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Dipyridophenazine Complexes of Ruthenium(II) as Luminescent Reporters of DNA

Citation

Jenkins, Yonchu (1996) Dipyridophenazine Complexes of Ruthenium(II) as Luminescent Reporters of DNA. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/n4jx-hp63. https://resolver.caltech.edu/CaltechTHESIS:11082019-094749072

Abstract

The search for novel diagnostics for DNA detection has generated interest in the potential applications of polypyridyl complexes of ruthenium(II). Recently, it was reported that dipyridophenazine complexes of ruthenium(II) may serve as molecular light switches for DNA. These complexes, which bind DNA avidly through intercalation, show no luminescence in aqueous solutions. Upon intercalation into double-helical DNA and the concomitant protection of the phenazine ring from quenching by interaction with water, intense photoluminescence is apparent. The light switch effect as a function of nucleic acid sequence and conformation was examined for [Ru(phen)2dppz]2+ and [Ru(bpy)2dppz]2+. The emission properties of these complexes were found to be extremely sensitive to the nature of the intercalation environment with strong correlations between the luminescence parameters and the level of water protection afforded by the double helix. In order to impart sequence specificity to the light switch effect, various methods have been developed for appending a functionalized [Ru(phen)2dppz]2+ to the 5' terminus of oligonucleotides, both on the solid support and in solution. Assays for analyzing the structural integrity of the resulting conjugates are described. These ruthenated oligonucleotides can serve as enzyme substrates, enabling the construction of long metalated oligonucleotides not easily prepared using chemical synthesis. In order to evaluate their utility as useful DNA diagnostics, a series of ruthenated oligonucleotides were synthesized and their photophysical properties characterized. Biochemical analysis of oligonucleotide duplexes containing ruthenated strands showed no significant structural perturbation of the duplex as a result of the ruthenium modification. The overall results of this investigation suggest that an oligonucleotide functionalized with a dppz complex of ruthenium may be used to target single-stranded DNA in a sequence-specific fashion and that this derivative could be extremely valuable in the development of novel hybridization probes for both heterogeneous and homogeneous assays.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Chemistry
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Barton, Jacqueline K.
Thesis Committee:
  • Gray, Harry B. (chair)
  • Barton, Jacqueline K.
  • Imperiali, Barbara
  • Richards, John H.
Defense Date:19 January 1996
Other Numbering System:
Other Numbering System NameOther Numbering System ID
UMI9800427
Record Number:CaltechTHESIS:11082019-094749072
Persistent URL:https://resolver.caltech.edu/CaltechTHESIS:11082019-094749072
DOI:10.7907/n4jx-hp63
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:11902
Collection:CaltechTHESIS
Deposited By: Melissa Ray
Deposited On:10 Dec 2020 23:21
Last Modified:10 Dec 2020 23:22

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