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Electrochemistry and electrogenerated chemiluminescence of Ru(phen)(2)dppz fluoborate both free and intercalated into DNA

Posted on:2008-08-19Degree:Ph.DType:Dissertation
University:The University of Texas at AustinCandidate:Calhoun, Robert Lee, JrFull Text:PDF
GTID:1441390005954833Subject:Chemistry
Abstract/Summary:
Ruthenium (II) bisphenanthroline dipyridophenazine, Ru(phen) 2dppz2+, exhibits first oxidation and reduction voltammetric responses which correlate well with the UV-vis 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.
Keywords/Search Tags:Electrogenerated chemiluminescence, Free and intercalated
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