Dissertations / Theses on the topic 'Hydrogen bond network analysis'

As propriedades físicas incomuns exibidas por fluidos confinados em meios porosos desempenham um papel importante em diversos processos químicos, geoquímicos e ambientais. Atualmente, muitos aspectos da estrutura e dinâmica dos fluidos espacialmente confinados ainda são pouco compreendidos. Nesse contexto, fenômenos interfaciais influenciam consideravelmente os processos que ocorrem em meios nanoporosos, podendo resultar em efeitos relevantes para o desenvolvimento dos dispositivos nanofluidicos. Esses sistemas multifásicos e com fenômenos multifísicos podem apresentar propriedades eletrônicos e dinâmicos envolvendo diferentes escalas de tamanho e tempo na interface sólido/fluido. Atualmente, uma única metodologia não é capaz de resolver toda a complexidade encontrada em tais sistemas pelo fato de cada qual estar restrita a uma escala ou demanda computacional específica. Além disso, as metodologias habitualmente aplicadas para investigar as fases bulk através da modelagem computacional, em geral, não são adequadas para acessar sistematicamente os efeitos de superfície que ocorrem na interface sólido/fluido. Os desafios impostos à modelagem molecular pelos sistemas nanofluídicos requerem iniciativas inovadoras (dentre as metodologias disponíveis) para acessar as propriedades de interface. Nessa tese, desenvolvemos e aplicamos novas abordagens computacionais em nível atômico a fim de modelar e caracterizar sistemas nanofluidicos. Nesse contexto, introduzimos um método multinível hierárquico top-down, que combina simulações de dinâmica molecular com cálculos ab initio de transporte eletrônico, para abordar fenômenos de multiescala. O potencial dessa implementação foi demonstrado em um estudo de caso envolvendo o fluxo de água e o transporte de íons através de um nanotubo de carbono tipo (6,6). Mostramos que o traço iônica pode representar uma mudança na condutância elétrica do nanocanal, e levar a uma medida indireta da corrente iônica. Também implementamos uma versão modificada da análise de rede de ligações de hidrogênio baseada em teoria de grafos, a fim de fazer o estudo das propriedades estruturais e dinâmicas em diferentes regiões do poro. Com essa abordagem, nós fomos capazes de explorar sistematicamente os efeitos de interface em fluidos espacialmente confinados. Combinando-se simulações de dinâmica molecular com a análise da rede de ligações de hidrogênio em camadas, nós pudemos avaliar a extensão dos efeitos de superfície nas propriedades dinâmicas e os detalhes da interface calcita/salmoura. Com a abordagem desenvolvida, conseguimos isolar os efeitos específicas dos íons da solução aquosa na rede de ligações de hidrogênio. Mostramos que a camada superficial exibe uma topologia de rede semelhante à observada em água pura, uma vez que a barreira eletrostática e física exibida por essa região, inibe a adsorção de íons na superfície da calcita. Fora dessa faixa, os íons influenciam consideravelmente a rede de ligações de hidrogênio: observamos a formação caminhos geodésicos mais extensos em relação àqueles observados em água pura. Esses ramos, que são formados por ligações de hidrogênio contíguas, podem conectar moléculas de baixa a alta dinâmica. Tal estrutura, pode explicar as propriedades mecânicas adesivas observadas em fluidos altamente confinados. Nossas principais contribuições decorrem na descrição da estrutura do solvente, dos íons da solução aquosa na interface calcita/fluido; e suas indicações físicas, e seu potencial significado nos processos de crescimento e dissolução de cristais. Nossas implementações fornecem contribuições interessantes para a compreensão atual dos processos que ocorrem em meios porosos. Especialmente, podendo contribuir para um desenvolvimento racional de novos dispositivos nanofluidicos.
The unusual physical properties exhibit by fluids within nanoscopic porous media play an important role in the plethora of chemical, geochemical and environmental processes. Currently, many aspects of the structure and dynamics of the spatially constrained fluids are still poorly understood. Additionally, the interfacial phenomena considerably influences the processes occurring in nanoporous media, which can have a major effect on nanofluidics devices. These multiphase systems and multi-physics phenomena occurs at solid/solution interfaces, with electronic and dynamic effects taking place across size and time scales. Currently, a single methodology is not capable to disentangle all the complexity find in such systems because it is restricted to a specific scale or computationally demand. In addition, the usual computational modeling methodologies applied to investigate bulk phases, they are, in general, not suitable to systematically access the surface effects occurring at solid/fluid interfaces. The challenges imposed by the nanofludics-based systems within the molecular modeling framework require innovative initiatives (among the available methodologies) to correctly access the interface properties. In this thesis, we develop and apply novel computational approaches to properly design and characterize nanofluidics-based systems at atomic level. In this context, we introduced an hierarchical top-down multilevel method by combining molecular dynamics simulations with first principles electronic transport calculations to address the multiscale phenomena problem. The potential of this implementation was demonstrated in a case study involving the water and ionic (Na, Li, and CL) flow through a (6,6) carbon nanotube. We showed that the ionic trace, observed on the electronic transmittance, it may handle an indirect measurement of the ionic current that is recorded as a sensing output. We implemented also a layered version of hydrogen bond network analysis based on graph theory. With this approach, we were able to properly explore interface effects arising on spatially confined fluids. By combining molecular dynamics simulations with the layered hydrogen bond network analysis, we evaluated the extension of surface effects on the fluids dynamics properties and the interaction details at calcite/brine interface. With the developed approach, we have been able to isolate the specific features of the aqueous solutions ions on the hydrogen bond network. We showed that the surface layer near the calcite/brine interface displays similar network topology as observed in pure water, since the electrostatic and physical barrier displayed by this layer inhibit the adsorption of ions on the calcite surface. Outside that region, these ions affect the hydrogen bond network. We observed a more extended geodesic paths with respect to that observed in pure water. Such hydrogen bond branches may connect low to high dynamics molecules across the pore and hence, it may explain the glue-like mechanical properties observed in confinement environment. Our main contributions in this work relies on describing the structure of solvent and electrolyte aqueous solution at calcite/fluid interface and their physical indications and potential significance on the crystal growth and dissolution processes. Our implementations provide interesting contributions to the current understanding of processes occurring in porous media. Specially, it may contribute on the rational design of novel nanofluidics devices.

Chloroperoxidase (CPO) is one of the most versatile heme enzyme isolated from the marine fungus, Caldariomyces fumago. Functionally, CPO can catalyze four types of reactions: peroxidation (peroxidase-like), dismutation (catalase-like), halogenation (halogenase-like), and peroxygenation (P450-like). Structurally, CPO has a distal and proximal pockets that can be best described as a hybrid of classical peroxidase and P450s. As a heme-thiolate protein, CPO contains the conserved proximal Pro28-Cys29-Pro30 stretch found in other members of the family. However, the structural and functional roles of these proline residues remain poorly understood. Site-directed mutagenesis was undertaken to generates three CPO mutants, P28A-, P30A-, P28A/P30A-CPO. The replacement of the rigid proline with a more flexible alanine residue, freed up the back bone amide for the formation of additional amide-sulfur hydrogen bond, allowing the investigation of the importance of these residues in CPO catalysis. The three CPO mutants displayed dramatic difference in ligand binding affinity and catalytic activities relative to WT-CPO. Any mutations on the proline resides within the proximal loop eliminated the halogenation and dismutation activities but enhanced the vii epoxidation and peroxidation activities by 4-14 fold. As the binding affinity for cyanide, the CPO mutants displayed significantly higher dissociation constant relative to WT-CPO. Our results revealed that Pro28 and Pro30 play important roles in maintaining the versatility of CPO. As a versatile enzyme, CPO has great application potential in pharmaceutical and chemical industry due to its ability to catalyze the formation of chiral epoxides. Phe103 and Phe186 located on the distal pocket have been proposed to guard the access of substrates to the ferryl oxygen of the heme center. The interactions of these two phenylalanine residues restricted the size of substrates and regulates CPO’s enantioselectivity. F186A- and F103A/F186A-CPO were generated and characterized where the rate of peroxidation and epoxidation were significantly enhanced at the expense of halogenation and dismutation activities. Our results demonstrated that Phe186 played a subtler role relative to Phe103 in terms of substrate specificity and product enantioselectivity of CPO.

Chloroperoxidase (CPO) from Caldariomyces fumago is a versatile heme enzyme with great potential for environmental and pharmaceutical applications. It catalyzes a plethora of reactions including halogenation, dismutation, epoxidation, and oxidation. The diverse catalytic capabilities of CPO have long been attributed to the protein’s distinct active site that combines structural features of peroxidases and cytochromes P450. Particularly, the role of the axial thiolate ligand in CPO catalysis has been much debated. Furthermore, no data are available on the role of hydrogen bonding between Arg 26-Asn 37 and Ala 27-Asn 33 of the proximal helix in defining the structural and catalytic properties of CPO. In order to investigate the influence of the proximal thiolate and the proximal hydrogen bond network on the structural and biochemical properties of CPO, several mutant CPOs were constructed and characterized using various spectroscopic techniques and enzymatic assays. Cysteine 29, which coordinates to the heme, was replaced with a His (C29H) to mimic the proximal ligation of classical peroxidases. The UV-Vis spectrum of the carbon monoxide complex of ferrous C29H mutant remained essentially identical to that of wild type (WT) CPO and P450 although the ferric state of the variant enzyme showed a spectral pattern reminiscent of a classical histidine ligated heme peroxidase. Histidine ligation was further confirmed by paramagnetic NMR spectroscopy. Contrary to a previous report, the specific chlorination activity of C29H was essentially abolished (less than 1% of that of WT CPO) but the epoxidation and peroxidation activities were enhanced 10-fold and 55-fold, respectively. These findings demonstrate for the first time that the heme ligand, Cys 29 in CPO, is not a prerequisite for CPO’s unique P450-like spectroscopic signatures but is constitutive for the protein’s versatile catalytic activities. Arginine 26 and Asparagine 33 in the proximal heme pocket were replaced with Ala (R26A, N33A, and R26A/N33A) to disrupt hydrogen bonding. Tertiary structures and heme environments of R26A, N33A, and R26A/N33A differed from those of WT CPO as determined by CD spectroscopy. The specific chlorination and dismutation activities of all mutants were almost abolished but the peroxidation and epoxidation rates were increased. These results show that the proximal hydrogen bond network plays an important role in maintaining the structure and catalytic diversity of CPO.

Water is one of the most common compounds on earth and is essential for all biological activities. Water has, however, been a mystery for many years due to the large number of unusual chemical and physical properties, e.g. decreased volume during melting and maximum density at 4 °C. The origin of the anomalies behavior is the nature of the hydrogen bond. This thesis will presented an x-ray absorption spectroscopy (XAS) study to reveal the hydrogen bond structure in liquid water.

The x-ray absorption process is faster than a femtosecond and thereby reflects the molecular orbital structure in a frozen geometry locally around the probed water molecules. The results indicate that the electronic structure of liquid water is significantly different from that of the solid and gaseous forms. The molecular arrangement in the first coordination shell of liquid water is actually very similar as the two-hydrogen-bonded configurations at the surface of ice. This discovery suggests that most molecules in liquid water have two-hydrogen-bonded configurations with one donor and one acceptor hydrogen bond compared to the four-hydrogen-bonded tetrahedral structure in ice. This result is controversial since the general picture is that the structure of liquid water is very similar to the structure of ice. The results are, however, consistent with x-ray and neutron diffraction data but reveals serious discrepancies with structures based on current molecular dynamics simulations. The two-hydrogen-bond configuration in liquid water is rigid and heating from 25 °C to 90 °C introduce a minor change in the hydrogen-bonded configurations. Furthermore, XAS studies of water in aqueous solutions show that ion hydration does not affect the hydrogen bond configuration of the bulk. Only water molecules in the close vicinity to the ions show changes in the hydrogen bond formation. XAS data obtained with fluorescence yield are sensitive enough to resolved electronic structure of water molecules in the first hydration sphere and to distinguish between different protonated species. Hence, XAS is a useful tool to provide insight into the local electronic structure of a hydrogen-bonded liquid and it is applied for the first time on water revealing unique information of high importance.

La thèse se compose de trois essais, abordant chacun la dichotomie entre la liaison et l'adhérence à partir d'un angle théorique différent. Dans le premier essai, je pose la question Comment Lier et Comment Adhérer et je propose un nouveau cadre théorique pour analyser le capital social, qui déconstruit sa principale fonction au-delà de la liaison ou de l'adhérence dans sa substance comme les relations sociales par rapport à la position dans la structure du réseau. Compte tenu de ces deux dimensions de l'analyse des réseaux sociaux, je propose quatre sources distinctes du capital social qui ont une valeur prédictive différente pour les réalisations individuelles - le réseau de liaison, les relations de liaison, le réseau d'adhérence et les relations d'adhérence - et j'examine leur valeur à la performance individuelle. La question du plomb dans le deuxième essai de ma thèse est Quand faut-il lier et Quand faut-il adhérer? Rejoignant la recherche sur la valeur éventuelle du capital social, je cherche comment l'organisation et les facteurs liés à l'emploi modèrent la relation entre chaque source de capital social à la performance et théorisent sur les stratégies que les individus devraient poursuivre afin d'obtenir de meilleures performances. Dans le troisième essai, je pose la question Sur Quelle Source devrais-je me fonder ? J'examine la puissance individuelle de chaque source de capital social et de la complémentarité entre les quatre d'entre eux. Je démontre que, bien que toutes les sources de capital social doivent avoir un impact positif sur la performance, certains d'entre eux pourraient supprimer le déploiement des autres formes
My dissertation expands the line of inquiry of the contingent value of social capital to individual performance by raising three novel questions. In the first essay of my dissertation I focus on “How to bridge and how to bond” and propose a new theoretical framework for analyzing social capital, which deconstructs its major function beyond bridging or bonding into its substance as social relations versus position in network structure. Considering these two dimensions of social network analysis I propose four distinct sources of social capital that have different predictive value for individual achievements: bridging network, bridging relations, bonding network and bonding relations. The lead question in the second chapter of my dissertation is “When to bridge and when to bond”. Joining the research on the contingent value of social capital, I look at organization and individual level factors to predict the value of each social capital source to performance and theorize about the strategies individuals should pursue in order to achieve better performance. In the third essay I ask “Should one start with bridging or with bonding?” Building on the categorization proposed in the first chapter I investigate the most successful social capital path to on-the-job performance

En stor samling dimolekylära vätebindningar med formen A – H … B, där AH är en alkyn, alkohol eller tiol och B = [Br–, Cl–, NH3, HCN] beräknas och utvärderas med Kohn-Sham täthetsfunktionalteori tillsammans med bassetet m062x/6-311+g(2df.2p). Dessa komplex utvärderas även med en punktladdningsmodell (som använder samma metod och basset), där atomerna i vätebindningsmottagaren B byts ut mot laddningar som passats för att återskapa laddningsfördelningen runt molekylen, med målet att separera och isolera de elektrostatiska och polariserande energikomponenterna från de totala interaktionsenergierna. Med hjälp av detta tillvägagångssätt visade det sig att vätebindningars komplexeringsenergi (i.e. interaktionsenergin med energikostnaden för att deformera atomkärnornas rymdgeometri borttagen), oberoende av karaktären hos monomeren AH eller B, till stor del består av elektrostatik och polarisation, medan laddningsutbyte, dispersion, och andra resttermer endast utgör en liten del av den totala interaktionen. Fördelningen mellan elektrostatik och polarisation varierar beroende på typen av monomerer i vätebindningen, men deras summa, den resulterande punktladdningsenergin, korrelerar linjärt (ΔECompl = 0.85ΔEPC ) med R2 = 0.995 över energiomfånget 0 < ΔECompl < 50 kcal mol–1. Detta blir ännu mer anmärkningsvärt då inkluderingen av komplexeringsenergierna från halogenbindningar i samma korrelation inte förändrar korrelationskoefficienten avsevärt, vilket indikerar att båda bindningstyperna består av samma energikomponenter även då bindningarna i sig är väldigt olika.
A large set of dimeric hydrogen bonds of the type A – H … B, where AH is an alkyne, alcohol, or thiol and B = [Br–, Cl–, NH3, HCN]  are computed and evaluated using Kohn-Sham density functional theory together with the m062x/6-311+g(2df.2p) basis set. These complexes are also evaluated using a point charge (PC) approach (using the same method and basis set), where the atoms of the hydrogen bond acceptor B are substituted for charges that are optimized to reproduce the charge distribution of the molecule, with the purpose of separating and isolating the electrostatics- and polarization energy components of the interaction energies. Using this approach it was discovered that the complexation energy of hydrogen bonds (i.e.the interaction energy with the energy cost of nuclear deformation corrected for), independent on the nature of either monomer AH or B, are largely made up of electrostatics and polarization, while charge transfer, dispersion, and other rest terms only make up a small fraction of the total interaction. The composition of electrostatics and polarization vary depending on the type of monomers in the hydrogen bond, but their sum, the PC interaction energy, correlates linearly (ΔECompl = 0.85ΔEPC )  with R2 = 0.995 over an energy span of 0 < ΔECompl < 50 kcal mol–1. This is made even more remarkable by the inclusion of halogen bonded complexation energies in the same correlation without changing the correlation coefficient significantly, indicating that the two bond types are comprised of the same components even though they are remarkably different in origin.

Os métodos existentes para a previsão da posição de átomos de hidrogênio em proteínas são todos baseados na simulação computacional de modelos construídos a partir de características físicas e (ou) químicas das moléculas. A abordagem proposta neste trabalho faz uso de técnicas inteligentes para a predição da posição de átomos de hidrogênio contidos em grupos hidroxilas (OH) pertencentes à cadeias laterais dos aminoácidos serina, treonina e tirosina. Estas técnicas inteligentes são utilizadas em duas fases para a solução do problema proposto: o preprocessamento dos dados e a predição da posição do átomo de hidrogênio. Na fase de preprocessamento, informações sobre os padrões de ligações hidrogênio existentes em moléculas de proteínas são extraídas da base PDB (Protein Data Bank) e reunidas em agrupamentos. A base de dados PDB é a principal base internacional que disponibiliza publicamente a estrutura espacial de biomoléculas, principalmente proteínas e ácidos nucléicos, cujas estruturas espacias foram determinadas através de métodos experimentais. Os padrões de ligações hidrogênio obtidos da base de dados são agrupados por similaridade através de um novo algoritimo proposto, o algoritmo de agrupamento por fusão. Este novo algoritmo de agrupamento foi criado com o propósito de tratar dados com distribuição não uniforme, isolando padrões de entrada muito diferentes da média em agrupamento separados. Após o agrupamento, os padrões de ligações hidrogênio contidos em um grupo têm suas estruturas espaciais superpostas (alinhamento das geometrias dos padrões) através de operações espaciais de translação e rotações, coordenadas pelo uso de um algoritmo genético. Na fase de predição, os padrões já superpostos contidos em cada agrupamento gerado, são utilizados para o treinamento de uma rede neural de arquitetura MLP (multi layer perceptron) para a predição da posição do átomo de hidrogênio contido no padrão. Uma parte dos padrões contidos no agrupamento não são usados para o treinamento da rede e reservados para o teste da capacidade da rede neural inferir a posição do hidrogênio após o treinamento. Para cada agrupamento é treinada uma rede individual, de forma que os parâmetros livres da rede neural sejam calibrados para os dados específicos do agrupamento para o qual a rede neural foi treinada. Após diversas alterações de metodogia ao longo dos experimentos computacionais realizados, a nova abordagem proposta mostrouse eficaz, com um bom índice de acerto na predição da posição do hidrogênio após o treino da rede neural, para padrões de ligações hidrogênio previamente superpostos em agrupamentos
The existing methods for the prediction of the position of hydrogen atoms in proteins are all based on computer simulation models constructed from physical and(or) chemical properties of molecules. The approach proposed in this paper makes use of intelligent techniques for clustering the patterns of hydrogen bonds by similarity, these patterns extracted from the spatial structure of protein molecules, recorded in the files of the PDB (Protein Data Bank). A new algorithm, which allows clustering of data with nonuniform distribution was developed for this purpose. To align spatialy these patterns already grouped in a cluster is used a genetic algorithm that rotates the patterns each other in a way to obtain the aligment of them. The prediction of the position of atoms of hydrogen is done by the training of a MLP (multi layer perceptron) neural network that uses as input the data of the patterns of hydrogen bond contained in a given cluster, previously aligned. The new approach proved to be effective, with a good rate of success in the prediction of the position of hydrogen atoms contained in a cluster after training the neural network

El texto completo de este trabajo no está disponible en el Repositorio Académico UPC por restricciones de la casa editorial donde ha sido publicado.
PURPOSE: To assess the long-term effect of a 2% aqueous chlorhexidine (CHX) solution on bond strength to artificially eroded dentin compared to sound dentin. MATERIALS AND METHODS: Flat mid-coronal dentin surfaces of extracted third molars (n = 28) were subjected only to grinding with a 600-grit SiC paper for 1 min (sound dentin S, n = 14) or additionally to erosive pH cycling with a cola-based soft-drink (eroded dentin E, n = 14). After acid etching, rinsing, and air drying, S and E were rehydrated with 1.5 μl of 2% CHX (S2%, n = 7; E2%, n = 7) or of distilled water (control SC, n = 7; EC, n = 7). Composite buildups were incrementally constructed with Filtek Z350 following Adper Single Bond 2 application. Specimens were sectioned into beams, which were subjected to microtensile testing immediately or after 6 or 12 months of aging. Fractured surfaces were observed under a digital microscope (50X magnification). Microtensile bond strength (μTBS) (MPa) was analyzed by three-way ANOVA and Tukey's tests (α = 0.05) and failure mode by the Kruskal-Wallis test (α = 0.05). RESULTS: Compared to sound dentin, eroded dentin was consistently related to lower μTBS. Immediately and after 12-month aging, the effect of CHX was insignificant, but it was significant after 6-month aging, when it conserved the bond strength to both eroded and sound dentin. The percentage of adhesive and mixed failures were equivalent, and significantly more frequent than cohesive failures, whether in dentin or in composite. CONCLUSION: The 2% CHX effect on bond strength conservation to both eroded and sound dentin was not found to be persistent.
Revisión por pares

A interação da água com a celulose e com o amido é de grande importância para a compreensão das propriedades de ambos polissacarídeos e fundamental para o desenvolvimento de novas aplicações tecnológicas. Entre as novas aplicações estão em destaque a nanocelulose, como os nanocristais e microfibrilas. A preparação desses materiais é fortemente influenciada pela interação das ligações de hidrogênio presente nas fibras de celulose, tanto de caráter intra como intermolecular. Essas interações são responsáveis pelas propriedades mecânicas desses materiais uma vez que as moléculas estão ligadas umas às outras por meio de ligações de hidrogênio onde a água pode participar como elemento de ligação. Para o amido, dependendo da concentração da água, pode modifica-lo em termos da solubilidade e em propriedades pelo processo de gelatinização ou atuar como plastificantes como parcial despolimerização em amido termoplástico. Neste trabalho é descrito o estudo da interação do sistema água com a celulose e com o sistema água com amido por meio da análise termogravimétrica para a identificação de diferentes espécies de água: i) água livre, ii) água ligada congelável iii) água ligada não congelável. Para a realização deste estudo foi utilizado o método auto stepwise, método que permite uma maior resolução dos diversos fenômenos separadamente que ocorrem durante a dessorção da água. A dessorção da água no amido se demostrou mais complexa que a celulose devido à alternância da parte amorfa e cristalina em sua estrutura. Para o cálculo da energia de ativação da dessorção da água ligada e da degradação do polissacarídeo foi utilizado o método cinético de Osawa-Flynn-Wall, sendo possível estimar a energia de ativação dos fenômenos. Variando de 35-65 kJ/mol para dessorção da água ligada e 144,6-184 kJ/mol para degradação dos materiais.
The interaction of water with cellulose and starch are of great importance for understanding the properties of both polysaccharides and fundamental to the development of new technological applications. Among the new applications are highlighted to nanocellulose such as nanocrystals and microfibrils. The preparation of these materials is strongly influenced by the interaction of hydrogen bonds present in the cellulose fibers, both intra as intermolecular. These interactions are responsible for the mechanical properties of these materials since the molecules are linked to each other through hydrogen bonds where water can participate as a connecting element. For starch, depending on the concentration of the water, can modify it in terms of solubility and properties by gelatinization process or act as plasticizers as partial depolymerization of thermoplastic starch. This paper describes the study of the interaction of the water/cellulose system and the starch/water system by means of thermogravimetric analysis for the identification of different species of water: i) the free water or freezing water, ii) the freezing bound water and iii) the non-freezing bound water. For this study we used the auto stepwise method, that allows greater resolution of the various phenomena separately that occur during the water desorption. The water desorption in the starch is more complex that cellulose, due to alternating crystalline and amorphous parts of the structure. To calculate the bound water desorption activation energy and polysaccharide degradation energy was used kinetic method of Osawa-Flynn-Wall, that possible to estimate the phenomena of the activation energy, ranging from 35-65 kJ / mol for bound water desorption and from 144.6 to 184 kJ / mol for material degradation.

La précipitation et la dissolution du carbonate de calcium (CaCO3) sont des processus clés dans les systèmes naturels en raison de leur association intime avec le cycle du carbone terrestre. La précipitation se produit généralement sur des substrats étrangers en abaissant les barrières énergétiques qui contrôlent la nucléation. Ce processus appelé nucléation hétérogène résulte d'une interaction entre la sursaturation du fluide et les différentes énergies d’interface entre substrat-noyau-fluide. Malgré l’importance des énergies d’interface sur le devenir de la nucléation hétérogène, la littérature actuelle reste rare dans leurs valeurs absolues, limitant la précision de la modélisation du transport réactif. La formation des biominéraux constitue un réservoir majeur des carbonates dans la lithosphère. Des études récentes ont révélé des nucléations par multi-étapes impliquant la formation du carbonate de calcium amorphe (ACC), un intermédiaire métastable durant les premiers stades de la formation des biominéraux. De tels précurseurs amorphes permettent de réaliser les formes complexes des biominéraux, tandis que leur stabilité et leur cinétique de cristallisation sont contrôlées par de multiples facteurs. L'élucidation des mécanismes sous-jacents est bénéfique pour le développement de matériaux biomimétiques.Le premier objectif est de développer une compréhension prédictive des valeurs d'énergie d’interface régissant la nucléation hétérogène du CaCO3 en fonction des propriétés physico-chimiques spécifiques des substrats, comme l'hydrophobicité. Cette dernière est étudiée en utilisant de la phlogopite avec et sans substitution par le fluor produisant des substrats hydrophobes et hydrophiles. La technique de diffusion des rayons X aux petits angles en incidence rasante a été employée in situ pour obtenir des valeurs d’énergie effective d’interface. Il est intéressant de noter que les valeurs extraites pour les deux substrats sont similaires, et thermodynamiquement les deux fournissent un bon modèle pour la nucléation, alors que leurs mécanismes sont différents. La caractérisation ex situ par microscopie à force atomique a montré que le substrat hydrophile favorise la formation et la stabilisation d’ACC, tandis que le substrat hydrophobe favorise la formation de calcite. Ces résultats soulignent la flexibilité structurelle intrinsèque du CaCO3 et son avantage dans les processus de nucléation hétérogènes.Le deuxième objectif est de fournir une description atomistique de l'hydrophobicité du substrat. L'adsorption d'eau sur la phlogopite a été réalisée in situ par spectroscopie de photoélectrons à pression ambiante pour étudier l'effet de la substitution par le fluor et de différents types de contre-ions (K+, Na+ vs. Cs+). Ces résultats ont été interprétés par des simulations de dynamique moléculaire et la théorie de bond-valence. La combinaison de ces techniques montre que l'hydrophobicité du substrat provient d'une compétition entre deux facteurs: l'hydratation des contre-ions par rapport à celle du substrat.Le but final est d'étudier les mécanismes moléculaires par lesquels Mg2+, une impureté chez les précurseurs amorphes biogéniques, augmente la persistance cinétique d’ACC. La technique de diffusion inélastique incohérente des neutrons a été combinée avec la spectroscopie de corrélation de photons X pour élucider la dynamique à l'échelle nanométrique de l'eau et des ions dans les ACC. Les résultats montrent que la présence de Mg2+ augmente la diffusion atomique dans le solide tout en amplifiant la rigidité du réseau des liaisons hydrogène. Ces résultats contre-intuitifs sont abordés en considérant différents facteurs cinétiques inclus dans l’équation décrivant le taux de nucléation au sein de la théorie classique de la nucléation. Dans l'ensemble, ces résultats indiquent l'importance de l'eau comme stabilisant cinétique de la structure amorphe et de l'existence de barrières stériques qui abaissent le taux de cristallisation
Precipitation and dissolution of calcium carbonate (CaCO3) are key processes in both natural and engineered systems due to their intimate association with the Earth’s carbon cycle. Precipitation usually occurs on foreign substrates since they lower the energetic barriers controlling nucleation events. This so-called heterogeneous nucleation results from the interplay between the fluid supersaturation and the interfacial free energies present at the substrate-nucleus-fluid interfaces. Despite the relevance of interfacial energies for the fate of heterogeneous nucleation, the current literature remains scarce in their absolute values, which limits the accuracy of reactive transport modelling. Of particular relevance to the carbon cycle, the formation of biominerals accounts for a major reservoir of the carbonate minerals in the lithosphere. Recent studies have revealed the existence of multistep nucleation pathways that involve formation of amorphous calcium carbonate (ACC), a metastable intermediate during the early stages of biomineral formation. Such amorphous precursors allow molding of the intricate shapes of biominerals, while their stability and crystallization kinetics are effectively controlled by multiple factors. Elucidating the underlying mechanisms is beneficial for the development of biomimetic materials.The first goal of this dissertation is to develop a predictive understanding of interfacial energy values governing CaCO3 heterogeneous nucleation as a function of specific physico-chemical properties of the substrates, such as hydrophobicity. This last was investigated using phlogopite, a common mica, with and without fluorine substitution yielding hydrophobic and hydrophilic substrates. In situ time-resolved Grazing-Incidence Small Angle X-ray Scattering experiments were performed to obtain effective interfacial energy values. Interestingly, the extracted values for both substrates were similar, and thermodynamically these substrates provide a good template for nucleation, but the pathways differ. By ex situ Atomic Force Microscopy characterization, the hydrophilic substrate was shown to promote the formation and stabilization of ACC, whereas the hydrophobic one favored the formation of calcite. These results point to the intrinsic structural flexibility of CaCO3 and its advantage in heterogeneous nucleation processes.The second goal is to provide an atomistic description of the substrate hydrophobicity/hydrophilicity. Water adsorption on phlogopite was studied in situ using Near-Ambient Pressure X-ray Photoelectron Spectroscopy to investigate the effect of fluorine substitution and the influence of different types of counterions (K+, Na+ vs. Cs+). The results of the spectroscopy experiments were further interpreted using molecular dynamics simulations and bond-valence theory. The combination of these techniques shows that the substrate hydrophobicity stems from a competition between two factors: hydration of counterions vs. that of substrate.The final goal is to study the molecular mechanisms by which Mg2+, a common impurity in biogenic amorphous precursors, increases the kinetic persistence of ACC. Inelastic Incoherent Neutron Scattering and X-ray Photon Correlation Spectroscopy were combined to elucidate the nanoscale dynamics of water and ions within ACC. The presence of Mg2+ was shown to enhance the atomic diffusion within the solid while simultaneously increasing the stiffness of the hydrogen bond network. These counter-intuitive results are addressed by considering the different factors included in the pre-exponential term of the nucleation rate equation within the framework of the classical nucleation theory. Overall, the results point to the importance of water as a kinetic stabilizer, and to the existence of steric barriers that lower the crystallization rate

Gegenstand der vorliegenden Arbeit ist die Synthese und Charakterisierung neuartiger elektrophiler Barbiturate. In diesen Zielverbindungen sollte die kovalente Verknüpfung eines elektrophilen bzw. Lewis-aciden Zentrums mit einer Wasserstoffbrückensequenz realisiert sowie deren gegenseitige Beeinflussung untersucht werden. Im Mittelpunkt standen dabei Barbitursäure-funktionalisierte Triarylmethylium-Ionen sowie Merocyanine. Die Charakterisierung der synthetisierten Verbindungen erfolgte mittels NMR-Spektroskopie, Einkristall-Röntgenstrukturanalyse sowie solvatochromen Messungen. Besonderes Augenmerk lag auf der Wechselwirkung mit verschiedenen Rezeptoren über Wasserstoffbrückenbindungen, wobei sowohl die Anzahl als auch die Stärke der Wasserstoffbrücken variiert wurden. Die Reaktion der elektrophilen Barbiturate mit ausgewählten Nucleophilen wurde NMR- und UV/Vis-spektroskopisch verfolgt. In ternären Systemen bestehend aus Elektrophil, Nucleophil und Rezeptor wurde systematisch der Einfluss der Komplexierung über Wasserstoffbrücken auf die Gleichgewichts- und Geschwindigkeitskonstante der Elektrophil-Nucleophil-Rekombination erfasst. Daneben erfolgte die Bestimmung der Nucleophilie-Parameter substituierter Barbiturat-Anionen unter Berücksichtigung des ambidenten Verhaltens dieser Nucleophile.

La conception et la préparation de réseaux moléculaires organiques et hybrides à l'état cristallin ont été envisagées par un processus itératif d'auto-assemblage entre des briques de construction moléculaires préprogrammées et complémentaires appelées tectons. Cette approche est basée sur la reconnaissance moléculaire de modules dicationiques, donneurs de liaisons hydrogène, et d'unités anioniques, accepteurs de liaisons hydrogène. Ainsi, la combinaison des tectons moléculaires de la famille des bis-benzimidazoliums, intrinsèquement luminescents, avec des anions polycyanométallates conduit à la formation de réseaux moléculaires hybrides luminescents à l'état cristallin. Il a été procédé à l'étude des propriétés photophysiques de ces réseaux à l'état solide. De même, l'association de bis-amidiniums,briques dicationiques, à des anions de type azodibenzoates mène à des assemblages cristallins possédant la propriété de photo-commutation, c'est-à-dire conduisant à une isomérisation sous stimulus lumineux.

碩士
國立清華大學
化學系
87
The hybrid density functional calculations (B3LYP) have been performed to elucidate the profound meanings of hydrogen-bonding cooperativities in the modeling systems of serine protease and we further proposed the three significant ideas about enzyme catalysis, especially hydrolases. It is found that molecules, with electron donors and electron acceptors, have qualitatively and structurally intrinsic hydrogen-bonding cooperativities. Further, the results are extended to far indirect hydrogen-bonding cooperativities. The direct and indirect hydrogen-bonding cooperativities can provide a global and novel interacting picture of acid/base catalysis and general acid/base catalysis. Subsequently, the three significant ideas (brave and elegant hypotheses) of enzyme catalysis are primarily based on hydrogen-bonding cooperativities. First, there is a rule of thumb about qualitative predictions of local pKa values, resulting in optimal pH value of enzyme catalysis, of active site residues in reference to those of free amino acids. Second, the cation-anion ion pair (His+-Asp-) of serine protease possesses a short-strong hydrogen bond (SSHB), not a low-barrier hydrogen bond (LBHB), under the investigation of theoretical calculations of the modeling systems. The SSHB has the extremely asymmetric single well with ~2 kcal/mol barrier, in contrast to LBHB. Moreover, with regulation of SSHB and (His)C(2)H---O hydrogen bond, the proton-donating group (imidazolium) of His57 seems to have evolutional administration mode in order to preferentially facilitate the removal of leaving group. Third, the distance of side chains, between His57 and Ser195, seems to be pulled apart by comformational compression of oxyanion hole and SSHB in tetrahedral intermediate during enzyme catalysis of serine protease. This may build certain more favorable water-assisted mechanism, which can overcome the steric hindrance between leaving group and proton-donating group, in tetrahedral intermediate.

博士
國立臺北科技大學
電機工程系研究所
98
Modeling and simulation play an integral role in determining dynamic system performance. An accurate mathematical description of a dynamic system provides the researchers with the flexibility required to perform trade studies quickly and accurately in order to expedite the design process. However, many system analytical methodologies still rely on the model approximation procedures and numerical simulations. Due to the lack of physical insights, these approaches not only defer the conception of better system models but also may lead to the identification of the unnecessary loss of transfer efficiency. The aim of this research work is to develop an energy-based methodology with which to provide a unified representation for the dynamical modeling and analysis of electric network domain systems. These problems will be studied through the simulation analysis of time and frequency responses. By the use of its energy interactions and causality implications, it is possible to understand the inherent system properties early in the design/redesign stage before detailed component characteristics and equations are determined. The obtained information in turn suggests feasible directions for dynamic system design/redesign improvements for deriving better overall system performance. The research in this dissertation is significant because it is one of the first endeavors to address the challenging issue of realizing a structural modeling and analysis for electric network systems via a BG approach. It is shown that the novel BG/SEBD (Simulink Energy-based Block Diagram) structural modeling approach requires neither mathematical higher-order reduction nor physically-based model reduction. Two main topics are presented in this thesis to demonstrate the capability of the proposed structural modeling, simulation and analysis procedures. The first topic addresses the BG modeling concepts, whether they will prove to be very convenient and powerful in describing complex electric network systems analysis. An investigation into the creation of a BG model using the circuit diagram model of the higher-order electric network system is provided herein. The research of this dissertation examines the ability of a modeling, simulation and analysis methodology; a BG model with a Simulink Energy-based Block Diagram (SEBD) algorithm is developed. Through both SEBD and MATLAB simulation results, the physical insights contained within the BG models can be exploited to create a measurement for system efficiency. The second topic is the identification of system order and relative degrees for higher-order electric network systems. A method is proposed to derive the system order and relative degrees of electronic and electrical network systems from BG models, respectively; this way, the state equations of the system order can be easily obtained. Thus, the design/redesign and analysis of physical electric network systems, including the consideration of the system order and relative degrees, becomes straightforward. Several case studies of higher-order electronic and electrical network systems design problems, in micro-domains, have been used as examples to test the feasibility of the BG/SEBD approach. The VLSI interconnect network with a 20th-order RLC tree circuit modeling shows the efficiency and effectiveness of the proposed approach. A low voltage (LV) two-core 1.5 mm2 non-shielded power cable system design demonstrates that the BG/SEBD approach can also be used for redesign and is very effective in exploring a subsystem-interconnected topology space and capable of providing researchers with a variety of better design candidates for further analysis and tradeoff. From the results of this research, it is shown that the BG/SEBD method is a powerful synergistic approach, for modeling and analysis of electric network systems which can be conducted in a systematic way by studying the structure conceptual design. An energy-based structural modeling, simulation and analysis through BG/SEBD methodology that can handle these types of dynamical systems might be used in a direct fashion to extract added information from the BG/SEBD models. The proposed procedures can be easily coded and analytical results used for system design and component selection.

碩士
東吳大學
經濟學系
92
As new financial products are constantly evolving under the financial liberation policy of government, among them the convertible bond owns the characteristics of bonds and stocks, and has emerged as a viable investment tool for providing minimum protection and infinite potential yield. Compared to the traditional financial commodities, the issuing criteria and provisional conditions of this convertible bond vary greatly. In the past literatures, the market value of convertible bond has been consistently rated to be under the theoretic value; it has often leaded to severe bias in valuation. Therefore, as a combination product, the convertible bond does need a more complex valuation model. Fortunately as technology continues to progress, the rapid development of computers that are capable of swift and voluminous processing has also propelled the application of artificial intelligence to become more widespread. Coupled with the Ministry of Finance’s lifting the 0.1% transaction surtax on convertible bonds, and the government’s deregulating the insurance industry to invest in convertible bonds and shortening the stipulations governing convertible bonds’ close-ended period from the previous 3 to 6 months to now down to one month, This has excelled convertible bonds to be a red-hot investment tool for its tax exemption status and of a greater liquidity. In light of few prior studies on the valuation of convertible bonds and none taking to the genetic algorithms and the fuzzy theory, this paper has attempted to conduct the valuation on convertible bonds by integrating the various artificial intelligence methods to find the most accurate and systematic model that can be offered to the industry for valuation in convertible bond issues and to the investors as references for their trading decisions. The weekly data of this study has chosen from June 2000 to March 2004, and divided into the difference between closing and conversion prices, adjusted discount rate, ratio of the putable period to the issuing years, adjusted putable yield ratio, the extent of time-to-maturity, average return rate, average return volatility, cash dividends, and stock dividends as nine input variables, and the price of the convertible bond as the output variable, which are put through the following three artificial intelligence models to test the valuation of convertible bonds, 1.Artificial Neural Network (ANN): This chiefly pertains to mimicking the organic neural network’s information processing system. In which, the concept of the gradient steepest descent method derived from back-propagation neural network is adopted to minimize the error function. 2.Genetic Artificial Neural Network (GANN): Besides using the ANN to minimize the error, the mutual competitive method based on the gene evolution with Darwin’s “survival of the fitness” derived from the genetic algorithms (GA) in an attempt to find an optimal networking framework. 3.Fuzzy Genetic Artificial Neural Network (FGANN): In addition to the ANN and the GA, the fuzzy theory is incorporated to grasp the characteristic of fuzzy logic using membership function to describe the feature of a certain concept and to gain further understanding to the input variables in an attempt to derive more useful information, and to help prediction for the valuation of the convertible bond. In this research, root mean-square error (RMSE) is incorporated to serve as valuation performance indicator. Besides, the Wilcoxon sign-rank test method is used to analyze whether the performance significant different between the various artificial intelligent method and the multiple regression model. In this empirical study it concludes that, except for the stocks Hwa-Tung 1 and Wei- Shen 1, there is no significant different between GANN and FGANN, However, there are significant variations found to exist among all other test models. Furthermore, when putting the data all together, there are also significant through the Wilcoxon sign-rank testing. In addition, the performances of the ANN, GANN and FGANN models are found to be superior to that concluded by the conventional linear multiple regression model. Among them, FGANN is found superior to GANN, and GANN superior to ANN. In sensitivity analysis, The factors influencing the price of convertible bonds chiefly by ANN and GANN models is the “Closing price — conversion price” and “The extent of time-to-maturity”, while FGANN offers no consistent conclusion, which may chiefly be the result of introducing the fuzzy Logic that tends to lead to the changes among the variable inputs. Finally, in the future study we may consider changing all the parameters of the artificial neural network and genetic algorithms to improve the valuation performance of convertible bonds. In addition, the adaptation of the different fuzzy rules and the membership functions might change the results. Besides, given an adequate adaptation of sophisticated programs in the future, combining all artificial intelligent methods might provide a greater flexibility in practical applications.

碩士
國立臺灣大學
國際企業學研究所
89
This research aims to explore (1)the important variables for forecasting government bond price and the leading periods in which those variables influence government bond price. (2)whether the relative importance of every variables would change with time.(3)to fine tune the input variables for neural network and to examine the improvement of prediction performance ,according to the importance of variables in every interval. The key characteristics of this research methodology include (1)using unit root test for input variables in order to avoid spurious regression. (2)using adjusted Granger causality test to screen input variables and simultaneously to find out the leading periods of every variables. (3)dividing the variables into major and minor variables. If the major variables couldn’t be selected, they would be kept as the input variables to avoid the pitfall of the linear model for unpurposely screening out the important un-linear related variables. (4)designing the dynamic Sensitivity Analysis and Granger Causality test and illustrating the time track of the importance of every input variables. (5)constructing the neural network by adjusting dynamically the set of input variables. This study contributes to both academic and application researching in the following four aspects.(1)when using neural network for forecasting, latest variables should not be directly input but to consider the periods the input variables lead output variables. (2)whether the importance of variables will change in different interval should be considered. If the importance of every variable changes with time, the same variables should not be input for a long time during forecasting.(3)Improving the prediction performance by capturing the change of the importance of the input variables. (4)describing every variables in influencing government bond price (ex. positive or negative relation between them or mainly long term influence or mainly short term influence)

碩士
義守大學
工業工程與管理學系碩士班
97
Prevalently fierce competition in business environment, the decision making of executive will directly determine the development of one enterprise. However, there are myriad uncertainties even from the predictable future for each business establishment. It’s always an important task for an entrepreneur on how to precisely predict the future trend and making correct decision for the enterprise. The objective of this research has aimed to setup a more accurate prediction system which can be used to forecast production output, to increase the elasticity of supply and demand, and to provide the consultation of inventory control for executives. Maintaining a proper inventory level will be a key to avoid the operation cost increases due to unnecessarily high inventory level and ultimately results in heavy burden of the company. There are many methods of prediction analyses. The most valued one is Intelligence Prediction System in the recent years, such as the Artificial Neural Network (ANN), Fuzzy theory…etc. Among them, the Artificial Neural Network is a mathematical model widely applied on prediction. And in these massive researches, it also shows higher prediction accuracy than other traditional methods. Therefore, I would like to setup a prediction system with high accuracy by Artificial neural network and apply it to forecast the production output of package assembly. In this research, Grey Relational Analysis will be applied to select highly relative elements among numerous factors and place these elements into the prediction model of Artificial neural network for training and prediction analyses. Hence, a highly accurate prediction model will be established as a result.

This thesis provides macro-, meso- and micro-level analyses of a potential hydrogen refuelling network with a case study for the Kitchener census metropolitan area in Canada. It provides recommendations on the appropriate number of stations required to meet estimated demand for hydrogen refuelling. Furthermore, scenarios are produced using geographic information systems (GIS) to show possible networks. Micro-level analysis brings in the planning aspect of hydrogen specific zoning codes and the possible impacts of citizen and stakeholder resistances to hydrogen.

The thesis entitled “Unravelling the Nature of Halogen and Chalcogen Intermolecular Interactions by Charge Density Analysis" consists of five chapters. A basic introductory section describes the topics relevant to the work and the methods and techniques utilized. The main focus of the present work is to characterize the interaction patterns devoid of strong classical hydrogen bonds. The case studies include halogen bonds and hydrogen bonds involving bromine (as a halogen bond donor and hydrogen bond acceptor), intermolecular chalcogen bond formation involving sulphur, type I Br Br contacts, type II F F and F S interactions and S-H S hydrogen bonds. Chapter 1 discusses experimental and theoretical charge density analyses on 2,2-dibromo-2,3-dihydroinden-1-one which has been carried out to quantify the topological features of a short C Br···O halogen bond with nearly linear geometry (2.922Å, C Br···O=172.7) and to assess the strength of the interactions using the topological features of the electron density. The electrostatic potential map indicates the presence of the “- hole” on bromine while the interaction energy is comparable to that of a moderate O-H O hydrogen bond. In addition, the energetic contribution of C-H···Br interaction is demonstrated to be on par with that of the C-Br···O halogen bond in stabilizing the crystal structure. Chapter 2 discusses an organic solid, 4,7-dibromo-5,6-dinitro-2,1,3-benzothiadiazole that has been designed to serve as an illustrative example to quantitatively evaluate the relative merits of halogen and chalcogen bonding in terms of charge density features. The compound displays two polymorphic modifications, one crystall zing in a non-centrosymmetric space group (Z =1) and the other in a centrosymmetric space group with two molecules in the asymmetric unit (=2). Topological analysis based on QTAIM clearly brings out the dominance of chalcogen bond over the halogen bond along with an indication that halogen bonds are more directional compared to chalcogen bonds. The cohesive energies calculated with the absence of both strong and weak hydrogen bonds as well as stacking interaction are indicative of the stabilities associated with the polymorphic forms. Chapter 3 discusses the role of a type I C-Br Br-C contact and what drives the contact i.e. how a dispersive interaction is stabilized by the remaining contacts in the structure. In the process we observe the role the Br2Cl motif which is quite unique in its nature. Also the role of the bromine atoms in stabilizing the stacking interactions has been shown by the electrostatic potentials which are oriented perpendicular to the plane of the benzene ring. Chapter 4 discusses the enigmatic type II C-F F-C and C-FS-C interactions in pentafluorophenyl 2,2- bithiazole. Both the interactions are shown to be realistic “-hole” interactions based on high resolution X-ray charge density analysis. As fluorine is the most electronegative element, its participation in halogen bonding wherein the electrostatic potential around the atom gets redistributed to form regions of electron depletion and accumulation had time and again been speculated but never observed. In this chapter the experimental charge dnsity analysis clearly identifies the “-hole” on fluorine and distinguishes the C-F S-C interaction as a halogen bond rather than the chalcogen bond. Chapter 5 discusses the experimental charge density analysis of the hitherto unexplored S-H S hydrogen bond in crystal structures. The work highlights how relatively small is the number of crystal structures which are constructed by the S-H S hydrogen bond compared to the X-H S hydrogen bond via Cambridge Structural Database (CSD) analysis. The potential S-H S hydrogen bond is studied in three isomeric mercaptobenzoic acids with experimental charge density collected on 2-mercaptobenzoic acid and theoretical estimates made on 3- and 4-mercaptobenzoic acid. The strength and directionality of the S-H S hydrogen bond is demonstrated to be mainly due to the conformation locking potential of intramolecular S O halogen bond.

We report a Raman technique applicable for the in situ analysis of the development of hydrogen bonds in the liquid water‐rich phase just before the onset of gas hydrate formation. Herewith, the phase transition as well as the working principle of hydrate formation inhibitors and promoters can be analyzed.

The research work reported in this thesis is focused on the chiral analysis, quantification of enantiomeric composition, assignment of absolute configuration of molecules with chosen functional groups. The weak intra-molecular hydrogen bonding interactions are detected by exploiting several multinuclear and multi-dimensional techniques. Pulse sequences have been designed to manipulate the spin dynamics to derive specific information from the complex NMR spectra encountered in diverse situations. Broadly, the thesis can be classified in to three sections. The section I containing two chapters reports the introduction of new chiral auxiliaries and protocols developed for enantiomeric discrimination, measurement of enantiomeric contents, assignment of absolute configuration for molecules possessing specific functional groups using chiral solvating and derivatizing agents. The section II, reports NMR experimental evidence for the observation of the rare type of intramolecular hydrogen bonds involving organic fluorine in biologically important organic molecules, that are corroborated by extensive DFT based theoretical calculations. The section II also discusses the H/D exchange mechanism as a tool for quantification of HB strengths in organic building blocks. The section III reports the two different novel NMR methodologies designed for deriving information on the scalar interaction strengths in an orchestrated manner. The designed sequences are able to completely eradicate the axial peaks, prevents the evolution of unwanted couplings and also yields ultrahigh resolution in the direct dimension, permitting the accurate measurement of scalar couplings for a particular spin. The brief summary about each chapter is given below. Chapter 1 provides a general introduction to one and two dimensional NMR spectroscopy. The pedagogical approach has been followed to discuss the conceptual understanding of spin physics and the NMR spectral parameters. The basic introduction to chirality, existing approaches in the literature for discrimination of enantiomers and the assignment of absolute configuration of molecules with chosen functional groups and their limitations are briefly discussed. The brief introduction to hydrogen bond, experimental methods to obtain the qualitative information about the strengths of hydrogen bonds, and the theoretical approaches employed in the thesis to corroborate the NMR experimental findings have been provided. The mechanism of H/D exchange, the utilization of exchange rates to derive strengths of intra-molecular hydrogen bond in small molecules have also been discussed. This chapter builds the bridge for the rest of the chapters. Each of these topics are discussed at length in the corresponding chapters. Part I: NMR Chiral Analysis: Novel Protocols Chapter 2 discusses a simple mix and shake method for testing the enantiopurity of primary, secondary and tertiary chiral amines and their derivatives, amino alcohols. The protocol involves the in-situ formation of chiral ammonium borate salt from a mixture of C2 symmetric chiral BINOL, trialkoxyborane and chiral amines. The proposed concept has been convincingly demonstrated for the visualization of enantiomers of a large number of chiral and pro-chiral amines and amino alcohols. The protocol also permits the precise measurement of enantiomeric composition. The significant advantage of the protocol is that it can be performed directly in the NMR tube, without any physical purification. The structure of the borate complex responsible for the enantiodifferentiation of amines has also been established by employing multinuclear NMR techniques and DFT calculations. From DOSY and 11B NMR experiments it has been ascertained that there are only two possible complexes or entities which are responsible for differentiating enantiomers. From the combined utility of DFT calculations and the 11B NMR chemical shifts, the structure of the borate complex has been determined to be an amine-coordinated complex with the N atom of the amine. Chapter 3 discusses a simple chiral derivatizing protocol involving the coupling of 2-formylphenylboronic acid and an optically pure [1,1-binaphthalene]-2,2-diamine for the rapid and accurate determination of the enantiopurity of hydroxy acids and their derivatives, possessing one or two optically active centers. It is established that this protocol is not only rapid method for discrimination of enantiomers but also highly effective for assigning the absolute configuration of various chiral hydroxy acids and their derivatives. The developed protocol involves the coupling of 2-formylphenylboronic acid with (R)-[1,1-binaphthalene]-2,2-diamine, and 2-formylphenylboronic acid with (S)-[1,1-binaphthalene]-2,2-diamine as chiral derivatizing agents. The absence of aliphatic peaks from the derivatizing agent, large chemical shift separation between the discriminated peaks of diastereomers, and the systematic change in the direction of displacement of peaks for an enantiomer in a particular diastereomeric complex, permitted the unambiguous assignment of absolute configuration. Part II : Rare Type of Intramolecular Hydrogen Bonding In chapter 4 The rare occurrence of intramolecular hydrogen bonds of the type N–H˖˖˖F–C, in the derivatives of imides and hydrazides in a low polarity solvent, is convincingly established by employing multi-dimensional and multinuclear solution state NMR experiments. The observation of 1hJFH, 2hJFN, and 2hJFF of significant strengths, where the spin polarization is transmitted through space among the interacting NMR active nuclei, provided strong and conclusive evidence for the existence of intra-molecular hydrogen bonds. Solvent induced perturbations and the variable temperature NMR experiments unambiguously supported the presence of intramolecular hydrogen bond. The two dimensional HOESY and 15N–1H HSQC experiments reveals the existence of multiple conformers in some of the investigated molecules. The 1H DOSY experimental results discarded any possibility of self or cross-dimerization of the molecules. The results of DFT based calculations, viz., Quantum Theory of Atoms In Molecules (QTAIM) and Non Covalent Interaction (NCI), are in close agreement with the NMR experimental findings. In chapter 5 the rates of hydrogen/deuterium (H/D) exchange determined by 1H NMR spectra have been utilized to derive the strength of hydrogen bonds and to monitor the electronic effects in the site-specific halogen substituted benzamides and anilines. The theoretical fitting of the time dependent variation in the integral areas of 1H NMR resonances to the first order decay function permitted the determination of H/D exchange rate constants (k) and their precise half-lives (t1/2) with high degree of reproducibility. The comparative study also permitted the determination of relative strengths of hydrogen bonds and the contribution from electronic effects on the H/D exchange rates. Part III: Novel NMR Methodologies for the Precise Measurement of 1H-1H Couplings Chapter 6 describes two novel NMR methodologies developed for the precise measurement of 1H-1H couplings. Poor chemical shift dispersion and the pairwise interaction among the entire coupled network of protons results in the severely complex and overcrowded one dimensional 1H NMR spectra, hampering both the resonance assignments and the accurate determination of nJHH. The available two-dimensional selective refocusing (SERF) based experiments suffer from the evolution of magnetization from uncoupled protons as intense uninformative axial peaks. This creates ambiguity in the identification of peaks belonging to the coupled partners of a selectively excited proton, hindering the extraction of their interaction strengths. This challenge has been circumvented by designing two novel experimental technique, cited as “Clean-G-SERF” and “PS-Clean-G-SERF”. The Clean-G-SERF technique completely eradicates the axial peaks and suppresses the evolution of unwanted couplings while retaining only the couplings to the selectively excited proton. The method permits the accurate determination of spin-spin couplings even from a complex proton NMR spectrum in an orchestrated manner. The PS-Clean-G-SERF technique has been designed for the complete elimination of axial peaks and undesired couplings, with a blend of ultra-high resolution achieved by real time broad band homonuclear decoupling has been discussed in this chapter. The spin dynamics involved in both these pulse sequences have been discussed. The diverse applications of both these novel experiments have been demonstrated.