Malonaldehyde, a very reactive member of the homologous series of dialdehydes, is associated with the autoxidative deterioration of lipids. Its measurement, in autoxidized lipid systems is an expression of the extent of oxidation, in lipids. Malonaldehyde lends itself well to such determinations because of the sensitivity and specificity of its quantification in complex lipid systems. Complete knowledge of the formation of malonaldehyde in autoxidized lipids. is lacking. Such knowledge would undoubtedly promote a better understanding of lipid autoxidation mechanisms. In this investigation, a method for detecting malonaldehyde through the use of its reaction with p-aminobenzoic acid was developed. This was adapted for use in measuring malonaldehyde in lipids and in tissue samples. The reaction between p-aminobenzoic acid and malonaldehyde was partially characterized, and a mechanism for the formation of the reaction product was postulated. The quantification of malonaldehyde in lipid systems by the use of p-aminobenzoic acid involves the use of a mild reducing agent such as stannous chloride to prevent interference from hyd roperoxides present in the system. The p-aminobenzoic acid reaction is highly specific for malonaldehyde and proceeds smoothly and rapidly at room temperature in a non-aqueous chloroform-methanol solvent system to yield a highly colored compound having a maximum absorbance at 406 mμ. and with a molar absorptivity of 73,500. The absorbance value may be converted directly to parts-per-million malonaldehyde through the use of a conversion factor in a simple equation. The limits of detectability of themethod are on the order of one ppm malonaldehyde. The measurement of malonaldehyde in the lipid fraction of tissue samples involves the prior extraction of the lipid with a non-aqueous chloroform-methanol solvent, by an extraction method which was developed for this purpose. The reaction of malonaldehyde with p-aminobenzoic acid involves the condensation of two molecules of p-aminobenzoic acid with one molecule of malonaldehyde. The reaction exhibits a rate maximum at a hydrogen ion concentrations of about 0.1 molar, and also exhibits rate dependencies upon the concentrations of both malonaldehyde and p-aminobenzoic acid. This strongly suggests that the reaction proceeds according to an S [subscript N] 2 mechanism. A postulated mechanism involves nucleophilic 1,4-addition of the amino nitrogen of p-aminobenzoic acid to the enol of malonaldehyde followed by-loss of water to form the enamine. The reaction with a second molecule of p-aminobenzoic acid involves nucleophilic substitution of the amino nitrogen at the carbonyl function of malonaldehyde followed by loss of water to form an imine linkage. / Graduation date: 1968

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No description available.

The overall goal of this research is to characterize the potential-dependent structure and composition of the alcohol-Ag electrochemical interface. The approach involves the use of a variety of electrochemical and spectroscopic tools to arrive at a consistent model for a series of straight-chain alcohols (methanol, ethanol, 1-propanol, and 1-pentanol) at Ag electrodes. There are essentially four areas of investigation presented in this dissertation. The first portion of this work has been directed at the development of charge coupled device detection in Raman spectroscopy so that many of the interface investigations could be performed. The advantages and limitations of these detectors in Raman spectroscopy are addressed. The second area involves the characterization of in-situ alcohol-Ag electrochemical interfaces using Raman spectroscopy and associated surface selection rules for the evaluation of solvent orientation and bonding. Since the series of alcohols offers a systematic variation in solvent properties, these studies provide substantial insight regarding some of the chemical interactions which can dictate orientation. The development of emersed electrode technologies is also presented as a means to improve selectivity for surface molecular species over bulk molecular species. The utility of this approach is demonstrated for a variety of straight-chain alcohols at both rough and smooth Ag electrodes. Conditions for emersing the molecular interface, intact, under potential control are presented. Finally, double layer capacitance measurements are performed to offer additional insight regarding alcohol solvent structure and interfacial composition as a function of electrode potential. In addition, capacitance-potential plots are used along with the Hurwitz-Parsons analysis to determine absolute surface coverage of Br⁻ as a function of electrode potential. These results are correlated with the Raman spectroscopic results to obtain a consistent model for the structure and composition of the alcohol-Ag electrochemical interface.

M.S. / Environmental Science / A technique to measure arsenobetaine and arsenocholine in fish tissue by fast atom bombardment mass spectrometry was developed with particular attention to quantitative analysis. Experiments were performed which demonstrate analysis of the compounds desorbed directly from thin layer silica chromatography matrices, quantitative analysis of arsenobetaine in real fish samples, and accurate mass measurement of arsenobetaine in normal FAB/MS using peaks from the glycerol matrix as mass references. Improvements to the technique to quantitatively measure these important arsenic metabolites are suggested including optimization of the extraction/isolation procedures and use of isotopically labelled internal standards or surrogates for more accurate measurements.

No description available.

M.Sc. (Geology) / This study involves the quantitative analysis of fluorspar-containing slurries by two X-ray diffraction methods, whereby these two methods of on-stream analysis are compared. The first method involves a single counter with a diffracted beam monochromator, and the second method involves a fixed geometry with an incident beam monochromator. The second method is a cheaper and more robust apparatus, which can withstand the harsh environment of the flotation plants. A new algorithm was developed for a more accurate calibration method. Programmes for calibration, recalibration and measuring of unknown samples were developed. The measuring apparatus was interfaced with a microcomputer for computerised operation of the system. Results from both methods were comparable, with more accurate results obtained for the feed and tailings than for the concentrate samples. The single detector apparatus can thus be replaced by the fixed geometry model, which is less expensive and more robust.

Please read the abstract in the section 00front of this document / Dissertation (MSc (Water Utilization))--University of Pretoria, 2006. / Chemical Engineering / unrestricted

Indiana University-Purdue University Indianapolis (IUPUI) / Microspectrophotometry is a quick, accurate, and reproducible method to compare colored fibers for forensic purposes. The use of chemometric techniques applied to spectroscopic data can provide valuable discriminatory information especially when looking at a complex dataset. Differentiating a group of samples by employing chemometric analysis increases the evidential value of fiber comparisons by decreasing the probability of false association. The aims of this research were to (1) evaluate the chemometric procedure on a data set consisting of blue acrylic fibers and (2) accurately discriminate between yellow polyester fibers with the same dye composition but different dye loadings along with introducing a multivariate calibration approach to determine the dye concentration of fibers. In the first study, background subtracted and normalized visible spectra from eleven blue acrylic exemplars dyed with varying compositions of dyes were discriminated from one another using agglomerative hierarchical clustering (AHC), principal component analysis (PCA), and discriminant analysis (DA). AHC and PCA results agreed showing similar spectra clustering close to one another. DA analysis indicated a total classification accuracy of approximately 93% with only two of the eleven exemplars confused with one another. This was expected because two exemplars consisted of the same dye compositions. An external validation of the data set was performed and showed consistent results, which validated the model produced from the training set. In the second study, background subtracted and normalized visible spectra from ten yellow polyester exemplars dyed with different concentrations of the same dye ranging from 0.1-3.5% (w/w), were analyzed by the same techniques. Three classes of fibers with a classification accuracy of approximately 96% were found representing low, medium, and high dye loadings. Exemplars with similar dye loadings were able to be readily discriminated in some cases based on a classification accuracy of 90% or higher and a receiver operating characteristic area under the curve score of 0.9 or greater. Calibration curves based upon a proximity matrix of dye loadings between 0.1-0.75% (w/w) were developed that provided better accuracy and precision to that of a traditional approach.