Carbohydrates are essential biomolecules that decorate cell membranes and proteins in organisms. They are important both as structural elements and as identification markers. Many biological and pathogenic processes rely on the identification of carbohydrates by proteins, thereby making them attractive as molecular blueprints for drugs. This thesis describes how NMR spectroscopy can be utilized to study carbohydrates in solution at a molecular level. This versatile technique facilitates for investigations of (i) shapes, (ii) motions and (iii) interactions. A conformational study of an E. coli O-antigen was performed by calculating atomic distances from NMR NOESY experiments. The acquired data was utilized to validate MD simulations of the LPS embedded in a membrane. The agreement between experimental and calculated data was good and deviations were proven to arise from spin-diffusion. In another study presented herein, both the conformation and the dynamic behavior of amide side-chains linked to derivatives of D-Fucp3N, a sugar found in the O-antigen of bacteria, were investigated. J-couplings facilitated a conformational analysis and 13C saturation transfer NMR experiments were utilized to measure rate constants of amide cis-trans isomerizations. 13C NMR relaxation and 1H PFG diffusion measurements were carried out to explore and describe the molecular motion of mannofullerenes. The dominating motions of the mannofullerene spectral density were found to be related to pulsating motions of the linkers rather than global rotational diffusion. The promising inhibition of Ebola viruses identified for a larger mannofullerene can thus be explained by an efficient rebinding mechanism that arises from the observed flexibility in the linker. Molecular interactions between sugars and caffeine in water were studied by monitoring chemical shift displacements in titrations. The magnitude of the chemical shift displacements indicate that the binding occurs by a face to face stacking of the aromatic plane of caffeine to the ring plane of the sugar, and that the interaction is at least partly driven by solvation effects. Also, the binding of a Shigella flexneri serotype Y octasaccharide to a bacteriophage Sf6 tail spike protein was investigated. This interaction was studied by 1H STD NMR and trNOESY experiments. A quantitative analysis of the STD data was performed employing a newly developed method, CORCEMA-ST-CSD, that is able to simulate STD data more accurately since the line broadening of protein resonances are accounted for in the calculations. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Manuscript. Paper 4: Manuscript. Paper 5: Manuscript.</p>

Das Ziel der vorliegenden Arbeit war die Klärung der Fragestellung, ob sich die quantitative NMR-Spektroskopie zur Bestimmung von Identität, Reinheit und Gehalt von Arzneistoffen eignet, und wie sich Präzision und Empfindlichkeit dieser Methode im Vergleich zu etablierten chromatographischen Verfahren verhalten. Die quantitative Untersuchung der drei strukturell jeweils verwandten Mehrkomponentengemische Codergocrinmesilat, Clomifencitrat und Flupentixoldihydrochlorid bewies eindrucksvoll die Eignung der 1H-NMR-Spektroskopie als orthogonale, analytische Messmethode im Vergleich zu validierten HPLC-Arzneibuchmethoden. Die im Rahmen einer Validierung der 1H-NMR-Methode ermittelten Ergebnisse erfüllten bezüglich Präzision und Richtigkeit die an eine im pharmazeutischen Bereich eingesetzte analytische Methode gestellten Anforderungen; zudem wurden weitere Prüfparameter wie Selektivität, Linearität, Robustheit und Stabilität verifiziert. Externe-Standard-Experimente wie "Zwei-Röhrchen-Methode" und ERETIC-Verfahren bestätigten die quantitativen Ergebnisse der Internen Standardisierung; jedoch wurde hier -- insbesondere für die ERETIC-Technik -- eine höhere Fehleranfälligkeit und somit eine größere Streuung der Einzelergebnisse beobachtet. Am Beispiel von Codergocrinmesilat und Flupentixoldihydrochlorid konnte zudem die Eignung anderer NMR-aktiver Kerne wie 13C und 19F für die quantitative Analyse von komplexen Substanzgemischen aufgezeigt werden. Das Potential der 1H-NMR-Spektroskopie für die Reinheitsprüfung von Arzneistoffen wurde am Beispiel der Aminosäure L-Alanin aufgezeigt. Die zu erwartenden Verunreinigungen Glutamin-, Asparagin-, Äpfel- und Fumarsäure konnten im Gegensatz zu den "veralteten" Prüfmethoden des Europäischen Arzneibuches eindeutig identifiziert und quantifiziert werden; mit einer Bestimmungsgrenze von <= 0.03% wurden die Vorgaben der ICH-Richtlinie Q3A(R2) erfüllt. Die deutliche Übereinstimmung der NMR-spektroskopisch ermittelten Ergebnisse einer quantitativ untersuchten Alanin-Modellmischung mit einer für den Routinebetrieb geeigneten HPLC-Methode unter Einsatz verschiedener Detektoren wie CAD, NQAD, ELSD und MS, sowie der Vergleich wichtiger Prüfparameter wie Linearität und Nachweisgrenze bestätigten die Eignung der 1H-NMR-Spektroskopie im Rahmen der routinemäßig durchgeführten Qualitätskontrolle. Die Aufdeckung von Arzneimittelfälschungen mit Hilfe der NMR-Spektroskopie wurde im Rahmen dieser Arbeit anhand der zwei aktuellen Fallbeispiele Heparin und Glycerin näher untersucht. Die in Zusammenhang mit dem Heparin-Skandal verantwortliche Kontaminante OSCS konnte neben Dermatansulfat und weiteren natürlich vorkommenden Glykosaminoglykan-Verunreinigungen im 1H-NMR-Spektrum eindeutig identifiziert und auf 0.1% OSCS bzw. 0.5% Dermatansulfat begrenzt werden. Eine präzise und richtige quantitative Bestimmung der beiden Glykosaminoglykane wurde über die N-Acetyl-Resonanzen mit Hilfe der Signalhöhenbestimmung und dem Standard-Additionsverfahren ermöglicht; deutliche Abweichungen vom "wahren" Gehalt wurden hingegen, bedingt durch starke Signalüberlagerungen, nach Flächenvergleich beobachtet. Weitere Verunreinigungen, insbesondere Lösungsmittelrückstände, die während des Extraktions- und Reinigungsprozesses des Heparins eingesetzt werden, konnten ebenfalls über charakteristische Resonanzen identifiziert und mit Hilfe der Internen-Standard-Methode quantitativ erfasst werden. Eine umfangreiche Untersuchung von 145 Heparin-API-Mustern mittels NMR-Spektroskopie und weiteren, neuentwickelten Verfahren wie HPLC, CE, IR- und Raman-Spektroskopie konnte die Eignung der entwickelten 1H-NMR-Methode bestätigen. Potentielle Glycerin-Kontaminanten wie Diethylenglycol und Ethylenglycol konnten ebenso wie eine weitere, natürlich vorkommende Verunreinigung, Propylenglycol, mittels 1H- und 13C-NMR-Spektroskopie identifiziert und quantifiziert werden. Beide Methoden erfüllten die in der USP beschriebenen Anforderungen, die für pharmazeutisch eingesetztes Glycerin jeweils höchstens 0.1% Diethylenglycol bzw. Ethylenglycol erlaubt. Während die quantitative Reinheitsprüfung beim Einsatz der 1H-NMR-Spektroskopie mit einer Messdauer im Bereich von etwa 30 min für den Routineeinsatz geeignet ist, ist die entwickelte quantitative 13C-NMR-Methode beim Einsatz von Spektrometern geringer Magnetfeldstärke aufgrund einer geringen Nachweisempfindlichkeit und der NOE-Problematik für den Routinebetrieb nur bedingt anwendbar. Abschließend kann zusammengefasst werden, dass die untersuchten Beispiele die NMR-Spektroskopie als in hohem Maße geeignet für die quantitative Analyse von Arzneimitteln ausweisen. / The main objective of the present thesis was the investigation of the suitability of quantitative NMR spectroscopy for identification, purity assay, and quantification of a given drug, as well as a comparison of precision and sensitivity of this method with well-established chromatographic routines. The quantitative analysis of the three multi-component drug mixtures codergocrine mesylate, clomiphene citrate, and flupentixol dihydrochloride strikingly demonstrates the suitability of the 1H NMR spectroscopy as an independent analytical measurement technique in comparison to validated HPLC methods of international pharmacopoeias. Concerning precision and accuracy, the results obtained from validation of the 1H NMR method met the requirements that are made on an analytical routine for pharmaceutical purposes; additionally, further validation parameters such as selectivity, linearity, robustness, and stability have been verified. Experiments like the "twin tube" and ERETIC techniques utilizing external standards confirm these results; however, in this context an increased error rate and therefore larger variance was observed, especially in the case of ERETIC. By means of codergocrine mesylate and flupentixol dihydrochloride, additionally the suitability of other NMR active nuclei as 13C or 19F for quantification of complex mixtures was shown. The potential of the 1H NMR spectroscopy for purity assays was demonstrated for the example of the amino acid L-alanin. Identification and quantification of the expected impurities glutamic acid, aspartic acid, malic acid, and fumaric acid was possible, in contrast to "out-dated" test methods of the European Pharmacopoeia; achieving a limit of quantification <= 0.03%, the demands of the ICH guideline Q3A(R2) have been met. Concerning the quantification of an alanine model mixture, the clear agreement between the results obtained by means of NMR spectroscopy and a HPLC method using various detectors like CAD, NQAD, ELSD, and MS, suited for routine analysis, as well as the comparison of various relevant parameters such as linearity and limit of quantification confirmed the qualification of 1H NMR spectroscopy in the field of routine quality assurance. Within the scope of this work, the disclosure of counterfeit drugs by means of NMR spectroscopy was investigated in detail utilizing two current case studies, namely heparin and glycerin. Besides dermatan sulfate and other natural occurrences of glycosaminoglycan impurities, the contaminant OSCS revealed in connection with the recent heparin affair was clearly identified in the 1H NMR spectrum and these contaminants could be limited to 0.1% OSCS and 0.5% dermatan sulfate, respectively. A precise and accurate quantification of these two glycosaminoglycanes was achieved using signal height and standard addition methods applied to the N-acetyl resonances; comparison of signal areas however yielded considerable deviations from the "true" content, which are due to strong signal overlap. Further contaminants, especially solvent residues originating from the extraction and purification processes of heparin, have been able to be identified with the help of characteristic resonances; their quantification was possible. An extensive study of 145 heparin API samples by means of NMR spectroscopy and other novel techniques such as HPLC, capillary electrophoresis, IR and Raman spectroscopy confirmed the qualification of the developed 1H NMR method. Potential contaminants in glycerin such as diethylene glycol and ethylene glycol have been able to be identified as well as quantified by means of 1H and 13C NMR spectroscopy, as was the case for propylene glycol, which is naturally present. Both methods met the requirements of the USP, limiting the amount of diethylene glycol and ethylene glycol for pharmaceutical purposes to 0.1%, respectively. While 1H NMR spectroscopy with a measurement time of about 30 min is well suited for routine application, the applicability of the 13C NMR method is limited due to the NOE effect and the low sensitivity at low field strengths. In conclusion, each of the attended topics showed, that NMR spectroscopy is a powerful tool within the framework of quantitative drug analysis.

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.

Nesta dissertação, apresentamos uma aplicação simples de RMN de 1H no domínio do tempo (TD-NMR) de baixo campo para caracterização de dinâmica molecular variando do regime intermediário ao rápido. O método se baseia no filtro dipolar seguido da aplicação do Mixed Magic Sandwich Echo(MSE), o qual denominamos DF-MSE. O filtro dipolar suprime os sinais oriundo de segmentos com mobilidade abaixo de kHz, de modo que somente segmentos móveis sejam detectados. Assim, a dependência com a temperatura da intensidade do sinal mostra diretamente a temperatura em que movimentos moleculares ocorrem ao atingirem taxas maiores que kHz. Para que não ocorra variação da intensidade com a temperatura, mas somente pelos movimentos moleculares, os sinais são normalizados por uma intensidade de referência obtida pela aquisição de DF-MSE sem aplicação do filtro dipolar. A intensidade normalizada DF-MSE pode ser descrita adequadamente por uma expressão analítica baseada na aproximação de Anderson-Weiss, de forma a permitir que parâmetros de ativação de movimentos sejam avaliados. Ademais, também propomos um método baseado na diferença entre sinais DF-MSE normalizados adquiridos com tempos de filtro distintos, permitindo assim quantificar a largura da ditribuição de tempos de correlação de uma forma independente. A aplicação geral foi testada de forma bem sucedida em polímeros monofásicos e multifásicos. De fato, o método apresentado é um prosseguimento da análise feita pelo MSE já presente na literatura, porém sondando movimentos mais rápidos e com uma forma aprimorada para avaliação de heterogeneidades de movimento. / In this dissertation, we present a simple NMR approach for characterizing intermediate to fast regime molecular dynamics using 1H time-domain NMR (TD-NMR) at low magnetic field. The method is based on a dipolar filter followed by a Mixed Magic Sandwich Echo and FID acquisition, which is symbolized DF-MSE. The dipolar filter suppresses the signals of segments presenting sub kHz mobility, so only signals from mobile segments are detected. Thus, the temperature dependence of the signal intensities directly evidences the onset of molecular motions with rates higher than kHz. In order to avoid temperature variation of the signal intensities other than that due to motions, the signals are normalized by a reference intensity obtained in a DF-MSE acquisition without the dipolar filter. The normalized DF-MSE intensity can be well described by an analytical function based on the Anderson-Weiss approach, so the activation parameters of the motion can be evaluated. Furthermore, we also propose a method based on the difference between normalized DF-MSE signals acquired with different dipolar filter times, which provide evaluation of the width of the distribution of correlation times in an independent fashion. The general approach was successfully tested in single and multiphase polymer systems. Indeed, the presented method is a follow up of the MSE analysis previously reported, but probing faster motions and with an improved way of evaluating the motion heterogeneities.

L’émergence des méthodes de déréplication comme moyen d’identification rapide des substances naturelles connues implique le développement conjoint d’outils informatiques dédiés au traitement et à l’analyse des données spectrales. Dans ce contexte, les travaux présentés dans ce mémoire ont porté sur le développement de deux méthodes in silico de déréplication par résonance magnétique nucléaire (RMN). La première méthode, DerepCrud, permet l’identification des molécules naturelles à partir d’extraits naturels bruts en utilisant des données de RMN du 13C. La méthode permet de comparer des spectres de RMN 1D du 13C issus de l’analyse d’un extrait naturel à ceux des molécules naturelles répertoriées dans une base de données locale afin de pouvoir identifier les composés majoritaires. La deuxième méthode, BCNet, permet d’exploiter les données RMN bidimensionnelles (HMBC et HSQC) pour la déréplication de molécules naturelles. L’algorithme construit un réseau de corrélations HMBC formés par les signaux appartenant aux différentes molécules constituant un extrait puis isole les signaux de chaque molécule grâce à l’utilisation d’algorithmes de détection de communautés. Les molécules sont enfin identifiées en effectuant une recherche dans la base de données des corrélations HMBC. A la fin de la procédure, la présence des molécules identifiées est confirmée par une comparaison de leurs corrélations HSQC théoriques (aussi issues de la base de données) avec les corrélations expérimentales correspondantes afin de renforcer la précision de l’identification. / The emergence of dereplication strategies as a new tool for the rapid identification of the natural products from complex natural extracts has unveiled a great need for cheminformatic tools for the treatment and analysis of the spectral data. The present thesis deals with the development of in silico dereplication methods based on Nuclear Magnetic Resonance (NMR). The first method, DerepCrud, is based on 13C NMR spectroscopy. It identifies the major compounds contained in a crude natural extract without any need for fractionation. The principle of the method is to compare the 13C NMR spectrum of the analyzed mixture to a series of 13C NMR chemical shifts of natural compounds stored in a local database. The second method, BCNet, is designed to exploit the richness of 2D NMR data (HMBC and HSQC) for the dereplication of the natural products. BCNet traces back the network formed by the HMBC correlations of the molecules present in a naturel extract, then isolates the groups of correlations belonging to the individual molecules using a community detection algorithm. The molecules are identified by searching these correlations within a locally constructed database that associates natural product structures and 2D NMR peak positions. Finally, the HSQC correlations of the molecules identified during the previous step are compared to the experimental HSQC correlations of the studied extract in order to increase the quality of identification accuracy.

Silicon (in the form of lithium silicides) has almost ten times the theoretical charge storage capacity of graphite, the anode material used in most commercially-available lithium-ion batteries. Replacing graphite with silicon therefore promises a substantial improvement over the state-of-the-art in electrochemical energy storage. However, it has proved difficult to realise this high theoretical capacity in a practical electrochemical cell and maintain it over repeated charge-discharge cycles. This dissertation presents experimental work probing the changes in local structure occurring during the electrochemical reactions of lithium with silicon, using neutron total scattering and nuclear magnetic resonance, together with novel processing methodologies for analysing the resulting data, in the hope of suggesting ways of improving the performance of silicon-based lithium-ion batteries. Neutron total scattering patterns were obtained from silicon-based anode materials extracted from cells at various states of charge. These samples were composed of a heterogeneous mixture of amorphous, crystalline and disordered crystalline materials. Reverse Monte Carlo is a technique for obtaining structural information from experimental data (particularly total scattering patterns) from amorphous and disordered crystalline materials. However, previously existing Reverse Monte Carlo software could only handle homogeneous materials. Therefore, the RMCprofile software package was extended to handle data from heterogeneous samples. The improved RMCprofile was applied to the aforementioned total scattering patterns, but the much stronger scattering from the other components (themselves not well-characterised) swamped that from the lithium silicide. Future work should attempt to reduce the scattering from the inactive components, particularly the hard-to-model incoherent scattering. NMR data were acquired in situ from silicon-nanowire-based lithium-ion batteries during repeated charge-discharge cycles, achieving much better electrochemical performance than had been seen in previous in situ experiments with silicon. Owing to the large quantities of data obtained, an automated, model-free dimensionality reduction technique was needed. The NMR data were processed using principal component analysis and a variant of non-negative matrix factorisation. With both of these methods, one of the components was found to be associated with high voltages vs. ${Li \vert{} Li^{+}}$ (i.e. a fully discharged anode). This region has seen very little interest by comparison with the low voltage (high levels of lithiation) region of the charge-discharge cycle, so this discovery suggests a new avenue for future research.

Nesta dissertação, apresentamos uma aplicação simples de RMN de 1H no domínio do tempo (TD-NMR) de baixo campo para caracterização de dinâmica molecular variando do regime intermediário ao rápido. O método se baseia no filtro dipolar seguido da aplicação do Mixed Magic Sandwich Echo(MSE), o qual denominamos DF-MSE. O filtro dipolar suprime os sinais oriundo de segmentos com mobilidade abaixo de kHz, de modo que somente segmentos móveis sejam detectados. Assim, a dependência com a temperatura da intensidade do sinal mostra diretamente a temperatura em que movimentos moleculares ocorrem ao atingirem taxas maiores que kHz. Para que não ocorra variação da intensidade com a temperatura, mas somente pelos movimentos moleculares, os sinais são normalizados por uma intensidade de referência obtida pela aquisição de DF-MSE sem aplicação do filtro dipolar. A intensidade normalizada DF-MSE pode ser descrita adequadamente por uma expressão analítica baseada na aproximação de Anderson-Weiss, de forma a permitir que parâmetros de ativação de movimentos sejam avaliados. Ademais, também propomos um método baseado na diferença entre sinais DF-MSE normalizados adquiridos com tempos de filtro distintos, permitindo assim quantificar a largura da ditribuição de tempos de correlação de uma forma independente. A aplicação geral foi testada de forma bem sucedida em polímeros monofásicos e multifásicos. De fato, o método apresentado é um prosseguimento da análise feita pelo MSE já presente na literatura, porém sondando movimentos mais rápidos e com uma forma aprimorada para avaliação de heterogeneidades de movimento. / In this dissertation, we present a simple NMR approach for characterizing intermediate to fast regime molecular dynamics using 1H time-domain NMR (TD-NMR) at low magnetic field. The method is based on a dipolar filter followed by a Mixed Magic Sandwich Echo and FID acquisition, which is symbolized DF-MSE. The dipolar filter suppresses the signals of segments presenting sub kHz mobility, so only signals from mobile segments are detected. Thus, the temperature dependence of the signal intensities directly evidences the onset of molecular motions with rates higher than kHz. In order to avoid temperature variation of the signal intensities other than that due to motions, the signals are normalized by a reference intensity obtained in a DF-MSE acquisition without the dipolar filter. The normalized DF-MSE intensity can be well described by an analytical function based on the Anderson-Weiss approach, so the activation parameters of the motion can be evaluated. Furthermore, we also propose a method based on the difference between normalized DF-MSE signals acquired with different dipolar filter times, which provide evaluation of the width of the distribution of correlation times in an independent fashion. The general approach was successfully tested in single and multiphase polymer systems. Indeed, the presented method is a follow up of the MSE analysis previously reported, but probing faster motions and with an improved way of evaluating the motion heterogeneities.

This thesis investigates the chemistry of ammonia borane (NH3BH3) relevant to the development of hydrogen storage systems for vehicular applications. Because of its high hydrogen content and low molecular weight ammonia borane has the potential to meet stringent gravimetric hydrogen storage targets of gt;9 wt%. Two of the three moles of H2 in ammonia borane can be released under relatively mild conditions, with the highest gravimetric yield obtained in the solid-state. However, ammonia borane does not deliver sufficient H2 at practical temperatures and the products formed upon H2 loss are not amenable to regeneration back to the parent compound. The literature synthesis of ammonia borane was modified to facilitate large scale synthesis, and the deuterated analogues ND3BH3 and NH3BD3 were prepared for the purpose of mechanistic studies. The effect of lithium amide on the kinetics of dehydrogenation of ammonia borane was assessed by means of solid-state reaction in a series of specific molar ratios. Upon mixing lithium amide and ammonia borane, an exothermic reaction ensued resulting in the formation of a weakly bound adduct with an H2N...BH3-NH3 environment. Thermal decomposition at or above temperatures of 50eg;C of this phase was shown to liberate gt;9 wt% H2. The mechanism of hydrogen evolution was investigated by means of reacting lithium amide and deuterated ammonia borane isotopologues, followed by analysis of the isotopic composition of evolved gaseous products by mass spectrometry. From these results, an intermolecular multi-step reaction mechanism was proposed, with the rates of the first stage strongly dependent on the concentration of lithium amide present. Compounds exhibiting a BN3 environment (identified by means of solid-state sup1;sup1;B NMR spectroscopy) were formed during the first stage, and subsequently cross link to form a non-volatile solid. Further heating of this non-volatile solid phase ultimately resulted in the formation of crystalline Li3BN2 - identified by means of powder X-ray diffractometry. This compound has been identified as a potential hydrogen storage material due to its lightweight and theoretically high hydrogen content. It may also be amenable to hydrogen re-absorption. The LiNH2/CH3NH2BH3 system was also investigated. Thermal decomposition occurred through the same mechanism described for the LiNH2/NH3BH3 system to theoretically evolve gt;8 wt% hydrogen. The gases evolved on thermal decomposition were predominantly H2 with traces of methane detected by mass spectrometry.

Even though electrophoretic NMR (eNMR) experiments may provide unique chemical information and have been performed for three decades, the technique is still rarely applied, mainly because several experimental sources of artifacts have to be controlled to achieve accurate results. In this thesis, new experimental setups and protocols for accurate and precise eNMR experiments are presented. These include a novel eNMR sample cell, a radiofrequency filter and methods to suppress bulk flow effects. These developments improved the signal-to-noise ratio by roughly an order of magnitude compared to the U-tube setup previously used for eNMR. Convection-compensated pulse sequences in combination with a phase correction method were found to efficiently suppress bulk flow effects in the experiments and greatly increase experimental accuracy. These experimental setups and protocols were applied to probe association of ions and molecules in solution. It is particularly illustrated that the combination of diffusion and eNMR has great potential to provide quantitative results on ionic and molecular association in a variety of systems. The extent to which ionic surfactants associate with uncharged cyclodextrin probed by eNMR yielded very similar results to those obtained by diffusion NMR experiments. Complexation of a large set of small mono- and polyvalent metal cations to poly(ethylene oxide) was quantified by estimating the effective charge of the polymer through combined diffusion and eNMR information. Significant association was found for cations that have a surface charge density below a critical value. Ion pairing between tetramethylammonium cations and a series of anions in several solvents was also probed by diffusion NMR and eNMR experiments. For the monovalent anions in ethanol and ethanol-water mixture a dependence on ionic size was demonstrated. In water, dimethylsulfoxide, and methanol no such trend and very little pairing was observed. In acetonitrile, a different pattern was seen that did not correlate well with any single ionic parameter. An experimental cell and procedures for electrokinetic studies of solvated proton-conducting polymer materials is also presented. Electro-osmotic flow and diffusion were studied for each molecular component in water-methanol mixtures that swell Nafion membranes. / Elektroforetisk NMR (eNMR) är en experimentell metod som funnits i tre decennier och som kan ge unik kemisk information. Ändå används den sällan då flera experimentella artefakter måste korrigeras för, om man ska få korrekta resultat. I denna avhandling presenteras nya experimentella uppställningar och protokoll ämnade att uppnå korrekta och noggranna resultat. Dessa inkluderar en ny mätcell, ett radiofrekvensfilter och metoder för att minimera effekten av samtidiga bulkflöden i provlösningen. Sammantaget uppnås ungefär en storleksordning högre signal-brus-förhållande jämfört med den U-rörsuppställning som tidigare använts. Konvektions-kompenserande pulssekvenser i kombination med en faskorrektionsteknik minskade också bulkflödeseffekter effektivt, vilket ökade resultatens noggrannhet högst avsevärt. De experimentella uppställningarna och protokollen användes här för att mäta association av joner och molekyler i lösning. Mätningarna visar att kombinationen diffusions- och eNMR har en stor potential att kvantitativt kunna bestämma associationgraden i många olika typer av kemiska system. Associationsgraden mellan joniska tensider och cyklodextriner undersöktes både med eNMR och diffusions-NMR, och resultaten var mycket lika. Komplex-bildningen mellan en serie enkel- och flerladdade metalljoner och poly-(etylenoxid) kvantifierades genom att uppskatta polymerens effektiva laddning från kombinerad diffusions- och eNMR. Betydande komplexbildning hittades för katjoner med ytladdningstäthet under ett kritiskt värde. Jonparbildning mellan tetrametylammoniumjoner och en serie av anjoner i flera olika lösningsmedel undersöktes också med diffusions- och eNMR. För de monovalenta anjonerna i etanol och etanol-vatten-blandning påvisades ett samband med jonstorleken. I vatten, dimetylsulfoxid och metanol var däremot jonparbildningen låg och inget liknande samband hittades. I acetonitril observerades ett annat mönster, som inte korrelerade bra med någon av anjonernas normala joniska karakteristika. Slutligen presenteras en mätcell och procedurer för elektrokinetiska studier i de solvatiserade protonledande polymermaterial som bland annat används i bränsleceller. Elektroosmotiskt flöde och diffusion uppmättes för varje molekylär komponent i Nafion-membran solvatiserade av vatten-metanol-blandningar. / QC20100709

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.