Creatine (Cr) is a nitrogen-containing compound endogenously synthesised in the kidneys, liver and pancreas from the amino acid arginine, with further additions from glycine and methionine. Optimal levels of muscle Cr and PCr may delay the onset of fatigue during muscle contraction that relies on the ATP-PCr energy system. Cr supplementation is considered necessary to increase skeletal muscle’s capacity to generate energy quickly, thereby enhancing maximal exercise performance. Researchers have paid little attention to the effect of Cr supplementation on aerobic endurance performance. Cr supplementation is also associated with an enhanced cellular anabolic state that may potentially prevent or lessen muscle atrophy associated with high-mileage training in ultradistance runners. The aim of this research was to investigate the ergogenic effects and safety of Cr supplementation over the short-, moderate-, and long term. For this purpose two population groups of interest were identified, namely well-trained male ultradistance runners and highly active male university students. Seventeen well-trained male ultradistance runners were paired and then, in a double-blind fashion, assigned to either a group consuming Cr monohydrate (CRE group; 38 ± 7.8 yrs; n = 9) or a group consuming placebo (PLA group; 37 ± 8.2 yrs; n = 8). Participants ingested 6 g/day supplement for six days. After post-test 1 (on day 7), the maintenance dosage was ingested at 3 g/day for 9 weeks. Participants adhered to an individually-tailored, high-intensity, high-volume sport-specific training programme. / Thesis (DPhil)--University of Pretoria, 2013. / gm2013 / Biokinetics, Sport and Leisure Sciences / unrestricted

In Part I of this thesis an irradiated single crystal of dipotassium difluoromalonate monohydrate has been studied by Electron Spin Resonance. On X-irradiation the crystal yields CF(COO¯)2 radical with a highly anisotropic hyperfine tensor, characteristic of a (19)F nucleus. In addition, some other lines were also observed which were too weak to be analyzed. On γ-irradiation, the crystal yields mainly the same radical in addition to two types of CF(2)COO¯ radicals. In one type, the carboxyl group was found to be nearly coplanar with the CF(2) fragment while in the other, it was nearly perpendicular. A broad central line in each spectrum indicated also the possibility of the presence of CO(2)¯ radical. An unrestricted Hartree-Fock calculation, using the approximation of Intermediate Neglect of Differential Overlap was carried out on a number of fluorinated radicals to correlate the (19)F hyperfine tensors obtained in the present study with those obtained previously. The theory was used to calculate the theoretical hyperfine tensors for various radicals and was found to give a reasonably good agreement with the experimental results. On this basis the hyperfine tensor for CHFCOO¯ radical was predicted. The calculation also showed that one of the carboxyl groups in CF(COO¯)2 radicals is co-planar with the radical plane while the other makes an angle of 85°. In Part II, a crystal of zinc trifluoroacetate dihydrate, containing small amounts of Cu++ has been studied at 77°K and it was found that the Cu++ ion resides in an approximately tetragonal environment with the ground state consisting of mainly d(z2) orbital which is coupled to d(x2)-(y2) orbital, perhaps through vibronic interactions. Also a solution of copper trifluoroacetate in trifluoroacetic acid was studied at room temperature and at 77°K and the results were interpreted by assuming a tetragonal symmetry with the ground state being pure d(x2)-(y2). / Science, Faculty of / Chemistry, Department of / Graduate

No processo de obtenção de níquel de fontes de minério limonita, a lixiviação ácida do minério resulta na dissolução de íons metálicos em uma solução aquosa. Com o uso da tecnologia apropriada, é possível recuperar esses íons metálicos em vez de descartá-los. O presente estudo tem como objetivo a recuperação de magnésio de uma solução contendo íons magnésio e sulfato utilizando-se a técnica da cristalização a alta temperatura. A aplicação da cristalização a alta temperatura para recuperar o magnésio na forma de sulfato de magnésio hidratado pode ser vantajosa uma vez que sua decomposição térmica resulta em MgO e SO2, produtos que podem ser reutilizados no processo de mineração da limonita. Isso reduz o volume de resíduo formado e custo de reagentes no processo. Foi projetado um sistema de cristalizador acoplado a filtração e foi verificado a influência da temperatura, tempo de residência e pH da solução na quantidade de magnésio cristalizado. A solução residual de cada batelada foi analisada por cromatografia de íons para quantificar o magnésio na solução. Os cristais formados foram analisados utilizando-se a técnica de difração de raios-X (DRX), por microscopia eletrônica de varredura (MEV-EDS) e agitamento de peneiras a fim de avaliar a composição química, morfologia e granulometria dos cristais. A solubilidade do sulfato de magnésio foi determinada experimentalmente com o intuito de ampliar a compreensão da solubilidade do sal e obter valores de Kps. Em 5 horas de tempo de residência o sistema foi estabilizado, indicando que não haverá mais crescimento cristalino em tempos de residência maiores que 5 horas. Em pH 5,7 a 230°C e em 5 horas de tempo de residência ocorreu a maior remoção de magnésio com cerca de 81% cristalizado. Os cristais apresentaram morfologia esférica com exceção do cristal obtido a 230 °C em pH 2, que apresentou formato retangular. A análise por DRX mostrou a presença de um produto constituído majoritariamente por sulfato de magnésio monohidratado. / In the process of obtaining nickel from sources of limonite ore, the acid leaching of the ore results in the dissolution of metallic ions in solution. With the use of appropriate technology, it is possible to recover these metal ions instead of discarding them. The present study aims to recover magnesium from a solution containing magnesium and sulfate ions using high temperature crystallization. The application of high temperature crystallization to recover magnesium in the form of hydrated magnesium sulfate may be advantageous since its thermal decomposition results in MgO and SO2, products which can be reused in the limonite mining process. This reduces the volume of waste formed and the cost of reagents in the process. A crystallizer coupled to a filtration system was designed and the influence of the temperature, residence time and pH of the solution on the amount of crystallized magnesium from solution was investigated. The residual solution was analyzed by ion chromatography to quantify the magnesium in the solution. The crystals formed were analyzed by X-ray diffraction (XRD), Scanning Electron Microscopy (SEM-EDS) and sieve shakers in order to evaluate the chemical composition, morphology and grain size of the crystals. The solubility of magnesium sulphate was determined experimentally to increase the understanding of the solubility of the salt and obtain values of Kps. In 5 hours of residence time the system was stabilized, indicating that there will be no more crystalline growth at residence times greater than 5 hours. At pH 5.7 at 230 ° C and in 5 hours of residence time 81% of Mg crystallized. The crystals presented spherical morphology except for crystals obtained at 230 °C, at pH 2, which presented a rectangular shape. XRD analysis showed the presence of a product consisting mainly of magnesium sulphate monohydrate.

The purpose of this thesis was to determine ways to maximize creatine uptake and retention during creatine supplementation. Since there are many factors that affect muscle creatine concentrations, a series of studies were performed. In the first study, the purpose was to determine if á-lipoic acid aided creatine uptake and retention. It was hypothesized that á-lipoic acid would increase creatine uptake, because it has been found to increase glucose disposal in animal studies and because creatine uptake has been found to be related to increased glucose transport. Results showed that phosphocreatine and total creatine increased following supplement intervention. In the second study, the purpose was to develop an optimal dose of creatine in order to minimize urinary excretion of creatine. It was hypothesized that individuals with more lean tissue mass would excrete less urinary creatine during consumption of the same loading dose. There was a high negative correlation between lean tissue mass and urine creatine excretion. Regression equations were developed for the relationship between lean tissue mass and urine total creatine and used to determine the amount of creatine to ingest relative to lean tissue mass that would result in minimal creatine losses in urine. Based on these results, a creatine dose of 0.22 [right arrow] 0.25 g/kg lean tissue mass/d was recommended. In the third study, the purpose was to determine if a habitual vegetarian diet resulted in lower muscle creatine and phosphocreatine concentrations compared to an omnivorous diet. A secondary purpose was to determine if creatine supplementation and weight training resulted in greater increases in muscle metabolite content, muscle fiber area, lean tissue mass, and strength in vegetarians compared to non-vegetarians. Results indicated that vegetarians had lower resting total creatine concentration, and that creatine supplementation and weight training led to greater increases in muscle phosphocreatine and total creatine in vegetarians compared to non-vegetarians (p < 0.0125). The supplement and exercise intervention eliminated the differences in intramuscular total creatine concentration that existed prior to the study. Type II muscle fiber area, lean tissue mass, total work output, and 1-RM bench press increased to a greater extent following creatine supplementation compared to placebo supplementation (p < 0.017), with no difference between vegetarians and non-vegetarians. (Abstract shortened by UMI.)

No processo de obtenção de níquel de fontes de minério limonita, a lixiviação ácida do minério resulta na dissolução de íons metálicos em uma solução aquosa. Com o uso da tecnologia apropriada, é possível recuperar esses íons metálicos em vez de descartá-los. O presente estudo tem como objetivo a recuperação de magnésio de uma solução contendo íons magnésio e sulfato utilizando-se a técnica da cristalização a alta temperatura. A aplicação da cristalização a alta temperatura para recuperar o magnésio na forma de sulfato de magnésio hidratado pode ser vantajosa uma vez que sua decomposição térmica resulta em MgO e SO2, produtos que podem ser reutilizados no processo de mineração da limonita. Isso reduz o volume de resíduo formado e custo de reagentes no processo. Foi projetado um sistema de cristalizador acoplado a filtração e foi verificado a influência da temperatura, tempo de residência e pH da solução na quantidade de magnésio cristalizado. A solução residual de cada batelada foi analisada por cromatografia de íons para quantificar o magnésio na solução. Os cristais formados foram analisados utilizando-se a técnica de difração de raios-X (DRX), por microscopia eletrônica de varredura (MEV-EDS) e agitamento de peneiras a fim de avaliar a composição química, morfologia e granulometria dos cristais. A solubilidade do sulfato de magnésio foi determinada experimentalmente com o intuito de ampliar a compreensão da solubilidade do sal e obter valores de Kps. Em 5 horas de tempo de residência o sistema foi estabilizado, indicando que não haverá mais crescimento cristalino em tempos de residência maiores que 5 horas. Em pH 5,7 a 230°C e em 5 horas de tempo de residência ocorreu a maior remoção de magnésio com cerca de 81% cristalizado. Os cristais apresentaram morfologia esférica com exceção do cristal obtido a 230 °C em pH 2, que apresentou formato retangular. A análise por DRX mostrou a presença de um produto constituído majoritariamente por sulfato de magnésio monohidratado. / In the process of obtaining nickel from sources of limonite ore, the acid leaching of the ore results in the dissolution of metallic ions in solution. With the use of appropriate technology, it is possible to recover these metal ions instead of discarding them. The present study aims to recover magnesium from a solution containing magnesium and sulfate ions using high temperature crystallization. The application of high temperature crystallization to recover magnesium in the form of hydrated magnesium sulfate may be advantageous since its thermal decomposition results in MgO and SO2, products which can be reused in the limonite mining process. This reduces the volume of waste formed and the cost of reagents in the process. A crystallizer coupled to a filtration system was designed and the influence of the temperature, residence time and pH of the solution on the amount of crystallized magnesium from solution was investigated. The residual solution was analyzed by ion chromatography to quantify the magnesium in the solution. The crystals formed were analyzed by X-ray diffraction (XRD), Scanning Electron Microscopy (SEM-EDS) and sieve shakers in order to evaluate the chemical composition, morphology and grain size of the crystals. The solubility of magnesium sulphate was determined experimentally to increase the understanding of the solubility of the salt and obtain values of Kps. In 5 hours of residence time the system was stabilized, indicating that there will be no more crystalline growth at residence times greater than 5 hours. At pH 5.7 at 230 ° C and in 5 hours of residence time 81% of Mg crystallized. The crystals presented spherical morphology except for crystals obtained at 230 °C, at pH 2, which presented a rectangular shape. XRD analysis showed the presence of a product consisting mainly of magnesium sulphate monohydrate.

The influence of plasticization and other formulation factors on the properties of hot-melt extruded dosage forms for the controlled release of water-soluble active compounds was investigated. Citric acid monohydrate was demonstrated to function as a solid-state plasticizer in hot-melt extruded Eudragit® RS PO tablets and in cast films when concentrations below the compatibility limit were employed. Melting of the organic acid and solubilization in the polymer during extrusion were necessary to observe the plasticizing effect. The release rate of diltiazem hydrochloride, used as a high-melting, water-soluble model drug, from melt extruded Eudragit® RS PO matrix tablets increased and became independent of the original drug particle size in the presence of citric acid monohydrate. Thermal analysis of physical mixtures demonstrated that citric acid promoted drug melting during extrusion by interaction and melting point depression. Diltiazem hydrochloride remained amorphous in the final dosage form, and leaching of citric acid monohydrate enhanced drug diffusion by increasing the matrix porosity. Delayed-release matrix pellets with particle sizes below one mm were prepared by hot-melt extrusion, and the influence of the matrix forming polymer and the type and level of plasticizer on the processibility and release properties was investigated. Pellets complied with the USP requirement for delayed release articles to release less than 10% drug at pH 1.2 after 2 hours when plasticized Eudragit® S100 was used as the release-controlling material. High levels of efficient plasticizers had to be employed to decrease the polymeric melt viscosity, increase the process yield and enable extrusion at moderate temperatures to avoid instabilities during processing and storage. The aqueous solubility of the plasticizer further impacted the drug release rate in acid. A novel application of hot-melt extrusion for the preparation of monolithic matrices comprising enteric coated particles was studied. The influence of the mechanical strength of the multiparticulates, pellet loading and nature of the hydrophilic carrier material on the preservation of the delayed-release properties after extrusion was investigated. Soft particles coated with brittle films remained intact when low-melting carriers that did not solubilize the enteric film during extrusion were used, and the dissolution profile was stable over one year. / text

<p>[missing page:45]</p> / <p>BACKGROUND: Creatine monohydrate (CrM) supplementation during resistance exercise results in a greater increase in fat free mass (FFM), total body mass (TBM), and strength in young men and women. The purpose of the present investigation was to examine the interactive effects of creatine supplementation and resistance training on body composition, strength, and intramuscular total creatine concentration in older men and women.</p> <p>METHODS: Twenty-eight older men and women were randomly allocated, in a double blind fashion, to receive either CrM (n=14; CrM: 5g + 2g dextrose) or placebo (n=14; PL: 7g dextrose). Subjects participated in a 14 wk progressive, whole-body resistance training program. Pre-and post-training measurements included: 1 RM strength, isometric strength, body composition (TBM, FFM, %BF), muscle fiber area, and muscle total creatine and phosphocreatine.</p> <p>RESULTS: Training resulted in an increase in 1 RM strength for each of the 4 exercises (range = 26 - 60%) (p < 0.001), an increase in knee and dorsiflexion isometric strength (p < 0.001) and an improvement of performance on functional tasks (p < 0.001). Knee isometric strength was increased more for CrM (46.2%) as compared to PL (22.5%) (p < 0.05). Total body mass and lean body mass increased more for CrM (TBM: +1.2 kg; LBM: +1.7 kg) as compared to PL (TBM: -0.2 kg; LBM: 0.4 kg) (p < 0.05)</p> <p>CONCLUSIONS: We conclude that erM supplementation results in a greater increase in isometric knee extensor strength, total body mass and lean body mass during resistance training in older adults.</p> / Master of Science (MSc)

No / The surface energy of a-lactose monohydrate measured by inverse gas chromatography (IGC) is reported along with a dynamic molecular modelling study of the interaction of the various molecular probes with different surfaces of a-lactose monohydrate. The IGC results show that a-lactose monohydrate is acidic in nature. Using quantitative calculations of the energy of adsorption, the acidic nature of the surface is confirmed and the calculated values agree closely with the experimentally measured values. Along with the acidic nature, dynamic molecular modelling also reveals that the presence of a channel and water molecules on a surface affects the surface energetics of that face. The presence of water on the surface can decrease or increase the surface energy by either blocking or attracting a probe molecule, respectively. This property of water depends on its position and association with other functional groups present on the surface. The effect of a channel or cavity on the surface energy is shown to depend on its size, which determines whether the functional groups in the channel are assessable by probe molecules or not. Overall molecular modelling explains, at the molecular level, the effect of different factors affecting the surface energy of individual faces of the crystal.

When proteins and DNA interact, arginine and lysine are the two amino acids most often in close contact with the DNA. In order to understand the radiation damage to DNA in vivo, which is always associated with protein, it is important to learn the radiation chemistry of arginine and lysine independently, and when complexed to DNA. This work studied X-irradiated single crystals of L-lysine monohydrochloride dihydrate (L-lysine·HCl·2H2O) and L-arginine monohydrochloride monohydrate (L-arginine·HCl·H2O) with EPR, ENDOR, EIE techniques and DFT calculations. In both crystal types irradiated at 66K, the carboxyl anion radical and the decarboxylation radical were detected. DFT calculations supported these assignments. Specifically, the calculations performed on the cluster models for the carboxyl anion radicals reproduced the proton transfers to the carboxyl group from the neighboring molecules through the hydrogen bonds. Moreover, computations supported the identification of one radical type as the guanidyl radical anion with an electron trapped by the guanidyl group. In addition, the radical formed by dehydrogenation of C5 was identified in the L-arginine·HCl·H2O crystals irradiated at 66K. For both crystal types, the deamination radicals and the dehydrogenation radicals were identified following irradiation at 298K. Different conformations of main-chain deamination radicals were detected at 66K and at 298K. In L-lysine·HCl·2H2O, these conformations are the result of the different rotation angles of the side chain. In L-arginine·HCl·H2O, one conformation at 66K has no O-H dipolar protons while the others have two O-H dipolar protons. In L-lysine·HCl·2H2O, two radicals with very similar sets of hyperfine couplings were identified as the result of dehydrogenation from C3 and C5. Two other radicals in low concentration detected only at 66K, were tentatively assigned as the radical dehydrogenated from C3 and the side-chain deamination radical. In L-argnine·HCl·H2O, the radicals from dehydrogenation at C5 and C2 also were identified. DFT calculations supported these assignments and reproduced conformations of these radicals.Finally, based on the radicals detected in the crystal irradated at 66K and at 298K, the annealing experiments from the irradiation at 66K, and the previous studies on the irradiated amino acids, the mechanisms of the irradiation damage on lysinie and arginine were proposed.

No description available.