This article reviews the properties and applications of a series of liquid crystal solvents for NMR spectroscopy of, particularly, biological compounds with emphasis placed on n-alkyl-poly(ethylene glycol)/n-alkyl alcohol, the most versatile liquid crystal system hitherto discovered. The applications of this solvent to mixtures, polymers and proteins are also mentioned.

This study contains four main parts. Part 1, poly(butylene succinate) (PBSu) rich random copolymers containing ~20% 2-methyl-1,3-propylene succinate (MPS), PBMPSu 80/20. The influence of minor MPS units on thermal properties and crystallization rate was investigated. Part 2, poly(butylene succinate) (PBSu) rich random copolymers containing ~5% 1,4-cyclohexanedimethylene succinate (CHDMS), PBCHDMSu 95/5. The influence of cyclohexane unit on thermal properties and crystallization rate was investigated. Part 3, Poly(butylene succinate) (PBSu) random copolymers containing ~50% 2-methyl-1,3-propylene succinate (MPS), PBMPSu 50/50. Blend of PBSu with poly(2-methyl-1,3-propylene succinate) (PMPSu). The weight ratio of PBSu and PMPSu were 1:1. The crystallization behavior and morphology was compared. Part 4, Poly(ethylene succinate) (PESu) random copolymers containing ~50¢H trimethylene succinate (TS), PETSu 50/50. Blend of PESu with poly(trimethylene succinate) (PTSu). The weight ratio of PESu and PTSu were 1:1. The crystallization behavior and morphology was compared. Molecular weights of copolymers were measured using capillary viscometer and gel permeation chromatography (GPC). The results indicate that polyesters used in this study have high molecular weights. The chemical composition and the sequence distribution of co-monomers in copolyesters were determined using 1H NMR and 13C NMR. The distribution in these copolyesters was found to be random from the evidence of a randomness value close to 1.0 for a random copolymer. Thermal properties of blends and copolyesters were characterized using differential scanning calorimeter (DSC) and thermogravimeter (TGA). The crystallization kinetics and mleting behaviors was analyzed after isothermal crystallization by DSC. Wide-angle X-ray diffractograms (WAXD) were obtained for specimens after complete isothermal crystallization. The growth rates, morphology were studied using polarized light microscope (PLM). The morphology of specimens after chemical etching was investigated using scanning electron microscope (SEM) and atomic force microscope (AFM). AS the ratio of MPS units increase, the degree of crystallinity and crystallization rate drop, it was due to decrease of butylene succinate sequence length. The spherulite growth rate of PBCHDMSu 95/5 is much slower compare with PBSu rich copolymers containing 5% TS or MPS. It was due to the steric effect of cyclohexane unit in the polymer chains. The crystalline morphology of PBMPSu 50/50 and PETSu 50/50 were quite different. It was due to the short sequence length of butylene succinate and ethylene succinate. From the analysis results by DSC and observation by PLM and SEM, it indicates that PBSu was miscible with PMPSu while PESu was partial miscible with PTSu.

Zugl.: Berlin, Freie Univ., Diss., 2009

Erlangen, Nürnberg, University, Thesis (doctoral), 1999.

Aachen, Techn. Hochsch., Thesis (doctoral), 2000.

Zugl.: Giessen, Univ., Diss., 2009

Zugl.: Berlin, Humboldt-Univ., Diss., 2009

The conformational preferences of several oligosaccharides are investigated herein using a combination of NMR spectroscopy and molecular dynamics (MD) simulations, focusing on the torsion angles associated with the glycosidic linkages. Strategies for obtaining usable J-HMBC spectra for carbons with an adjacent 13C label are described. By employing a selective pulse or a constant time modification, spectra free from interferences are obtained for site-specifically 13C labeled oligosaccharides. Intermolecular hydrogen bonding in sucrose is investigated using MD simulations performed at different concentrations. One of the most frequent intermolecular hydrogen bonds in the simulations, O3f∙∙∙HO3g, was detected using the HSQC-TOCSY NMR experiment. Based on MD simulations and NMR spectroscopy, the conformational ensemble for a trisaccharide segment of the LeaLex hexasaccharide is proposed to feature conformational exchange between conformations with positive and negative values for the ψ3 torsion angle in the β-D-GlcpNAc-(1→3)-β-D-Galp linkage. Using MD simulations, the conformation of the N-acetyl group is shown to influence the glycosidic conformation at a nearby linkage in two oligosaccharides. Short (1→6)-linked oligosaccharides are shown to exhibit conformational exchange at the ω and ψ torsion angles. Notably, the former torsion angle populates states with ψ ≈ ±90°. Conformationally sensitive homo- and heteronuclear coupling constants are determined using various NMR experiments. The experimental data, including effective distances from NOESY obtained for two of the compounds, is used to improve the representation of the ω torsion angle in the CHARMM36 force field. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 1: Manuscript. Paper 5: Accepted. Paper 6: Manuscript.</p>

Many of the current analytical techniques originally developed to characterize conventional reservoir rocks and fluid cannot adequately measure shale and source rocks. An example of this is Retort, where it is not feasible to get sufficient fluid from source rock to make useful measurements. The primary interest of this thesis is the exploration of other analytical techniques, two of which are previously unused in the oil and gas industry. These are Thermal Gravimetric Analysis (TGA), Pyrolysis-Gas Chromatography-Mass Spectrometry (Py-GC-MS), and Nuclear Magnetic Resonance (NMR). The techniques proposed offer valuable insight into the properties of the rock. TGA gives accurate weight of a sample as temperature is increased, Py-GC-MS is useful for identifying exact molecules in vaporized fluid, and NMR can be used to characterize viscosity and hydrocarbon chain length. The methods using these techniques can be utilized to further confirm mineralogy of a sample, identify the fluid constituents and quantify their weight, analyze changes in a sample between two different states, and calculate the free fluid saturations of oil and gas in shales. Procedures and results for each of these are presented in this thesis to show methodology and give the reader an idea of its useful applications. / text

Understanding pore network structure of a porous medium and fluid flow in the pore network has been an interest to researchers for decades. This study focuses on the characterization and simulation of the pore networks in petroleum reservoir rocks using conventional characterization techniques. A Representative Elemental Volume (REV) model is developed which simulates the pore network as a series of non-interconnected capillary tubes of varying sizes. The model implements mercury porosimetry (MP) results and capillary pressure principles to calculate the size of each bundle of capillary tubes based on a pore throat size distribution produced by the MP experiment. It also implements electrical properties of the rocks to estimate the average length of the capillary tubes. To verify the validity of the simulated network, permeability is calculated for the simulated network using Poiseuille’s flow principles for capillary tubes. Preliminary work showed that the model is capable of simulating the pore network reasonably well because permeability estimations for the simulated network matched measurements. In this study, MP and nuclear magnetic resonance (NMR) tests as well as centrifuge and permeability tests are performed on a suite of 11 sandstone and carbonate rock samples. Because electrical tests were not available, average length of flow paths is calculated with an alternative method that uses porosity to calculate tortuosity. Permeability estimations of the simulated network are compared with measurements. Estimations are also compared to other predictions using methods that implement MP and NMR data to simulate the pore network and the results show that the developed REV model out performs all the other techniques. / October 2015