Land mines are a major humanitarian problem with millions of active mines in place around the world. Since these mines can have little metal in them, novel detection techniques are needed. Nuclear Quadrupole Resonance (NQR) is one such technique. Unfortunately, NQR is highly succeptible to radio frequency interference (RFI). A significant contribution of this thesis is the development of a custom, experimental data acquisition system designed and built specifically for capturing RFI at frequencies significant to NQR land mine detection systems. Another major contribution is the development of data analysis techniques for determining the number of reference antennas required to effectively cancel out RFI at frequencies and in environments typical of an NQR land mine detection system.

No description available.

Selective gas-phase dissociation strategies have been developed for the characterization of cross-linked peptides and proteins in quadrupole ion trap mass spectrometers. An infrared chromogenic cross-linker (IRCX) containing a phosphotriester afforded rapid differentiation of cross-linked peptides from unmodified ones in proteolytic digests of cross-linked proteins by selective infrared multiphoton dissociation (IRMPD). Only the cross-linked peptides containing the chromogenic phosphate underwent IRMPD and unmodified peptides were not affected by IR irradiation. IRMPD of IRCX-cross-linked peptides yielded uncross-linked y-ion sequence tags of the constituent peptides due to secondary dissociation of all primary product ions which contained the chromophore, thus allowing successful de novo sequencing of the cross-linked peptides. Peptides cross-linked via a two-step conjugation strategy through the formation of a bis-arylhydrazone (BAH) bond were selectively dissociated by ultraviolet radiation at 355 nm. The BAH-cross-linked peptides could be distinguished from not only unmodified peptides but also dead-end modified peptides based on the selectivity of ultraviolet photodissociation. In a complementary approach, electron transfer dissociation of BAH-cross-linked peptides resulted in preferential cleavage of the hydrazone bond which produced two modified peptides. These modified peptides were subsequently interrogated by CID which allowed for the original site of cross-linking to be pinpointed. IRMPD was implemented in a dual pressure linear ion trap to demonstrate successful photodissociation of peptides having modest absorptivities. Peptides were observed to efficiently dissociation by IR irradiation exclusively in the low pressure cell whereas no dissociation was observed in the high pressure cell due to extensive collisional cooling. IRMPD provided greater sequence coverage of the peptides than CID and yielded product ion mass spectra which were predominantly composed of singly charged product ions which simplified spectral interpretation. IRMPD was further applied for the sequencing of small-interfering RNA. Complete sequence coverage was obtained and the results were compared to CID. / text

No description available.

In this work we constructed an experimental system to realize a BEC of sodium atoms. In the first part of the work, we study two atomic sources in order to choose the most suitable for our system. The comparison between a Zeeman slower and a bidimensional magnetooptical trap (2D-MOT) was performed to evaluate the capacity of producing an appropiate flux of atoms in order to load a tridimensional magneto-optical trap (3D-MOT). The experimental results show that the 2D-MOT is as efficient as the Zeeman slower with the advantage of being more compact and easier to operate, and for these reasons we choose it as our source of cold atoms. After this, the experimental apparatus to produce a Bose-Einstein condensate was constructed and characterized. With this experimental system we realized all the required stages to achieve the Bose-Einstein condensation (BEC). Initially, we characterized and compared the performance between the Bright-MOT and Dark-SPOT MOT of sodium atoms, observing the great advantages this last configuration offers. Afterward, we implemented the experimental sequence for the achivement of the BEC of sodium atoms. After the optical molasses process, the atoms are tranferred to an optically plugged quadrupole trap (OPT) where the process of evaporative cooling is performed. With this setup, we achive a sodium BEC with ∼ 5×105 atoms and a critical temperature of ∼ 1.1 μK. Finally, with the constructed and characterized machine, we started to perform experiments of cooperative absorption of two photons by two trapped atoms. With the new system, we wanted to take advantage of the higher densities in the magnetic trap and BEC to explore some features of this phenomenon in the classical and quantum regimes. We were interested in exploring some features of this nonlinear light-matter interaction effect. The idea of having two or more photons interacting with two or more atoms is the beginning of a new possible class of phenomena that we could call many photons-many body intercation. In this new possibity, photons and atoms will be fully correlated, introducing new aspects of interactions. / Neste trabalho, realizamos a construção de um sistema experimental para a realização de um condensado de Bose-Einstein de átomos de sódio. Na primeira parte do trabalho, realizamos o estudo de duas fontes átomicas com o intuito de escolher a mais adequada para nosso sistema experimental. A comparação foi realizada entre um Zeeman slower e uma armadilha magneto-óptica bidimensional (MOT-2D), que são técnicas usadas para fornecer um grande fluxo de átomos com distribuição de velocidades adequadas para serem capturados numa armadilha magneto-óptica tridimensional (MOT-3D). Os resultados experimentais da caracterização de ambos os sistemas mostra que o MOT-2D oferece um grande fluxo atômico da mesma ordem do Zeeman slower, mas com a vantagem de ser um sistema mais compacto em questão de tamanho, razão pela qual foi escolhido como fonte atômica no nosso sistema. A partir daqui, realizamos a construção do sistema experimental para a realização do condensado de sódio. Inicialmente realizamos o aprisionamento numa MOT-3D, realizando subsequentemente os passos de resfriamento sub-Doppler mediante o processo de molasses ópticas. Depois disto, os átomos são transferidos para uma armadilha magnética, que consiste de um par de bobinas em configuração anti-Helmholtz, as mesmas usadas para a MOT-3D mas com um gradiente de campo magnético ao redor de uma ordem de grandeza maior. Esta armadilha é combinada com um laser com dessintonia para o azul focado a 30 μm no centro da armadilha, onde o campo magnético é zero com o objetivo de evitar as perdas por majorana que acontecem nessa região. Com esta configuração, um condensado de ∼ 5 × 105 átomos é obtido a uma temperatura crítica de ∼ 1.1 μK. Por último, com a máquina construída e caracterizada, começamos re-explorar o experimento de absorção cooperativa de dois fótons por dois átomos aprisionados. Com nosso novo sistema, é possível explorar este efeito no regime clássico e quântico. Estamos interessados em explorar algumas características da interação não linear entre luz e matéria. A ideia de ter dois ou mais fótons interagindo com um ou mais átomos, é possivelmente o começo de uma nova classe de fenômenos que poderíamos chamar de interação de muitos fótons com muitos átomos.

Le travail effectué dans cette thèse a pour thème central la conception d’un aimant quadripolaire supraconducteur en Nb-Ti destiné à remplacer à l’horizon 2014 les aimants d’insertions actuellement utilisés dans le grand collisionneur de Hadrons (LHC) du CERN de Genève. Ce nouveau quadripôle, caractérisé par un diamètre d’ouverture encore jamais atteint (120 mm), ouvre la voie vers les quadripôles à grandes ouvertures. Tout d’abord, pour rapidement estimer l’énergie magnétique stockée dans un quadripôle de type cos2?, une formule analytique basée sur la décomposition en série de Fourier du courant et permettant d’estimer l’énergie avec une précision de 10 % est développée. Le design magnétique de la section transverse de la bobine du quadripôle est ensuite réalisé en utilisant une nouvelle méthode d’optimisation basée sur les équations analytiques du champ magnétique. Puis, pour la première fois, une estimation de la reproductibilité dans le positionnement des blocs de conducteurs dans des aimants Nb3Sn est faite. Elle a été réalisée à l’aide d’une méthode existante et grâce à la production récente de deux séries d’aimants Nb3Sn. Une comparaison avec les valeurs obtenues pour des aimants en Nb-Ti est présentée. Ensuite, une méthode analytique basée sur les statistiques et permettant d’expliquer certains phénomènes observés sur la dispersion des mesures magnétiques dans une série de quadripôles est développée. Enfin, on montre que l’incertitude sur la moyenne des harmoniques de champ est due pour la majorité des harmoniques à un phénomène statistique lié au nombre limité d’aimants dans la série et non à des erreurs systématiques / The main objective of the work presented in this thesis is the design of a quadrupole magnet based on Nb-Ti. It aims at replacing the current insertion quadrupoles used in the Large Hadron Collider (LHC) at CERN by 2014. This new quadrupole features an unprecedented large aperture (120 mm) and opens the way toward large aperture quadrupoles. First, to rapidly estimate the magnetic energy stored in a cos2?-type quadrupole, an analytical formula based on the Fourier transform of the current is developed. It allows estimating the energy with a precision of 10 %. Secondly, the magnetic design of the quadrupole coil cross-section is realized using a novel optimization method based on analytical equations of the magnetic field. Subsequently, for the first time, an estimate of the reproducibility in the coil-blocks positioning in Nb3Sn magnets is given. The estimate has been obtained by using an existing method and from tow recently built Nb3Sn magnet series. A comparison with values obtained for Nb-Ti magnets is also presented. Following this, an analytical method based on statistics is developed. It makes possible to explain some phenomenon observed on the dispersion of the magnetic measurement in a quadrupole series. Finally, we show that the uncertainty in the mean of the magnetic field errors is for most of the harmonics related to statistical errors due to the limited number of magnets in the series, and not because of systematic defects in the coil

A ênfase deste trabalho foi a aplicação da técnica de RMN em campo zero para a obtenção do acoplamento quadrupolar e dos espectros de RMN em banda larga dos núcleos de 27Al (amostra GdAl2), 139La e 55Mn (amostras de Manganita), à temperatura de 4,2 K. O objetivo do trabalho foi obter resultados confiáveis tanto em relação aos espectros quanto aos valores dos acoplamentos quadrupolares das amostras de GdAl2 e de Manganitas, e utilizar estes resultados para auxiliar a entender e a determinar algumas das propriedades físicas destes materiais (no caso do GdAl2 o comportamento tipo Spin-Glass e o efeito Magnetocalórico, no caso das Manganitas a Magnetoresistência Colossal). Para se determinar o valor do acoplamento quadrupolar utilizou-se a técnica de medida das oscilações quadrupolares. Os espectros de RMN, em banda larga, foram obtidos utilizando-se a técnica de eco de Hahn variando-se a frequência de excitação em uma faixa de 5 a 500 MHz. A maior sensibilidade do equipamento montado em nosso laboratório permitiu que se observassem os múltiplos ecos devidos à interação quadrupolar. Consequentemente, estes ecos permitiram a obtenção de espectros de RMNz de 27Al com alta resolução e a medida do valor do acoplamento quadrupolar diretamente do espectro. Também foi mostrado que os múltiplos ecos do 27Al são originados em regiões diferentes da amostra. Os resultados dos experimentos de oscilação quadrupolar em amostras de Manganitas permitiram que se observassem vários valores de acoplamento quadrupolar, que podem ser devido à desordem da estrutura cristalina dos octaedros de MnO6 ou à variação angular do ângulo entre o campo magnético hiperfino e a o eixo de fácil magnetização. Também foi mostrado que os valores de acoplamento quadrupolar mudam em função do elemento dopante utilizado. A aplicação do campo externo diminui a distribuição de acoplamento quadrupolar, mostrando que a aplicação do campo magnético externo causa mudanças ou na rede cristalina e/ou na orientação do campo magnético hiperfino e, consequentemente, sobre as propriedades físicas das Manganitas. A comparação entre os espectros de 139La e 55Mn das diferentes amostras de Manganita mostrou a coexistência de fases magnéticas. Estes resultados mostram que a técnica de RMNz é uma excelente ferramenta para se determinar o estado magnético fundamental dos materiais magnéticos e as mudanças na estrutura cristalina através da observação do acoplamento quadrupolar. / The emphasis of this work was the application of zero-field NMR technique to obtain the quadrupole coupling and NMR broadband spectra of the nuclei 27Al (GdAl2 sample), 139La and 55Mn (Manganites samples), at 4.2 K. The objective was to obtain reliable results for both spectra and quadrupole coupling values of samples GdAl2 and Manganites, and use these results to help understand and determine some of the physical properties of these materials (for GdAl2 the Spin-Glass type behavior and the Magnetocaloric effect and for Manganites the Colossal Magnetoresistance effect). To determine the value of the quadrupole coupling it was used the quadrupole oscillations technique. The NMR broadband spectra were obtained using the Hahn echo technique, in the frequency excitation range 5 to 500 MHz. The greater sensitivity of the equipment allowed observing multiples echoes due to quadrupole interaction, these echoes allowed to obtain spectra of zero field RMN of 27Al with high resolution and measure the value of the quadrupole coupling directly from the spectrum. It was also shown that the 27Al multiple echoes are generated in different regions of the sample. The quadrupole oscillation experiments results on Manganite samples have obtaned several values of quadrupole coupling, indicating that the Manganites Ferromagnetic Metallic Phase present high degree of disorder or, in the crystalline structures or in the hyperfine magnetic field direction. It was shown that the change in the value of the quadrupole coupling depends on the dopant used in the Manganites composition. The results of the quadrupole oscillations with application of an external magnetic field showed that the degree of disorder decreases due to the external magnetic field, showing the influence of the external magnetic field on the crystal network and/or in the hyperfine magnetic field direction, and consequently of some Manganites physical properties. The comparison between the spectra of 139La and 55Mn of the different Manganite samples shows the coexistence of different magnetic phases. These results showing that the technique of zero-field NMR is excellent to determine the fundamental magnetic state of the magnetic materials and observe changes in the crystal structure by the observation of the quadrupole coupling.

In this work we constructed an experimental system to realize a BEC of sodium atoms. In the first part of the work, we study two atomic sources in order to choose the most suitable for our system. The comparison between a Zeeman slower and a bidimensional magnetooptical trap (2D-MOT) was performed to evaluate the capacity of producing an appropiate flux of atoms in order to load a tridimensional magneto-optical trap (3D-MOT). The experimental results show that the 2D-MOT is as efficient as the Zeeman slower with the advantage of being more compact and easier to operate, and for these reasons we choose it as our source of cold atoms. After this, the experimental apparatus to produce a Bose-Einstein condensate was constructed and characterized. With this experimental system we realized all the required stages to achieve the Bose-Einstein condensation (BEC). Initially, we characterized and compared the performance between the Bright-MOT and Dark-SPOT MOT of sodium atoms, observing the great advantages this last configuration offers. Afterward, we implemented the experimental sequence for the achivement of the BEC of sodium atoms. After the optical molasses process, the atoms are tranferred to an optically plugged quadrupole trap (OPT) where the process of evaporative cooling is performed. With this setup, we achive a sodium BEC with ∼ 5×105 atoms and a critical temperature of ∼ 1.1 μK. Finally, with the constructed and characterized machine, we started to perform experiments of cooperative absorption of two photons by two trapped atoms. With the new system, we wanted to take advantage of the higher densities in the magnetic trap and BEC to explore some features of this phenomenon in the classical and quantum regimes. We were interested in exploring some features of this nonlinear light-matter interaction effect. The idea of having two or more photons interacting with two or more atoms is the beginning of a new possible class of phenomena that we could call many photons-many body intercation. In this new possibity, photons and atoms will be fully correlated, introducing new aspects of interactions. / Neste trabalho, realizamos a construção de um sistema experimental para a realização de um condensado de Bose-Einstein de átomos de sódio. Na primeira parte do trabalho, realizamos o estudo de duas fontes átomicas com o intuito de escolher a mais adequada para nosso sistema experimental. A comparação foi realizada entre um Zeeman slower e uma armadilha magneto-óptica bidimensional (MOT-2D), que são técnicas usadas para fornecer um grande fluxo de átomos com distribuição de velocidades adequadas para serem capturados numa armadilha magneto-óptica tridimensional (MOT-3D). Os resultados experimentais da caracterização de ambos os sistemas mostra que o MOT-2D oferece um grande fluxo atômico da mesma ordem do Zeeman slower, mas com a vantagem de ser um sistema mais compacto em questão de tamanho, razão pela qual foi escolhido como fonte atômica no nosso sistema. A partir daqui, realizamos a construção do sistema experimental para a realização do condensado de sódio. Inicialmente realizamos o aprisionamento numa MOT-3D, realizando subsequentemente os passos de resfriamento sub-Doppler mediante o processo de molasses ópticas. Depois disto, os átomos são transferidos para uma armadilha magnética, que consiste de um par de bobinas em configuração anti-Helmholtz, as mesmas usadas para a MOT-3D mas com um gradiente de campo magnético ao redor de uma ordem de grandeza maior. Esta armadilha é combinada com um laser com dessintonia para o azul focado a 30 μm no centro da armadilha, onde o campo magnético é zero com o objetivo de evitar as perdas por majorana que acontecem nessa região. Com esta configuração, um condensado de ∼ 5 × 105 átomos é obtido a uma temperatura crítica de ∼ 1.1 μK. Por último, com a máquina construída e caracterizada, começamos re-explorar o experimento de absorção cooperativa de dois fótons por dois átomos aprisionados. Com nosso novo sistema, é possível explorar este efeito no regime clássico e quântico. Estamos interessados em explorar algumas características da interação não linear entre luz e matéria. A ideia de ter dois ou mais fótons interagindo com um ou mais átomos, é possivelmente o começo de uma nova classe de fenômenos que poderíamos chamar de interação de muitos fótons com muitos átomos.

A química computacional apresenta a grande vantagem de prover informações fundamentais para espécies moleculares propostas, antes mesmo de sua síntese em laboratório. A Teoria do Funcional da Densidade é bastante utilizada nesta área, produzindo resultados satisfatórios para um grande número de propriedades e sistemas, mas com uma menor demanda por recursos computacionais que métodos mais avançados. Entretanto, o desenvolvimento de funcionais que incluem efeitos relativísticos ainda se encontra num estágio inicial. Em geral, tais efeitos são importantes em compostos de átomos pesados, embora devam ser considerados também em sistemas com átomos mais leves se a propriedade em estudo for particularmente sensível, como é o caso do gradiente de campo elétrico na posição de núcleos em moléculas. Assim, na primeira etapa desta dissertação foi avaliado o desempenho de funcionais comuns de troca-correlação não relativísticos, quando utilizados em conjunto com o formalismo de quatro componentes (tratamento relativístico), no estudo dos gradientes de campo elétrico em núcleos de átomos (índio, antimônio, iodo, lutécio e háfnio) constituindo moléculas diatômicas. Foram investigados funcionais baseados nas aproximações da densidade local e do gradiente generalizado, funcionais híbridos e que incluem correções em termos da atenuação com a distância. Nossos resultados, que estão em acordo com observações da literatura, ressaltam o melhor desempenho de funcionais híbridos e com correções de atenuação para esta propriedade e demonstram a importância do uso do método indireto. Posteriormente, foi feita uma nova parametrização de alguns dos melhores funcionais não relativísticos selecionados na etapa anterior (B3LYP, PBE0 e CAM-B3LYP), dentro do formalismo de quatro componentes, para uso no cálculo destes mesmos gradientes num grupo teste de átomos (cobre, iodo, lantânio e ouro) em moléculas lineares. Nestes casos, os funcionais modificados propostos tiveram um bom desempenho geral e foram particularmente bem sucedidos para cobre e ouro. Finalmente, é possível destacar o funcional híbrido PBE0 e sua modificação, proposta neste estudo, por conta de seu desempenho excelente, tanto para os metais como para os demais elementos que tiveram seus EFGs investigados aqui. / The computational chemistry has the great advantage of providing fundamental information for proposed molecular species even before their synthesis in laboratory. The Density Functional Theory is widely used in this area, producing satisfactory results for a large number of properties and systems, but with a lower demand for computational resources than that of more advanced methods. However, the development of functionals that include relativistic effects is still at an early stage. In general, these effects are important in compounds containing heavy elements, but they must also be considered in systems of lighter atoms if the studied property was particularly sensitive, as occurs for the electric field gradient at the position of nuclei in molecules. Thus, the first step of this dissertation was to evaluate the performance of common non-relativistic exchange-correlation functionals when used in conjunction with the four component formalism (relativistic treatment) in the study of electric field gradients at the nuclei of atoms (indium, antimony, iodine, lutetium and hafnium) forming diatomic molecules. Functionals based on the local density approximation and generalized gradient approximation, hybrid functionals and the ones that include attenuation corrections were investigated. Our results, which are in agreement with observations in the literature, highlight the best performance of hybrid functionals and attenuation corrections for this property and demonstrate the importance of using the indirect approach. Subsequently, there was a new parameterization of some of the best non-relativistic functionals selected in the previous step (B3LYP, PBE0 and CAM - B3LYP) within the four component formalism for calculations of these same gradients in a trial group of atoms (copper, iodine, lanthanum and gold) into linear molecules. In these cases, the modified functionals proposed had a satisfactory overall performance and were particularly successful for copper and gold. Finally, it is possible to mention the excellent performance of the hybrid functional PBE0 and its modification proposed in this study for both metals and the other elements that had their EFGs investigated here.

Performing quantitative analysis of targeted bioactive compounds in biological samples, such as blood plasma, cerebrospinal fluid or extracts from pig liver, put high demands on the ruggedness of the method acquiring the results. In addition to the complexity of the sample matrix, the bioactive compounds targeted for analysis usually have low levels of natural abundance, further increasing the demand on the analytical method sensitivity. Furthermore, quantitation of analytes at trace levels in the presence of large amounts of interfering species in biofluids must aim for repeatable precision, high accuracy ensuring the closeness to the true values, a linear response spanning over several orders of magnitude and low limits of quantitation to be valid for monitoring disease states in clinical analysis. An analytical method most commonly follow a certain order of events, called the analytical chain, which includes; experimental planning, sampling, sample pre-treatment, separation of species, detection, evaluation, interpretation and validation, all equally important for the outcome of the results. In this thesis, the scope has been to create novel methods, or to refine already existing methods, in order to achieve even better performances of the different events in the analytical chain. One of the aspects has been to sample and enrich analytes in vivo by the use of solid supported microdialysis, giving the advantage of almost real-time monitoring of analyte levels within a living host with targeted selectivity due to the analyte affinity for solid particles. Another aspect to selectively clean and enrich analytes in a complex matrix has been developed and automated on-line by the use of a column-switching technique before the analytical separation. By using several steps of extraction and separation coupled on-line to selected detection by the use of a triple quadrupole mass spectrometer facilitates great selectivity of species. The mass spectrometer also gives the ability to distinguish between isotopically labelled analogues coeluting with the analytes yielding the necessary accuracy for quantitative evaluation. Both development of analytical methods and clinical applications has been performed, as well as improvements of existing techniques, all to improve the quantitation of trace levels of targeted analytes in biofluids.