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1H NMR and potentiometric studies of copper (II) speciation in ruminants



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Copper is one of the most important trace elements in ruminant nutrition. Its deficiency causes certain pathologies that can be cured by supplementation, by either five ("inorganic") or complexed ("chelated") forms. With the objective of being able to quantitatively compare the distribution of copper between the two forms of supplements, the speciation of copper in ruminant fluids was studied here. For this study, copper lysine supplement was used. It was necessary to first study the acid-base and complexation chemistry of lysine with copper (II). In addition, the complexation chemistry of glycine and histidine, were investigated. Mass balance equations were used to describe the distribution of copper (II) amongst different ligands. The results of the distribution of copper (II) ions in McDougall's solution (a simulated form of bovine saliva), indicate no significant differences in the distribution of copper using the different form of supplements. 1H NMR was used to validate the results from the computer model. Using a combination of the results from the saliva simulation model and the chemical shifts from the NMR studies, the chemical shift changes that would accompany the addition of copper (II) to McDougall's solution were predicted. Results from the models do not show any appreciable differences from experimental values. Rumen samples were collected. Important peaks in the 1H NMR spectrum were assigned. The spectrum indicated that acetic acid, resulting from the fermentation in the rumen, was a good probe for monitoring the speciation pattern. Speciation calculation indicated that the bulk of the copper would be bound to ammonia in the rumen. Changes in chemical shifts that result from the introduction of copper (II) to the rumen contents were predicted. Results were compared with experimental values. Agreement between the two sets of results was found to be satisfactory. The study shows that any advantages that result from the use of copper lysine supplement are not as a result of its remaining intact. Though metal bioavailabilities are hard to predict this approach could help better our understanding of this process. The methods developed here could be extended to other metal complexation problems in biological fluids. (Abstract shortened by UMI.)



chemistry, copper metabolism, ruminants - digestion, rumen, copper (II) speciation



Doctor of Philosophy (Ph.D.)







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