered. Only Doppler data was used for studying Titan rotational state, even though there are other reliable techniques described in Chapter 3, that in general could be implemented.

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In the last decades the evolution of radio science has made it possible to infer the atmosphere composition, the surface and the internal structure of the planets. Since the arrival of the first landers on Mars it was possible to make accurate measurements of the dynamics of this planet; in this thesis we will focus on InSight, considering the data disclosed by the JPL relative to the period from November 26th, 2018 to August 15th, 2021. In particular, the Doppler and Range measurements conducted by the RISE (Rotation and Interior Structure Experiment) will be analyzed. Since the accuracy of these measurements was improved significantly the effects due to the atmosphere of Mars might be measured so it should thus be possible to obtain a better estimate of the parameters characterizing the rotational dynamic of Mars. A large part of this study will therefore be dedicated to the study, modeling, implementation and analysis of the atmosphere of Mars, in both its components: troposphere and ionosphere. Once the complete model of Mars had been built, i.e. including the atmosphere, it was then possible to analyze the residuals, obtained between the data of the measurements carried out and the values predicted by the developed model, in order to obtain an estimate of the rotational dynamic of Mars.

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From the discoveries of Pasteur, stereochemistry has played an increasingly important role in the chemical sciences. In particular conformational study of molecules with axial chirality is object of intense research. Through Dynamic-NMR analysis and simulation of the spectra, the energy rotational barriers value of conformers are obtained. When this barrier is high sufficiently, atropisomeric stable compounds can be reached. They can be separated and used in stereo-synthesis and in packing processes. 3,4-bis-aryl maleimides, in which the aromatic groups are sufficiently bulky, generate atropisomeric stable configurations, that can be isolated at room temperature. The assignment of absolute configurations is performed through ECD analysis and comparison with computational calculations. The biological activities of maleimide derivatives widen the field of atropisomers application also in biological systems.

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Le problematiche ambientali e socio – economiche legate alla costruzione di nuove infrastrutture viarie, impongono la progettazione e costruzione di strade che combinino ad elevati standard prestazionali, la riduzione dell’impatto ambientale in fase realizzativa e manutentiva. Quanto detto avvalora il crescente utilizzo di materiali bituminosi modificati con polimeri ed additivati con cere. I primi conferiscono alla miscela maggiore elastoplasticità, incrementandone la durabilità e la resistenza a fatica. Nei secondi la presenza del materiale paraffinico contribuisce a ridurre la viscosità del bitume, il che consente il notevole abbassamento della temperatura di produzione e stesa della miscela. Numerosi studi inoltre hanno dimostrato che le caratteristiche meccaniche della pavimentazione sono fortemente influenzate dal grado di ossidazione delle componenti organiche del bitume, ovvero dal fenomeno dell’invecchiamento o aging. Risulta pertanto fondamentale affiancare allo studio reologico del bitume, prove di simulazione dell’ invecchiamento nel breve e lungo termine. Nel corso della seguente ricerca si provvederà pertanto ad analizzare leganti modificati ed additivati secondo la teoria della viscoelasticità, simulando le reali condizioni di carico ed invecchiamento alle quali il bitume è sottoposto. Tutte le prove di caratterizzazione reologica avanzata prevederanno l’utilizzo del DSR (Dynamic Shear Rheometer) in varie configurazioni di prova e si simulerà l’invecchiamento a breve termine mediante RTFOT (Rolling thin film oven test). Si proporrà inoltre una nuova procedura di aging invecchiando il bitume alla temperatura di equiviscosità o Twork , ovvero a quel valore della temperatura tale per cui, in fase di messa in opera, si avrà una distribuzione molecolare omogenea del modificante all’interno del bitume. Verranno quindi effettuate ulteriori prove reologiche sui leganti invecchiati a tale temperatura. Si darà infine supporto ai risultati della ricerca effettuando prove chimiche con la tecnica analitica FTIR (Fourier Transform Infrared Spectroscopy), analizzando i cambiamenti molecolari avvenuti nel bitume a seguito dell’aggiunta del modificante e dell’invecchiamento.

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In this thesis we studied the stereodynamic behavior of 1,2-azaborines variously substituted on boron (7a, 7b, 13). Depending on the hindrance of the asymmetric aryl substituent the resulting conformations could be stereolabile or configurationally stable. Through dynamic NMR and lineshape simulation, the energy rotational barriers of the different conformers are obtained. When the barrier is higher than 22-23 kcal/mol stable atropisomers that are fisically separable could be obtained (case of compound 13) and the free activation energy barrier is determinable by kinetic analysis. Absolute configuration of two atropisomers were assigned by comparison between computational calculations and experimental ECD. Isosteric compound 21 is then synthesized in order to compare the rotational barrier around B-Caryl with the one around Cnaphth-Caryl bond.