Sulfonyl fluoride systems and their derivatives, RS02F, where R represents hydrocarbon/fluorocarbon moieties continue to be of considerable interest. The incorporation of the sulfonyl fluoride group (S02F) into molecular systems can lead to compounds that are useful as ion-exchange resins, surface active agents, fuel cell electrolytes, and strong sulfonic acids/salts. Interest in preparing SF5 containing sulfonyl fluorides led to the synthesis of the ᵝ-sultone, SF5CHCF20S02, and its rearranged product. Hydrolysis of the sultone gave SF5CH2S02F which led to the sulfonic acid and salt, SF5CH2S03H•H20 and (SF5CH2S03)2Ca. Esters of the sultone were prepared by reaction of the sultone with fluorinated alcohols in the presence of NaF to give SF5CH(S02F)C(O)OR where R = CH2CF3 and CH(CF3)2. Polymeric SF5/S02F containing esters were prepared by reaction of allyl esters, RCX(S02F)C(O)OCH2CH=CH2, in ultraviolet light where R = CF3 or SF5 and X= H or F. Fluorinated silver carboxylate salts have been useful in preparing fluoroesters from alkyl iodides. Therefore, a new silver salt, FS02CF2C(0)0Ag was prepared and characterized; its reaction with (CH3)3SiI, HOCH2CH2I and alkyl bromides and iodides are reported. In addition, new SF5 containing fluoropolymers were synthesized via reaction of fluorinated olefins with SF5Br. Reactions of SF5 containing olefins with CF30Cl, C1F and Cl2 provide reagents that may be of potential use as precursors to sulfonyl fluoride containing systems. All new compounds were characterized by their respective infrared, nmr and mass spectra.

The supply of drinking water in Gokwe District (NW Zimbabwe) is almost entirely based on groundwater drawn from boreholes and open dug wells. In certain areas of the district, the occurrence of dental fluorosis has been linked to excessive fluoride in the water supplies. A high prevalence of dental fluorosis (about 62%) was previously recorded among school children in the district. The aim of this study was to determine relationships between the spatial distribution of fluoride content in drinking water supplies in Gokwe, and lateral and vertical geological variation. A total of 224 water samples were collected from 196 water sources in the study area (a further 18 water sources just outside the study area were also sampled). All the samples were analysed for fluoride in the field using the fluoride ion selective electrode method (FISE). One hundred and fifty nine duplicate samples were analysed for fluoride and common anions and cations using High Performance Ion Chromatography (HPIC) in the laboratory. Two main groups of computer programmes were employed: (1) Geographic Information System (ArcView® GIS) was used to store, analyse and display multiple layers of surface geologic and geographic information, and (2) a three-dimensional visualisation programme (Rockworks) was used to interpret and illustrate site stratigraphy based on borehole information. Results indicated that the fluoride content of drinking water in the study area ranges from 0 to 9.65 mg/L. Forty-seven water sources (24%) yielded water containing fluoride in excess of the World Health Organisation's (WHO) health limit of 1.5 mg/L F. Of the 47 high fluoride water sources, 43 were boreholes (pumped or artesian). The shallower water sources (dug wells, streams and dams) largely yielded low-fluoride water. / The groundwater fluoride contamination is stratigraphically controlled and originates from carbonaceous material (carbonaceous shales, carbonaceous mudstones and coaly material) within the Lower Madumabisa and Middle Wankie Members of the Lower Karoo Group. It has been shown that in general the greater the proportion of carbonaceous material intersected by a borehole, the greater the fluoride concentration of the water. Probable mineral sources of fluoride within the carbonaceous material include fluorapatite, kaolinite and trona. Chemical parameters that appear to influence the concentration of dissolved F in the water supplies include total dissolved solids (TDS), NaCl and pH. In relatively low fluoride waters, F concentrations generally increase with TDS and NaCl concentrations, whereas the highest F concentrations are found in moderately alkaline (pH 7.8-9) waters. Based on ranges of fluoride concentration in drinking water, fluorosis-risk zones were identified and have been illustrated on a fluorosis-risk map. The zones are: No Risk Zone (0-1.5 mg/L F), Moderate Risk Zone (1.5-3.0 mg/L F), High Risk Zone (3.0-6.0 mg/L F) and the Very High Risk Zone (6.0-10.0 mg/L F). The map suggests that groundwater available to people occupying 3650 km z (60.8%) of the study area potentially contains excessive fluoride (F>1.5 mg/L), presaging the occurrence of dental fluorosis, skeletal fluorosis and crippling skeletal fluorosis in the area. Different strategies may be employed to ameliorate the fluoride problem in Gokwe. / These include sinking new boreholes to optimal depths and in appropriate locations, promoting the use of surface water and shallow groundwater, resettlement and defluoridation. However in order to fully understand the problem and to prescribe these or other solutions more comprehensively, multi-disciplinary studies may be required. Such studies may consider isotopic dating of water to investigate any relationships between fluoride concentration and residence time of water, geochemical analyses of rocks and soils, detailed fluorosis epidemiology studies and test-scale defluoridation investigations.

The research described in this thesis focuses on the catalytic asymmetric hydrogenation of prochiral olefins using N, P – chelated iridium catalysts. This catalytic system is tolerant to a wide range of substrates and performs better than the well-known ruthenium- and rhodium-catalytic systems for substrates devoid of coordinating groups in proximity of the olefin. Low catalytic loadings (often <1 %) and the high atom efficiency of this reaction make it a synthetically useful method of chiral molecule synthesis. The primary aim of this thesis was to develop new catalysts that rapidly and efficiently hydrogenate a broad range of alkenes asymmetrically. Papers I and II describe the synthesis and evaluation of new, highly efficient, chiral N, P – ligated iridium complexes. These catalysts were obtained in relatively few steps, while leaving open possibilities to modify and fine-tune their structure. Their versatility is ideally suited to both industrial uses and to equip any catalyst box. Paper III deals with a common problem of defluorination of vinylic fluorides during the hydrogenation. The catalyst designed in that work performs well for several substrates giving very low defluorination rates making it a good starting point for further improvements to cover a broader scope of vinyl fluorides. The structures of the catalysts from papers I and III also offers an easy approach to attach the catalyst ligands to a solid support. Paper IV explores hydrogenation of vinyl boronates, which gives synthetically interesting borane compounds with high enantioselectivities. Taking into account the rich chemistry of organic boranes, these compounds are very important. Paper V deals with hydrogenation of diphenylvinylphosphine oxides and vinyl phosphonates, another important classes of substrates that give chiral phosphorous containing compounds of interest in many fields of chemistry: such as medicinal chemistry and organocatalysis. In papers VI and VII we explore the Birch reaction as a source of prochiral olefins. By combining asymmetric hydrogenation with it, we obtain a powerful method to create chiral compounds with excellent enantioselectivities that are next to impossible to make by other routes. The products of the asymmetric hydrogenation are further modified by other well-known transformation to create other induced stereogenic centres.

Thesis (Ph. D.)--Florida State University, 2004. / Advisor: Dr. Samuel L. Tabor, Florida State University, College of Arts and Science, Department of Physics. Title and description from dissertation home page (viewed June 16, 2004). Includes bibliographical references.

No description available.

Protein folding pathways can be extraordinarily complex. In this study, circular dichroism (CD) and 19F NMR are used to investigate the folding network of calmodulin, a calcium-binding protein, which is biosynthetically enriched with 3-fluorophenylalanine. In calmodulin’s calcium-loaded state, CD experiments identify the existence of a folding intermediate along a heat-denaturation pathway. In comparison to the native state, 19F NMR solvent isotope shifts reveal decreased accessibility of water to hydrophobic core, whereas O2 paramagnetic shifts show increased hydrophobicity of this folding intermediate. 15N-1H and methyl 13C-1H HSQC NMR spectra demonstrate that this folding intermediate retains a near-native tertiary structure, whose hydrophobic interior is highly dynamic. 19F NMR CPMG relaxation dispersion measurements suggest that this near-native intermediate state is transiently adopted below the temperature associated with its onset. The folding network also involves an unproductive off-pathway intermediate. In contrast, calmodulin’s calcium-free state exhibits a simpler folding process which lacks discernible intermediates.

Protein folding pathways can be extraordinarily complex. In this study, circular dichroism (CD) and 19F NMR are used to investigate the folding network of calmodulin, a calcium-binding protein, which is biosynthetically enriched with 3-fluorophenylalanine. In calmodulin’s calcium-loaded state, CD experiments identify the existence of a folding intermediate along a heat-denaturation pathway. In comparison to the native state, 19F NMR solvent isotope shifts reveal decreased accessibility of water to hydrophobic core, whereas O2 paramagnetic shifts show increased hydrophobicity of this folding intermediate. 15N-1H and methyl 13C-1H HSQC NMR spectra demonstrate that this folding intermediate retains a near-native tertiary structure, whose hydrophobic interior is highly dynamic. 19F NMR CPMG relaxation dispersion measurements suggest that this near-native intermediate state is transiently adopted below the temperature associated with its onset. The folding network also involves an unproductive off-pathway intermediate. In contrast, calmodulin’s calcium-free state exhibits a simpler folding process which lacks discernible intermediates.

This thesis is a study of solid halogenated organic compounds by Nuclear Magnetic Resonance Spectroscopy (NMR) in an attempt to extract previously inaccessible information. The first part of the thesis is concerned with three fluorinated steroids, studied by observing (^1)H, (^13)C and (^19)F nuclei. A number of experimental techniques are employed to verify solution-state and solid-state spectral assignments, and spectral anomalies are discussed. Both proton-coupled and proton-decoupled (^19)F solid-state spectra, recorded using specially designed spectrometer hardware, are presented. The huge gain in resolution afforded by the implementation of proton decoupling allows static and MAS spectra to yield previously inaccessible information pertaining to various NMR parameters of the fluorine nuclei. Advantages of (^1)H→(^19)F cross-polarisation experiments over single-pulse experiments are explained and rotational resonance, dipolar dephasing, T(_1), measurement and spin-exchange experiments are presented from which information regarding phenomena such as spin diffusion and polymorphism is gleaned. The second part of the thesis focusses on the topic of residual dipolar coupling, the transfer of quadrupolar effects to spin-1/2 nuclei via dipolar coupling and/or anisotropy m indhect coupling. Unexpected, field-dependent, multiplicities for signals in spectra of spin-1/2 nuclei are observed, which can be used to evaluate certain fundamental NMR parameters including the quadrupolar coupling constant and, m favourable cases, anisotropy in indirect coupling. The phenomenon is comprehensively studied for the (^13)C, (^35,37)Cl and (^13)C, (^79,81)Br spin-pairs in a range of solid halogenated compounds. Coupling to more than one halogen nucleus and long- range (non-bonded) coupling are considered. First-order perturbation, inverse first- order and "exact" theories, that allow the multiplet line positions to be predicted, are introduced and their results are subsequently compared to the experimentally observed the positions. Rapid molecular motion is shown to negate the effects of residual dipolar coupling and the phenomenon is analysed with the aid of NQR measurements.

Thesis (Ph.D.)--University of Delaware, 2008. / Principal faculty advisor: Steven K. Dentel, Dept. of Civil & Environmental Engineering. Includes bibliographical references.

Thesis (M.Phil.)--Hong Kong University of Science and Technology, 2008. / Includes bibliographical references (p. 145-154).