Electrochemisty and electrogenerated chemiluminescence of Ru(phen)₂dppz(BF₄)₂ both free and intercalated into DNA

dc.contributor.advisorBard, Allen J.en
dc.creatorCalhoun, Robert Leeen
dc.date.accessioned2011-08-18T15:16:59Zen
dc.date.available2011-08-18T15:16:59Zen
dc.date.issued2007-05en
dc.descriptiontexten
dc.description.abstractRuthenium (II) bisphenanthroline dipyridophenazine, Ru(phen)2dppz2+, exhibits first oxidation and reduction voltammetric responses which correlate well with the UVvis spectroscopy and are typical to the compound class. The complex proves energy sufficient for electrogenerated chemiluminescence (ECL), and does so in aqueous media with co-reactants, also similar to its phenanthroline and bipyridine analogues. However, this behavior is curious since this compound’s aqueous photoluminescence (PL) is undetectable but exhibits ‘light switch’ behavior upon intercalation into both calf thymus DNA and other polynucleotides in that the PL greatly increases. The ECL of both the free and intercalated complex is presented as well as scanning electrochemical microscopy (SECM) studies to understand the complex’s kinetic behavior in water upon oxidation. In an effort to understand the SECM results, the program COMSOL Multiphysics is used to model the EC’ (catalytic) following reaction. The simulation results are validated using the ferrocyanide/cysteine system, which is known to exhibit the EC’ mechanism.
dc.description.departmentChemistryen
dc.format.mediumelectronicen
dc.identifier.urihttp://hdl.handle.net/2152/13180en
dc.language.isoengen
dc.rightsCopyright is held by the author. Presentation of this material on the Libraries' web site by University Libraries, The University of Texas at Austin was made possible under a limited license grant from the author who has retained all copyrights in the works.en
dc.subjectElectrochemistryen
dc.subjectRutheniumen
dc.subjectChemiluminescenceen
dc.titleElectrochemisty and electrogenerated chemiluminescence of Ru(phen)₂dppz(BF₄)₂ both free and intercalated into DNAen
thesis.degree.departmentChemistryen
thesis.degree.disciplineChemistryen
thesis.degree.grantorThe University of Texas at Austinen
thesis.degree.levelDoctoralen
thesis.degree.nameDoctor of Philosophyen

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