München, Techn. University, Diss., 2007.

Techn. Hochsch., Diss., 2001--Aachen.

NMR spectroscopy of paramagnetic solids provides detailed information about the local configuration and the chemical environment of the NMR observed center, as well as about the structural, magnetic and electronic properties of the coordianted paramagnetic centres. In the case of complex paramagnetic solids such as cathode materials for (rechargeable) batteries, NMR represents an invaluable tool to provide insight into the structural and electronic properties of the systems, which are at the base of the electrochemical performance of these materials. However, the paramagnetism makes the interpretation of the NMR data very challenging. This is primarily due to the interactions of the unpaired electrons with the NMR observed nucleus, and the interpretation of the NMR spectra often requires the aid of reliable theoretical and computational methods. Often the dominant interaction contributing to the measured isotropic shifts is the hyperfine interaction between the unpaired electrons and the observed nucleus, which results from the transfer of unpaired electrons from the paramagnetic centre(s) to the NMR observed site. In systems such as the ones studied here, in which the paramagnetic ions are a major constituent of the lattice, the multitide of different local environments results in a complex distribution of resonances. As in the case of the Li$_x$V$_6$O$_{13}$ cathode material, a methodical investigation of the configurational stability from first principles gives insight into the preferred site configurations. The combination of experimental $^7$Li NMR spectra and hyperfine shift DFT calculations of the so-found stable Li environments allows to unravel the complex lithiation mechanism of this material. In the other case of the LiTi$_x$Mn$_{2-x}$O$_4$ cathode materials, the $^7$Li hyperfine shifts calculated from first principles for a variety of Li environments are combined in a lattice model which allows to assign the isotropic regions of the experimental $^7$Li NMR spectra, helping to resolve the complex cation ordering as a function of Mn/Ti content in the series. For paramagnetic centres with an unquenched orbital component of the electron magnetic moment(s), the spin-orbit coupling effects also contribute to the paramagnetic NMR shift and shift anisotropy. A first principles model is derived, which describes how spin-orbit coupling and the single-ion $g$-tensor are defined and calculated in periodic paramagnetic solids, and how they can be coupled with the hyperfine interaction to model their effects on the NMR spectrum. The method is applied to a series of olivine-type LiTMPO$_4$ cathode materials (with TM = Mn, Fe, Co, and Ni) and the respective $^7$Li and $^{31}$P NMR spectra are simulated and compared with the experiments. The other paramagnetic effect considered in this thesis involves the bulk magnetic susceptibility (BMS), which is particularly important for paramagnetic single crystals and solids of complex shape. The BMS effect results from the discontinuity of the bulk susceptibility at the surface of the crystal, inducing a demagnetizing field throughout the sample which changes the measured NMR shift and shift anisotropy. A method to analytically calculate the demagnetising field and the BMS shift in crystals of different shapes is derived, and it is applied to a series of LiFePO$_4$ single crystals for which the $^7$Li NMR spectra are also measured experimentally. The study confirms that, particularly for $^7$Li NMR, the macroscopic shape-dependent BMS shift can indeed be a significant contribution to the measured resonances, determining the large variation in shift measured for the crystals of different shapes.

Neste trabalho, descrevemos o desenvolvimento do equipamento e o software necessários à implementação da técnica de obtenção de imagens por RMN. Nossos principais objetivos foram a construção de um sistema de controle e aquisição de dados que permitisse operar um espectrômetro de Fourier de RMN pulsada como um tomógrafo de RMN; por outro lado, visamos a construção de um espectrômetro que tivesse seus parâmetros facilmente reconfiguráveis pelo sistema de controle. O resultado foi um sofisticado equipamento que permite, além do proposto, trabalhar com técnicas de espectroscopia de alta resolução e espectroscopia em sólidos. Uma grande ênfase foi dada ao entendimento das técnicas De reconstrução de imagens, desde as convencionais até aquelas que constituem atualmente a fronteira de pesquisa nessa área. Os resultados obtidos com o sistema descrito são considerados bons, comparáveis aos das unidades construídas por empresas que operam comercialmente nessa área, em cooperação com centros localizados em universidades no exterior, pouco devendo a equipamentos similares (protótipos) desenvolvidos naqueles centros. / We describe in this work the development of hardware and software necessary to implement the Magnetic Resonance Imaging (MRI) techniques. Our major subjects were the construction of an acquisition and control system which allowed the operation of a pulsed Fourier NMR spectrometer as a NMR Tomograph; further we oriented the developing of a NMR spectrometer whose parameters could be easily reconfigured by the controlling system. As a result we obtained a sophisticated equipment which allows, more than the proposed, working with high resolution spectroscopic techniques and spectroscopy in solids. Since the basic techniques employed in NMR and CT Tomographs are well known, a great emphasis was also given on the understanding of the image reconstruction techniques that constitutes today the frontier of research in this area. The results obtained with the system described here are considered good, comparable to the results from commercial units developed in cooperation with imaging groups located in universities abroad.

Submitted by Luciana Ferreira (lucgeral@gmail.com) on 2018-01-11T11:34:22Z No. of bitstreams: 2 Tese - Mábio João Santana - 2017.pdf: 5831508 bytes, checksum: e1e52470fde694c18c0e418a051f7f3e (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2018-01-11T11:34:45Z (GMT) No. of bitstreams: 2 Tese - Mábio João Santana - 2017.pdf: 5831508 bytes, checksum: e1e52470fde694c18c0e418a051f7f3e (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2018-01-11T11:34:45Z (GMT). No. of bitstreams: 2 Tese - Mábio João Santana - 2017.pdf: 5831508 bytes, checksum: e1e52470fde694c18c0e418a051f7f3e (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2017-12-14 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The present study aims to trace the chemical profile and to quantify carbohydrates glucose, fructose and sucrose in both integral and nectar grape juices through 1H NMR experiments using two quantification methods – external and electronic (ERETIC) reference. Both methods were efficient and in one single experiment were able to quantify simultaneously the three carbohydrates, to characterize the main constituents, as well as allowed us to know the level of fruit maturity and ethanol content in the juices. We have also observed a high content of fructose in the integral grape juice, which can mean a healthy risk since at elevated concentrations this monosaccharide could lead to insulin resistance syndrome and hyperuricemia. Furthermore, an alarming fact is that among the 24 brands of nectar grape juices analyzed, only four brands fulfilled the established limits of sucrose content and two of them were present with a sucrose content higher than 10 times that allowed by current legislation, being such nonconformity undetectable by methods actually used. The statistical analyzes demonstrate the influence of relaxation time on the trend of grouping the data, associating the same sample in completely different groups when not observed the time of five times the relaxation time (T1). Other observation was also allowed us to observe the distinct grouping between the nectar samples, which were qualified as sweetened with apple juice, and this information was not included on the label at the time of analysis, even though it was established by legislation. / O presente estudo tem como objetivo avaliar o perfil químico e quantificar carboidratos de glicose, frutose e sacarose em sucos de uvas integrais e de néctar através de experimentos de RMN de 1H usando dois métodos de quantificação - referência externa e eletrônica (ERETIC). Ambos os métodos foram eficientes e em um único experimento foram capazes de quantificar simultaneamente os três carboidratos, para caracterizar os constituintes principais, além de nos permitir conhecer o nível de maturação da fruta e o teor de etanol nos sucos. Também observamos um alto teor de frutose no suco de uva integral, o que pode significar um risco à saúde, pois em concentrações elevadas este monossacarídeo pode levar a síndrome de resistência à insulina e hiperuricemia. Além disso, um fato alarmante é que, entre as 24 marcas de sucos de uva de néctar analisados, apenas quatro marcas preencheram os limites estabelecidos de teor de sacarose e dois deles apresentaram um teor de sacarose superior a 10 vezes permitido pela legislação atual, sendo essa não-conformidade indetectável por métodos oficialmente utilizados. As análises estatísticas demonstram a influência do tempo de relaxação na tendência de agrupamento dos dados, associando a mesma amostra em grupos completamente diferentes quando não observados o tempo de cinco vezes o tempo de relaxamento (T1). Outras observações também nos permitiram observar o agrupamento distinto entre as amostras de néctar, qualificadas como adoçadas com suco de maçã, e essa informação não foi incluída no rótulo no momento da análise, embora tenha sido estabelecida por legislação.

The results of a solid-state 11B NMR study of a series of boronic acids, boronic esters, and boronic acid catechol cyclic esters with aromatic substituents are reported in this thesis. Boron-11 electric field gradient (EFG) and chemical shift (CS) tensors obtained from analyses of spectra acquired in magnetic fields of 9.4 T and 21.1 T are demonstrated to be useful for gaining insight into the molecular and electronic structure about the boron nucleus. It can be concluded that when adequate electronic variation is present in the compounds being studied, Ω is generally the most characteristic boron NMR parameter of the molecular and electronic environment for boronic acids and esters. Importantly, these data are only reliably accessible in ultrahigh magnetic fields. The experimental span values result from a delicate interplay of several competing factors, including hydrogen bonding, the value of the dihedral angle, and the type of aromatic ring system present.

In the past decade, the field of NMR spectroscopy has seen the emergence of ever more powerful superconducting magnets, which has opened the door for the observation of many traditionally challenging or non-receptive nuclei. In this dissertation, a variety of ionic solids with organic coordination environments are investigated using quadrupolar solid-state NMR experiments with an ultrahigh-field magnet (21.1 T). Two general research directions are presented including a 79/81Br solid-state NMR study of a series of 6 triphenylphosphonium bromides for which single-crystal X-ray structures are reported herein. A second research direction is also presented wherein alkaline-earth metal (25Mg, 43Ca, and 87Sr) solid-state NMR is used to characterize a systematic series of 16 aryl and alkyl carboxylates. In both studies, the quadrupolar nuclei studied are deemed “exotic” due to their unreceptive nature to NMR spectroscopic analysis including low natural abundances, large quadrupole moments, or low resonance frequencies. A variety of coordination modes to alkaline-earth metals, including N-atom coordination, are characterized herein for the first time using alkaline-earth metal solid-state NMR. In all cases, the electric field gradient (EFG) and chemical shift (CS) tensors are characterized and correlated to structural features such as interatomic distances measured from the crystal structure of the compound under study. In all of the projects undertaken herein, the gauge-including projector-augmented-wave density functional theory (GIPAW DFT) method is used, which allows for the prediction and rationalization of the experimental EFG and CS tensor parameters based on the input crystal structure. In the case of 43Ca solid-state NMR experiments reported in this dissertation, a linear correlation between the calculated and experimental 43Ca quadrupolar coupling constants, CQ, is used as a calibration curve for GIPAW DFT calculations performed on the 18 structural models currently available for the vaterite polymorph of CaCO3. Vaterite cannot be fully characterized by X-ray diffraction alone; therefore an NMR crystallography protocol is used in order to identify the model that best accounts for 43Ca solid-state NMR experiments performed on vaterite. It is expected that the conclusions from this dissertation can be used for future studies involving structural refinement and elucidation of solid materials containing challenging quadrupolar nuclei.

Rhomboids are a family of intramembrane serine proteases that cleave transmembrane protein substrates within the lipid membrane. They are involved in a wide range of biological processes, including signal transduction, parasite invasion, bacterial quorum sensing and apoptosis. While previous X-ray crystal structures and functional studies have provided some detailed insights into the mechanism of intramembrane hydrolysis, it is still not clear how the transmembrane substrate can gain access into the active site from the lipid environment. While several modes of action have been suggested, one hypothesis proposes a lateral movement of the fifth transmembrane helix, causing a displacement that would allow transmembrane substrates to enter the rhomboid active site. A powerful method that has the potential to yield insights into rhomboid dynamics is solution NMR; however, the large size of rhomboid protease samples has complicated conventional methods typically used to assess protein structure and dynamics. ¹⁹F NMR could allow the study of rhomboid conformational dynamics by providing a simplified spectrum with high sensitivity to changes in local chemical environments. In this thesis various methods of ¹⁹F incorporation were evaluated for utility in studying rhomboid conformational dynamics, focusing on the GlpG rhomboid from E. coli. First, GlpG samples were prepared with ¹⁹F incorporated into tryptophan sidechains, and 1D ¹⁹F NMR spectra were acquired. While spectra with decent spectral dispersion were obtained, the assignment process was complicated by low signal-to-noise, and multiple changes in the spectrum introduced by the mutation. Chemoselective labelling of cysteine residues with probes containing a trifluoromethyl group was also investigated and found to give rise to well resolved ¹⁹F NMR spectra with promising characteristics. In addition, protocols for incorporation of trifluoromethyl-phenylalanine using unnatural amino acid incorporation at introduced amber codon sites were also explored, since one of the long-term goals of this work is to study ¹⁹F-labelled GlpG in its native lipid environment. For this purpose, some protocol development was also performed to introduce GlpG into lipid nanoparticles using styrene maleic acid co-block polymers. However, low expression yields of trifluoromethyl-phenylalanine-labelled GlpG and the large size of the lipid nanoparticles are not yet compatible with solution NMR. Nonetheless, this thesis lays the groundwork for further development of these samples to allow the future study of conformational exchange of GlpG in native lipid membranes.

Diese Arbeit befasst sich mit der Charakterisierung einer verhältnismäßig wenig beforschten Untergruppe der hochtemperatur-supraleitenden Kuprate (HTSCs-high-temperature superconducting cuprates), den elektronendotierten HTSCs, vermittels kernmagnetischer Resonanz (NMR-nuclear magnetic resonance). Die Untersuchungen umfassen 63Cu und 17O NMR an ausgerichteten Pulverproben und Einkristallen von Pr2−xCexCuO4 (x = 0, 0.05, 0.10, 0.15, 0.20) sowie auch Nd2−xCexCuO4 (x = 0, 0.13) in externen Magnetfeldern von 2.35 bis 17.6 T und Temperaturen zwischen 8 und 400 K. Durch eine Vielzahl von Experimenten wird die erste eindeutige spektrale Analyse für beide Nuklide vorgenommen. Es wird gezeigt, dass die indirekte, homonukleare Kopplung, wie sie beim Hahn-Echo-Zerfall von planarem 63,65Cu in lochdotierten HTSCs und auch im undotierten Pr2CuO4 gefunden wird, durch Elektronendotierung weitestgehend unterdrückt wird. Eine Analyse der Quadrupolaufspaltungen zeigt, dass nicht nur die lokale Verteilung der dotierten Elektronen und Löcher in den CuO2-Schichten quantitativ gemessen werden kann, sondern, dass auch Unterschiede in den 63Cu und 17O Aufspaltungen verschiedener undotierter Kuprate auf eine variable Ladungsverteilung zurückzuführen sind. Somit ist eine quantitative Messung der lokalen Ladungsverteilung in der CuO2 -Schicht der HTSCs möglich, welche ein neues, differenziertes Bild der unterschiedlichen Materialien ergibt.

Moderne Hochdruckforschung entwickelt sich rasant zu einer der vielfältigstens und überraschensten Disziplinen der Festkörperphysik. Unter Benutzung von Diamantstempelzellen können Drücke erreicht werden, die den Bedingungen im Inneren unserer Erde ähneln. Eine Anwendung von Kernmagnetischen Resonanzexperimenten (NMR) in Diamantstempelzellen galt jedoch fur lange Zeit als unmöglich. In der vorliegenden Arbeit wird ein neuartiger Ansatz weiterentwickelt, der Radiofrequenz-(RF)-Mikrospulen benutzt, die direkt zwischen den Diamantstempeln platziert werden, und somit zu einer signififikanten Sensitivitatssteigerung führen. Es ist gelungen, Hochdruckzellen zu entwickeln, die fur die speziellen Anforderungen der NMR zugeschnitten sind. Des Weiteren konnte eine nicht metallische, nicht magnetische Dichtung entwickelt werden, die zudem zu einer signififikanten Stabilisierung des Probenvolumens führt. Eine breit angelegte Analyse der Leistungsfähigkeit dieser neuartigen NMR-Hochdruckprobenköpfe zeigt deren Leistungsfähigkeit mit sehr hohen Empfifindlichkeiten sowie einer exzellenten RF Anregung und Zeitauflösung. Drei Anwendungsbeispiele, die das Potenzial dieses Ansatzes in dieser Arbeit unterstreichen, werden vorgestellt. Bei Drücken von bis zu 4 GPa werden die elektronischen und dynamischen Eigenschaften von elementarem Gallium untersucht. Unter höheren Drücken ist es gelungen, einen druckinduzierten Isolator-Metall-Übergang in dem ternaren Chalkogenid AgInTe2 zu beobachten. Schlussendlich ist es gelungen, die strukturellen und elektronischen Eigenschaften von Rubin bei Drücken von bis zu 30.5 GPa zu untersuchen, was einer Verdreifachung des bisher zugänglichen experimentellen Druckbereiches entspricht und die NMR fur moderne Hochdruckanwendungen möglich macht.