Introdução: O déficit de rotação interna glenoumeral, freqüentemente observado em praticantes de esportes que envolvem movimentos repetidos do membro superior sobre a cabeça, tem sido associado ao surgimento de lesões secundárias no ombro. Objetivos: Medir e comparar a amplitude de rotação interna glenoumeral em praticantes assintomáticos de tênis e natação, esportes com características diferentes, mas que envolvem esse tipo de movimento. Métodos: 54 voluntários assintomáticos do sexo masculino (108 ombros) divididos em 3 grupos (tenistas, nadadores, grupo-controle) foram submetidos à medida da amplitude de rotação interna glenoumeral através do método de exame clínico com estabilização da escápula (delineamento de pesquisa: estudo transversal). Foram comparadas as medidas dos ombros dominante e não dominante dentro de cada grupo e entre os grupos. Resultados: Em todos os grupos, o ombro dominante apresentou déficit de rotação interna se comparado com o não dominante. No grupo de tenistas o déficit médio foi de 23,9° ± 8,4° (P< 0,001), no de nadadores foi de 12° ± 6,8° (P< 0,001), e no grupocontrole de 4,9° ± 7,4° (P= 0,035). Comparados os membros dominantes entre os grupos, houve diferença entre todos, sendo o déficit apresentado pelos tenistas em relação ao grupo-controle (27,6°;P< 0,001) maior do que o dos nadadores (17,9°; P<0,001); entre tenistas e nadadores, foi de 9,7°;P=0,002). Conclusões: O membro dominante apresentou menor amplitude de rotação interna glenoumeral do que o não dominante em todos os grupos, sendo o déficit dos tenistas cerca de duas vezes maior do que o dos nadadores. A diferença média entre os membros no grupo controle foi menor do que 5°, o que está dentro do parâmetro de normalidade de acordo com a maioria dos estudos. Todos os grupos apresentaram diferenças se comparados os membros dominantes entre si. Os tenistas apresentaram a menor amplitude de rotação interna seguidos pelos nadadores. / Background: Glenohumeral internal rotation deficit, often diagnosed in players of overhead sports, has been associated with the development of secondary shoulder pathologies. Aim: To measure and compare the range of glenohumeral internal rotation motion in asymptomatic tennis players and in swimmers, different sports that share this overhead movements. Methods: Fifty-four asymptomatic male volunteers (108 shoulders) divided in 3 groups (tennis players, swimmers, control group) underwent measurements of glenohumeral internal rotation using clinical examination with scapular stabilization (study design: cross-sectional study). Measurements of dominant and nondominant shoulders were compared within and between groups. Results: In tennis players, mean déficit was 23.9° ± 8.4° (P< 0.001); in swimmers, 12° ± 6.8° (P< 0.001); and in the control group, 4.9° ± 7.4° (P= 0.035). Dominant shoulders showed significant difference between all groups, and the déficit of the group of tennis players in comparison with the control group (27.6°;P< 0.001) was greater than the deficit found in the group of swimmers (17.9°; P<0.001); between tennis players and swimmers, the deficit was 9.7°;P=0.002). Conclusions: Dominant limbs showed less glenohumeral internal rotation than the nondominant limbs in all groups, being the deficit in the group of tennis players about twice the deficit found for swimmers. Mean difference between limbs in the control group was less than 5°, which is within normal parameters according to most studies. There were statistically significant differences between all groups when dominant shoulders were compared to each other. Tennis players had the least range of motion, followed by swimmers.

The chemical complexity of the interstellar medium and combustion environments pose a challenge to the scientific community seeking to provide a molecular understanding of their combustion. More refined spectroscopic tools and methodologies must be developed to selectively detect and characterize the widening array of fuel and interstellar species. The direct relationship between molecular structure and rotational frequencies makes rotational spectroscopy highly structural specific; therefore, it offers a powerful means of characterizing polar molecules. However, rotational spectra usually contain transitions from multiple components with multiple conformations as well as other dynamical properties interleaved with one another, making the assignment of the spectra very challenging. This thesis describes experimental work using broadband microwave spectroscopy and vacuum ultraviolet time-of-flight mass spectrometry to address a number of challenging problems in the spectroscopy of gas complex mixtures.<div><br></div><div>In the first part of my work, we report details of the design and operation of a single apparatus that combines Chirped-Pulse Fourier Transform Microwave spectroscopy (CP-FTMW) with VUV photoionization Time-of-Flight Mass Spectrometry (VUV TOFMS). The supersonic expansion used for cooling samples is interrogated first by passing through the region between two microwave horns capable of broadband excitation and detection in the 2-18 GHz frequency region of the microwave. After passing through this region, the expansion is skimmed to form a molecular beam, before being probed with 118 nm (10.5 eV) single-photon VUV photoionization in a linear time-of-flight mass spectrometer. The two detection schemes are powerfully complementary to one another. CP-FTMW detects all components with significant permanent dipole moments. Rotational transitions provide high-resolution structural data. VUV TOFMS provides a gentle and general method for ionizing all components of a gas phase mixture with ionization thresholds below 10.5 eV, providing their molecular formulae. The advantages, complementarity, and limitations of the combined methods are illustrated through results on two gas-phase mixtures made up of (i) three furanic compounds, two of which are structural isomers of one another, and (ii) the effluent from a flash pyrolysis source with <i>o-</i>guaiacol as precursor. <br></div><div><br></div><div>The broadband spectrum of 3-phenylpropionitrile was recorded under jet-cooled conditions over the 8-18 GHz region. A novel multi-resonance technique called strong field coherence breaking (SFCB) was implemented to record conformer-specific microwave spectra. This technique involves sweeping the broadband chirp followed by selectively choosing a set of single frequencies pulses to yield a set of rotational transitions that belong to a single entity in the gas-phase mixture, aiding assignment greatly. Transitions belonging to anti and gauche conformers were identified and assigned and accurate experimental rotational constants were determined to provide insight on the molecular structure. Experimental rotational transitions provided relative abundances in the supersonic expansion. A modified line picking scheme was developed in the process to modulate more transitions and improve the overall efficiency of the SFCB multiple selective excitation technique.<br></div><div><br></div><div>The rotational spectrum of 2-hexanone was recorded over the 8-18 GHz region using a CPFTMW spectrometer. SFCB was utilized to selectively modulate the intensities of rotational transitions belonging to the two lowest energy conformers of 2-hexanone, aiding the assignment. In addition, the SFCB method was applied for the first time to selectively identify rotational transitions built off the two lowest energy hindered methyl rotor states of each conformer, 0a₁ and 1e. Since these two states have rotational energy levels with different nuclear spin symmetries, their intensities could be selectively modulated by the resonant monochromatic pulses used in the SFCB method. The difference spectra, final fit and structural parameters are discussed for the three assigned conformers of 2-hexanone.<br></div><div><br></div><div>Developing new experimental techniques that allow for species identification and quantification in the high-temperature environment of reacting flows is a continuing challenge in combustion research. Here, we combine broadband chirped-pulse microwave (rotational) spectroscopy with an atmospheric-pressure jet-stirred reactor as a novel method to identify key reactive intermediates in low-temperature and ozone-assisted oxidation processes. In these experiments, the gas sample, after being withdrawn from reactive dimethyl ether/O₂/Ar, dimethoxy methane/O₂/Ar, and ethylene/O₂/O₃/Ar mixtures, expands via a supersonic expansion into the high vacuum of a microwave spectrometer, where the rotationally cold ensemble of polar molecules is excited with short MW radiation frequency ramps (chirps). The response of the molecular ensemble is detected in the time domain and after a Fourier transformation, the spectral composition of the transient emission is obtained in the frequency domain. The observed rotational frequencies are uniquely correlated to molecular structures and allow for an unambiguous identification of the sampled species. Detection and identification of intermediates such as formaldehyde, methyl formate, formic acid, formic acid anhydride, and the primary ethylene ozonide via literature-known rotational frequencies are evidence for the superb identification capabilities of broadband chirped-pulse microwave spectroscopy. Strong-field coherence breaking is employed to identify and assign transitions due to a specific component. The observation of van der Waals complexes provides an opportunity to detect combustion intermediates and products that are impossible to detect by rotational spectroscopy as isolated molecules. <br></div><div><br></div><div>Lastly, preliminary data on important combustion precursors is studied including pentanal, <i>trans-</i>2-pentenal and <i>o-,m- </i>and <i>p</i>-vinylanisole. The rotational spectrum of these five molecules is recorded from the 8-18 GHz region under jet-cooled conditions. For pentanal and <i>trans-</i>2-pentenal, SFCB was utilized to dissect the broadband spectrum, identifying the four and two lowest energy structures, respectively. The structural parameters and finals fits are provided. <br></div>

Le but de cette thèse est d’explorer le potentiel sismique des étoiles naines blanches pulsantes, et en particulier celles à atmosphères riches en hydrogène, les étoiles ZZ Ceti. La technique d’astérosismologie exploite l’information contenue dans les modes normaux de vibration qui peuvent être excités lors de phases particulières de l’évolution d’une étoile. Ces modes modulent le flux émergent de l’étoile pulsante et se manifestent principalement en termes de variations lumineuses multi-périodiques. L’astérosismologie consiste donc à examiner la luminosité d’étoiles pulsantes en fonction du temps, afin d’en extraire les périodes, les amplitudes apparentes, ainsi que les phases relatives des modes de pulsation détectés, en utilisant des méthodes standards de traitement de signal, telles que des techniques de Fourier. L’étape suivante consiste à comparer les périodes de pulsation observées avec des périodes générées par un modèle stellaire en cherchant l’accord optimal avec un modèle physique reconstituant le plus fidèlement possible l’étoile pulsante. Afin d’assurer une recherche optimale dans l’espace des paramètres, il est nécessaire d’avoir de bons modèles physiques, un algorithme d’optimisation de comparaison de périodes efficace, et une puissance de calcul considérable. Les périodes des modes de pulsation de modèles stellaires de naines blanches peuvent être généralement calculées de manière précise et fiable sur la base de la théorie linéaire des pulsations stellaires dans sa version adiabatique. Afin de définir dans son ensemble un modèle statique de naine blanche propre à l’analyse astérosismologique, il est nécessaire de spécifier la gravité de surface, la température effective, ainsi que différents paramètres décrivant la disposition en couche de l’enveloppe. En utilisant parallèlement les informations obtenues de manière indépendante (température effective et gravité de surface) par la méthode spectroscopique, il devient possible de vérifier la validité de la solution obtenue et de restreindre de manière remarquable l’espace des paramètres. L’exercice astérosismologique, s’il est réussi, mène donc à la détermination précise des paramètres de la structure globale de l’étoile pulsante et fournit de l’information unique sur sa structure interne et l’état de sa phase évolutive. On présente dans cette thèse l’analyse complète réussie, de l’extraction des fréquences à la solution sismique, de quatre étoiles naines blanches pulsantes. Il a été possible de déterminer les paramètres structuraux de ces étoiles et de les comparer remarquablement à toutes les contraintes indépendantes disponibles dans la littérature, mais aussi d’inférer sur la dynamique interne et de reconstruire le profil de rotation interne. Dans un premier temps, on analyse le duo d’étoiles ZZ Ceti, GD 165 et Ross 548, afin de comprendre les différences entre leurs propriétés de pulsation, malgré le fait qu’elles soient des étoiles similaires en tout point, spectroscopiquement parlant. L’analyse sismique révèle des structures internes différentes, et dévoile la sensibilité de certains modes de pulsation à la composition interne du noyau de l’étoile. Afin de palier à cette sensibilité, nouvellement découverte, et de rivaliser avec les données de qualité exceptionnelle que nous fournissent les missions spatiales Kepler et Kepler2, on développe une nouvelle paramétrisation des profils chimiques dans le coeur, et on valide la robustesse de notre technique et de nos modèles par de nombreux tests. Avec en main la nouvelle paramétrisation du noyau, on décroche enfin le ”Saint Graal” de l’astérosismologie, en étant capable de reproduire pour la première fois les périodes observées à la précision des observations, dans le cas de l’étude sismique des étoiles KIC 08626021 et de GD 1212. / The goal of this thesis is to explore the seismic potential of pulsating white dwarf stars, and in particular those having an hydrogen-rich atmosphere, the ZZ Ceti stars. The technique of asteroseismology relies on the information contained in the normal modes of vibration that can be excited during specific phases of the evolution of a star. These modes modulate the emerging flux of the pulsating star and mainly present themselves as multi-periodic luminosity variations. Asteroseismology is the science that examines the luminosity of pulsating stars as a function of time, to better extract the periods, apparent amplitudes and relative phases of the detected pulsation modes, using standard methods of signal processing such as Fourier techniques. We then compare the observed pulsation periods to periods generated from a stellar model by searching the optimal match with a physically sound model that best describes the pulsating star. To better search in parameter space, it is primordial to have good physically sound models, an efficient algorithm comparing the periods, and significant computing power. The periods of the pulsation modes of white dwarf stellar models can be generally calculated very precisely on the basis of the linear theory of stellar pulsations in its adiabatic version. To define a static white dwarf model suitable for a seismic analysis, it is necessary to specify the surface gravity, the effective temperature, and the various parameters describing the onion-like structure of the star. By using a posteriori the informations obtained independently (effective temperature and surface gravity) with the spectroscopic technique, it is then possible to confirm the validity of the solution obtained. The asteroseismic exercise, when successful, precisely determines the various parameters of the global structure of the pulsating star, and gives unique information on the internal structure of the star and the current state of its evolutionary phase. We present in this thesis the complete and successful analyses, from frequency extraction to the finding of the seismic solution, of four pulsating white dwarf stars. It was possible to determine the structural parameters of these stars and to compare them to every possible independent constraints found in the literature, but to also infer on the internal dynamic and to reconstruct the internal rotation profile. At first, we analyse the pair of ZZ Ceti stars, GD 165 and Ross 548, to better understand the differences in their pulsation spectra, notwithstanding their identical spectroscopic properties. The seismic analysis reveals different internal structures, and unravels the sensitivity of some pulsation modes to the internal composition of the core of the star. To compensate for this newly discovered sensitivity, and to rival the exceptional quality of the data coming from the spatial missions Kepler and Kepler2, we develop a new parameterization of the core chemical profiles, and we validate the robustness of our technique and our models by various tests. Having in hand the new parameterization of the core, we reach the ”Holy Grail” of asteroseismology, by being capable of reproducing for the first time the observed periods to the precision of the observations, in the study case of the stars KIC 08626021 and GD 1212.

L’astérosismologie consiste à sonder les intérieurs stellaires en détectant les ondes sismiques qui s’y propagent. Les géantes rouges, des étoiles évoluées peu massives dont l’hydrogène du cœur est épuisé, sont des pulsateurs de type solaire présentant des modes mixtes qui nous permettent d’accéder directement aux propriétés physiques de leur cœur. Les mesures sismiques disponibles indiquent qu’un ou plusieurs mécanismes physiques encore mal compris contrebalancent l’accélération de la rotation du cœur sous l’effet de sa contraction, en transportant du moment cinétique. La majeure partie de cette thèse a été consacrée au développement d’une méthode permettant une mesure aussi automatisée que possible de la rotation moyenne du cœur des étoiles de la branche des géantes rouges observées par le satellite Kepler (NASA). Les mesures obtenues pour environ 900 étoiles mettent en évidence que la rotation du cœur est à peu près constante le long de la branche des géantes rouges,avec des valeurs indépendantes de la masse des étoiles. Le deuxième volet de cette thèse est consacré à l’interprétation de ces résultats basée sur la modélisation stellaire. L’enjeu consiste à utiliser les mesures à grande échelle obtenues durant la première partie pour caractériser la quantité de moment cinétique qui doit être extraite localement de chaque région du cœur, à différents instants sur la branche des géantes rouges, pour différentes masses stellaires. / Asteroseismology consists in probing stellar interiors through the detection of seismic waves. Red giants are evolved low-mass stars that have exhausted hydrogen in their core. These stars are solar-type pulsators presenting mixed modes that allow us to have a direct access to the physical properties of their core. The available seismic measurements indicate that one or several mechanisms that remain poorly understood counterbalance the acceleration ofthe core rotation, resulting from its contraction, by transporting angularmomentum. The greatest part of this PhD thesis was devoted to the development of a method allowing a measurement as automated as possible of the mean core rotation of stars on the red giant branch that were observed by the Kepler satellite (NASA). The measurements that were derived for almost 900 stars highlight that the core rotation is almost constant along the red giant branch, with values largely independent of the stellar mass. The second part of this PhD thesis is devoted to the interpretation of these results based on stellar modelling. The challenge consists in using the large-scale measurements obtainedin the first part to characterise the quantity of angular momentum that has to be extracted from each layer of the core, at different timesteps on the red giant branch, for different stellar masses.

Ces dernières décennies, la spectroscopie moléculaire a bénéficié du progrès des spectromètres, notamment en terme de sélectivité et sensibilité, et de méthodes d'analyse et de calculs de chimie quantique toujours plus avancés. Désormais, la spectroscopie rotationnelle s'oriente vers l'analyse de systèmes moléculaires plus complexes caractérisés spectralement par une forte densité de raies. La congestion spectrale des espèces étudiées dans ma thèse s'explique non seulement par de faibles constantes rotationnelles mais aussi par la présence d'états vibrationnels excités à température ambiante, une forte richesse isotopique, un haut degré de splittings dus aux mouvements de grande amplitude ou encore par un paysage conformationnel complexe. Cette thèse illustre ainsi divers scénarii à travers les études du chlorure de thionyle, des nitrotoluènes et des méthoxyphénols. Les spectres rovibrationnels des bandes v2 et v5 des isotopologues du chlorure de thionyle ont été mesurés dans l'infrarouge lointain au synchroton SOLEIL et analysés en utilisant une approche semi-automatique basée sur des algorithmes évolutionnaires. Les isomères du nitrotoluène ont été ciblés pour leur intérêt défense comme traceurs d'explosif (TNT), les spectres de rotation pure ont été mesurés dans les régions micro-ondes en jet moléculaire et millimétrique à température ambiante. Le spectre millimétrique du 3-nitrotoluène était particulièrement faible et congestionné avec des splittings dus à la rotation interne très importants (jusqu'à plusieurs GHz) en raison d'une barrière de rotation très faible ( Vз=6.7659(24)cmˉ ¹). La limite de détection a été estimée et une liste de raies établie. Les spectres millimétriques des 2-nitrotoluène et 4-nitrotoluène ont également été partiellement analysés. Enfin, les méthoxyphénols émis lors de feux de biomasse ont également étudiés comme précurseurs d'aérosols organiques secondaires pour leur détection atmosphérique future. Associée à des calculs de chimie quantique, l'analyse du spectre millimétrique du 3-méthoxyphénol mesuré à température ambiante dans la région millimétrique a permis de déterminer la stabilité relative de quatre conformères. / In recent decades, molecular spectroscopy has benefited from the progress of spectrometers, particularly in terms of selectivity and sensitivity, and from the continuous advancement of the analysis methods and quantum chemistry calculations. Today, rational spectroscopy is moving towards the analysis of more complex molecular systems spectrally characterized by a high density of lines. The spectral congestion of the species studied in this thesis is not only explained by low rotational constants, but also by the presence of vibrational states excited at room temperature, a high isotopic richness, a high degree of line splitting due to large amplitude motions or by a complex conformational landscape. This thesis thus illustrates various scenarios through the studies of thionyl chloride, nitrotoluenes and methoxyphenols. The rovibrational spectra of the v2 and v5 bands of the isotopologues of thionyl chloride were measured in far-infrared at the SOLEIL synchroton and analyzed using a semi-automatic approach based on evolutionary algorithms. The isomers of nitrotoluene have been targeted for military application as explosive taggants (TNT), the pure rotation spectra were measured in the microwave region in molecular jet and in the millimeter-wave region at room temperature. The millimeter-wave spectrum of 3-nitrotoluene was especially weak and congested with very large internal rotation splittings (up to several GHz) due to a very weak rotational barrier (V3=6.7659(24)cmˉ ¹). The detection limit was estimated and a linelist established. The 2-nitrotoluene and 4-nitrotoluene millimeter-wave spectra have been also partially analyzed. Finally, methoxyphenols emitted during biomass fires have also been studied as they are secondary organic aerosol precursors for their future atmospheric detection. Combined with quantum chemistry calculations, the analysis of the millimeter-wave spectrum of the 3-methoxyphenol measured at room temperature permitted the relative stability of four conformers to be determined.

Title: Effect of the range of the shoulder joint rotation in volleyball players on the development of functional changes. Objectives: The aim of this thesis is to confirm the presence of the glenohumeral internal rotation deficit in beach volleyball players and to determine whether it affects the development of functional changes of the shoulder joint located in the dominant upper limb. Methods: The thesis was a quantitative study with the character of an experiment. There were 60 active volleyball players aged 18-30 years who were deliberately selected for the purposes of the study. The essence was to ascertain whether GIRD affects the pain in the shoulder joint of volleyball players and whether it was deemed positive for all participants of the study. In order to examine the range of motion, the goniometer in the external and internal rotation according to Janda and Pavla, Janda and Sachse was used, as well as hypermobility tests and a shoulder joint pain questionnaire. The statistical data processing was performed by Microsoft Excel 2010. The sum and average functions were used. Subsequently, graphs and tables were created from the results Results: The established hypotheses were confirmed in two cases. GIRD is determined positive for beach volleyball players. From the results of hypermobility...

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