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 Title: Analytical Applications of Catalysis and Suppressed Catalysis of Luminol Chemiluminescence Author(s): Nussbaum, Mark Alan Department / Program: Chemistry Discipline: Chemistry Degree Granting Institution: University of Illinois at Urbana-Champaign Degree: Ph.D. Genre: Dissertation Subject(s): Chemistry, Analytical Abstract: Luminol chemiluminescence (CL) has been used in a variety of determinations of species which catalyze the luminol CL reaction. The research reported here examined analytical applications related to catalysis of the luminol CL reaction with respect to three primary areas.First, the potential of combining chemical catalysis and electrocatalysis of the luminol CL reaction was investigated. Electroactive chemical catalysts were examined for the possibility of immobilizing them on electrode surfaces and controlling their activity by changing the electrode potential. No species was found which possessed both the desired CL characteristics and electroactivity within an allowed window of potential bounded by oxygen reduction and luminol oxidation.Next, luminol CL was investigated as a means of determining exposure of cobaltioxalate and ferrioxalate actinometer solutions. A means of assaying ferrioxalate solutions by flow-injection was developed, utilizing Fe$\sp{2+}$-catalyzed luminol CL. The method was found to be superior to the traditional Fe$\sp{2+}$-phenanthroline absorbance method in terms of speed ($\sim$1 min. assay time) and sample size (less than 100 $\mu$L).Finally, the analytical utility of Cu$\sp{2+}$ suppression of Fe$\sp{2+}$-catalyzed luminol CL was examined. Amino acids were detected by their complexation with Cu$\sp{2+}$, giving rise to positive signals as the Cu$\sp{2+}$ suppression was diminished. Detection limits of 2-35 pmol were obtained in a flow-injection configuration, and the method was also shown to be applicable to high performance liquid chromatography. The extension of this technique to the determination of other species which also complex Cu$\sp{2+}$ was briefly investigated and shown to be possible. Issue Date: 1987 Type: Text Description: 268 p.Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1987. URI: http://hdl.handle.net/2142/70376 Other Identifier(s): (UMI)AAI8721725 Date Available in IDEALS: 2014-12-15 Date Deposited: 1987
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