Wood is our most important renewable resource. We need better quality and quantity both according to the wood itself and the processes that are using wood as a raw material. Hence, the understanding of the chemical composition of the wood is of high importance. Improved and new methods for analyzing wood are important to achieve better knowledge about both refining processes and raw material. The combination of NMR and multivariate analyses (MVA) is a powerful method for these analyses but so far it has been limited mainly to 1D NMR. In this project, we have developed methods for combining 2D NMR and MVA in both wood analysis and metabolomics. This combination was used to compare samples from normal wood and tension wood, and also trees with a down regulation of a pectin responsible gene. Dissolving pulp was also examined using the same combination of 2D-NMR and MVA, together with FT-IR and solid state 13C CP-MAS NMR. Here we focused on the difference between wood type (softwood and hardwood), process type (sulfite and sulfate) and viscosity. These methods confirmed and added knowledge about the dissolving pulp. Also reactivity was compared in relation to morphology of the cellulose and pulp composition. Based on the method and software used in the wood analysis projects, a new method called HSQC-STOCSY was developed. This method is especially suited for assignment of substances in complex mixtures. Peaks in 2D NMR spectra that correlate between different samples are plotted in correlation plots resembling regular NMR spectra. These correlation plots have great potential in identifying individual components in complex mixtures as shown here in a metabolic data set. This method could potentially also be used in other areas such as drug/target analyses, protein dynamics and assignment of wood spectra.

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京都大学 / 新制・課程博士 / 博士(農学) / 甲第24906号 / 農博第2569号 / 新制||農||1102(附属図書館) / 京都大学大学院農学研究科森林科学専攻 / (主査)教授 大村 和香子, 教授 髙野 俊幸, 教授 飛松 裕基 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DGAM

Abstract Modern NMR methods in liquids are based on the transfer of polarisation from nucleus to nucleus to generate multidimensional heteronuclear correlation spectra. The factors that influence the efficiency of heteronuclear polarisation transfer in multi-pulse experiments, and in that way the quality of spectra are the subject of this thesis. The flow of coherence through pulse sequences can be designed and analysed with the aid of product operator calculations. Results of the study include improvements to quantitative two-dimensional shift-correlated experiments, and demonstration of the benefits of closely spaced 180° pulse trains in polarisation transfer steps in long-range correlation experiments and isotope editing filters.

No / Three new xanthones, hypericorin C (1), hypericorin D (2) and 3,4-dihydroxy-5-methoxyxanthone (3), along with eight known compounds; 2,3-dimethoxyxanthone (4), 3,4-dihydroxy-2-methoxyxanthone (5), 3,5-dihydroxy-1-methoxyxanthone (6), 3-acetylbetulinic acid (7), 10H-1,3-dioxolo[4,5-b]xanthen-10-one (8), 3-hydroxy-2-methoxyxanthone (9), 3,4,5-trihydroxyxanthone (10) and betulinic acid (11) were isolated from the roots of Hypericum oblongifolium. The structures of the new compounds 1, 2 and 3 were deduced by spectroscopic techniques [ESI MS, (1)H NMR, (13)C NMR, and 2D NMR (HMQC, HMBC, COSY and NOESY)]. The entire series of compounds were evaluated for anti-ulcer activity.

Nuclear magnetic resonance (NMR) has become an effective borehole measurement option to assess petrophysical and fluid properties of porous and permeable rocks. In the case of fluid typing, two-dimensional (2D) NMR interpretation techniques have advantages over conventional one-dimensional (1D) interpretation as they provide additional discriminatory information about saturating fluids and their properties. However, often there is ambiguity as to whether fluids detected with NMR measurements are mobile or residual. In some instances, rapid vertical variations of rock properties (e.g. across thinly-bedded formations) can make it difficult to separate NMR fluid signatures from those due to pore-size distributions. There are also cases where conventional fluid identification methods based on resistivity and nuclear logs indicate dominant presence of water while NMR measurements indicate presence of water, hydrocarbon, and mud filtrate. In such cases, it is important to ascertain whether existing hydrocarbons are residual or mobile. The radial lengths of investigation of resistivity, nuclear, and NMR measurements are very different, with NMR measurements being the shallowest sensing. Even in the case of several radial zones of NMR response attributed to different acquisition frequencies and DC magnetic field gradients, the measured signal originates from a fairly shallow radial zone compared to that of nuclear and resistivity logs. Depending on drilling mud being used and the radial extent of mud-filtrate invasion, the NMR response of virgin reservoir fluids can be masked by mud filtrate because of fluid displacement and mixing. In order to separate those effects, it is important to reconcile NMR measurements with electrical and nuclear logs for improved assessment of porosity and mobile hydrocarbon saturation. Previously, Voss et al. (2009) and Gandhi et al. (2010) introduced the concept of Common Stratigraphic Framework (CSF) to construct and validate multi-layer static and dynamic petrophysical models based on the numerical simulation of well logs. In this thesis, the concept of CSF is implemented to reconcile 2D NMR interpretations with multi-layer static and dynamic petrophysical models. It is found that quantifying the exact radial zone of response and corresponding fluid saturations can only be accomplished with studies of mud-filtrate invasion that honor available resistivity and nuclear logs. This thesis indicates that the two interpretation methods complement each other and when applied in conjunction, improve and refine the overall petrophysical understanding of permeable rock formations. Examples of successful application include field data acquired in thinly-bedded gas formations invaded with water-base mud, where bed-boundary effects are significant and residual hydrocarbon saturation is relatively high. In such cases, numerical simulation of mud-filtrate invasion and well logs acquired after invasion enables reliable interpretations of petrophysical and fluid properties. The interpretation procedure introduced in this thesis also provides an explicit way to determine the uncertainty of petrophysical and fluid interpretations. / text

La migration de l’eau est un sujet générique dans divers domaines dont l'analyse permet de mieux comprendre les propriétés rhéologiques, sensorielles et de conservation des produits au cours du temps. Les apports de la relaxométrie et de la micro-imagerie par RMN dans ce domaine sont larges et d’un intérêt majeur au vue des caractéristiques non-invasives, non-destructives et quantitatives de ces méthodes, utilisables alors que le produit est en cours de transformation. Deux méthodologies ont été développées afin d’étudier les transferts de protons sur une large gamme de temps et de distance. La première a consisté à implémenter de nouvelles méthodes d’acquisition et de traitement du signal de RMN à bas champ (20 MHz) en 2D pour corréler non seulement les temps de relaxation T1 et T2 mais également les coefficients de diffusion translationnelle D et T2 sur des échantillons modèles amidon-eau de diverses origines botaniques (blé, pomme de terre et maïs cireux). Les mesures 2D se sont révélées suffisamment robustes pour quantifier les transferts de protons de l’eau et des polymères d’amidon pendant leur gonflement, leur gélatinisation et leur rétrogradation. Une approche complémentaire en micro-imagerie par RMN (500 MHz) a consisté à mesurer au cours du temps des profils de concentration de l’eau pénétrant sur plusieurs millimètres dans un extrudé d’amidon de pomme de terre contenant du glycérol. La diffusion de transport de l'eau et le taux de gonflement de l’extrudé ont été quantifiés à 22°C pendant plus de 20h. / Water migration is a generic subject in various fields, the analysis of which makes it possible to better understand the rheological, sensory and conservation properties of products over time. The contributions of relaxation and NMR micro-imaging in the field are broad and of major interest in view of the non-invasive, non-destructive and quantitative characteristics of these methods, which can be used while the product is under processing. Two methodologies have been developed to study the transfers in a wide range of time and length. The first consisted in implementing new methods of acquisition and processing of the NMR signal in 2D at low-field (20 MHz) to correlate not only the relaxation times T1 and T2 , but also the translational diffusion coefficients D and T2 on starch-water model samples from various botanical origins (wheat, potato and waxy corn). The 2D measurements have proved sufficiently robust to quantify the transfers of protons from water and starch polymers during their swelling, gelatinization and retrogradation. A complementary approach by MR micro-imaging (at 500 MHz) consisted in measuring, over time, the water uptake on several millimeters in an extrudate of potato starch containing glycerol. The diffusion transport of the water and the rate of the extrudate swelling were quantified at 22°C for more than 20 hours.

FundaÃÃo Cearense de Apoio ao Desenvolvimento Cientifico e TecnolÃgico / O presente trabalho relata o estudo quÃmico do caule de Cestrum laevigatum Schlecht (Solanaceae), coletado no municÃpio de Pacoti-CE. A partir da investigaÃÃo do extrato etanÃlico utilizando tÃcnicas clÃssicas de cromatografia de adsorÃÃo (gel de sÃlica e sÃlica flash) e exclusÃo (Sephadex LH-20) foi possÃvel o isolamento de esterÃides e um triterpeno. Os esterÃides de esqueleto espirostano foram caracterizados como uma mistura de sapogeninas 25(S)-5-espirostano-2,3-diol e 25(R)-5-espirostano-2,3-diol (gitogenina) (CL-1), a mistura de epÃmeros (25R)-5-espirostano-2,3-diol-3-O--D-galactopiranosÃdeo e (25S)-5-espirostano-2,3-diol-3-O--D-galactopiranosÃdeo (CL-2), e a mistura epimÃrica da saponina de carÃter inÃdito na literatura (25R,S)-5-espirostan-2,3-diol-3-O--D-galactopiranosil(1→4)- -D-galactopiranosil(1→4)--D-glicopiranosil (CL-3). AlÃm destes compostos, foram isolados ainda a mistura dos esterÃides -sitosterol e estigmasterol (CL-5) e seus derivados glicosilados (CL-6), alÃm do triterpeno pentacÃclico de esqueleto do tipo lupano β-lup-20(29)-en-3-ol (lupeol) (CL-4). A caracterizaÃÃo estrutural dos compostos isolados foi possÃvel atravÃs do uso de tÃcnicas espectroscÃpicas, principalmente RMN, incluindo seqÃÃncias de pulso uni e bidimensionais, e comparaÃÃo com dados relatados na literatura. Das saponinas investigadas quanto ao potencial antimicrobiano, apenas CL-3 mostrou-se ativa contra Bacillos subtilis, Pseudomonas aeruginosa e Enterobacter aerogenes. A atividade leishmanicida foi realizada com CL-1, CL-2 e CL-3, porÃm, apenas CL-3 mostrou-se ativa contra Leishmania amazonensis. Em relaÃÃo à atividade antifÃngica, CL-1 mostrou-se ativa apenas contra Microsporum canis. CL-2 apresentou excelentes resultados contra Candida albicans, Trichophyton rubrum e Trichophyton mentagrophytes, e uma atividade relativamente boa contra Microsporum canis. Jà CL-3 aparece revelou uma excelente atividade antifÃngica contra todas as cepas testadas. Os resultados promissores obtidos atà o momento a partir do extrato etanÃlico do caule de C. laevigatum confirmam o grande potencial quÃmico/farmacolÃgico das espÃcies deste gÃnero, e justificam a importÃncia do trabalho realizado / This work reports the chemical study of the stem of Cestrum laevigatum Schlecht (Solanaceae), collected at the Pacoti-CE. The investigation of the ethanol extract using conventional techniques of adsorption chromatography (silica gel and silica flash) and exclusion (Sephadex LH-20) was possible the isolation of steroids and triterpene. The spirostan steroids have been characterized as the mixture at the sapogenins 25(S)-5-espirostan-2,3-diol and 25(R)-5-espirostan-2,3-diol (gitogenin) (CL-1), a mixture of epimers (25R)-5-espirostan-2,3-diol-3-O--Dgalactopyranoside and (25S)-5-espirostan-2,3-diol-3-O--D-galactoyiranoside (CL-2), and the mixture of new epimer (25R,S)-5-espirostan-2,3-diol-3-O--Dgalactopyranosil(1→4)--D-galactopyranosil(1→4)--D-glicopyranosil (CL-3). Besides these compounds, were also isolated the mixture of steroids β-sitosterol and stigmasterol (CL-5) and its glycosides (CL-6), and the pentacyclic triterpene β-lup-20(29)-en-3-ol (lupeol) (CL-4). The structural characterization of the isolated compounds was possible through the use of spectroscopic techniques, mainly NMR, including sequences of uni and bidimensional pulse, and comparison with literature data. CL-3 was shown to be active against Bacille subtilis, Pseudomonas aeruginosa and Enterobacter aerogenes. The leishmanicide activity was performed with CL-1, CL-2 and CL-3, however, only CL-3 was shown to be active against Leishmania amazonensis. For the antifungical activity, CL-1 was shown to be active only against Microsporum canis. CL-2 showed excellent results against Candida albicans, Trichophyton rubrum and Trichophyton mentagrophytes, and a relatively good activity against Microsporum canis. CL-3 appears with excellent activity antifungical against all strains tested. The promising results obtained so far from the ethanol extract of the stem of C. laevigatum confirm the great potential chemical / pharmacological species of this genus, and justify the importance of work

Ce mémoire traite du développement d'outils informatiques d'aide à l'analyse structurale des petites molécules organiques par Résonance Magnétique Nucléaire (RMN). Il comprend deux volets axés sur l'automatisation de tâches auxquelles les chimistes des laboratoires de synthèse organique ou d'isolement de substances naturelles sont confrontés au quotidien, à savoir l'élucidation et la vérification de structure. Le premier volet concerne des améliorations apportées au logiciel de génération de structure LSD (Logic for Structure Determination). Ce logiciel est basé sur l'interprétation des corrélations des spectres de RMN 2D pour la détermination de structures complètement ou partiellement inconnues. Les progrès récents ont pour but d'augmenter la diversité des molécules analysables et d'améliorer le traitement des corrélations ainsi que la présentation des résultats. L'intégration de LSD avec la base de données SISTEMAT permet de bénéficier de la source d'information supplémentaire que constitue la valeur des déplacements chimiques. Cet avantage se traduit par un filtrage des solutions en fonction d'éléments de sous-structure sélectionnés dans une collection de squelettes de produits naturels. Le second volet présente le développement du logiciel CASA (Computer-Aided Spectral Assignment) dont le rôle est de réaliser une vérification automatique de structure par l'attribution des résonances. Il s'appuie sur des contraintes issues des spectres de RMN 2D et sur un module de prédiction des déplacements chimiques 13C. / This thesis deals with the development of computational tools for structural analysis of small organic molecules by Nuclear Magnetic Resonance (NMR). It consists of two parts that focus on the automation of tasks that chemists working in the fields of organic synthesis or natural substance isolation daily face, namely structure elucidation and verification. The first part reports improvements of the structure generation software LSD (Logic for Structure Determination). This software is designed for the determination of completely or partially unknown structures from the interpretation of 2D NMR correlation spectra. The present work aims to increase the diversity of the molecules that can be analyzed and to improve the processing of correlation data as well as the presentation of results. The integration of LSD with the SISTEMAT database introduces chemical shifts values as an additional information source. It allows the chemist to sort the possible solutions of a problem according to the presence of known natural product skeletons. The second part presents the development of the CASA (Computer-Aided Spectral Assignment) software as a tool for automatic structure assignment. It jointly makes use of constraints from 2D NMR spectra and from the matching between experimental and predicted 13C chemical shifts.

No description available.