Spectroscopic studies of some ruthenium(II) polypyridyl complexes in solution, on porous Vycor glass (PVG), and bound to calf thymus DNA.
Item
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Title
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Spectroscopic studies of some ruthenium(II) polypyridyl complexes in solution, on porous Vycor glass (PVG), and bound to calf thymus DNA.
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Identifier
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AAI9325158
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identifier
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9325158
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Creator
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Tysoe, Steven A.
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Contributor
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Adviser: Thomas C. Strekas
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Date
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1993
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Language
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English
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Publisher
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City University of New York.
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Subject
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Chemistry, Inorganic | Chemistry, Biochemistry
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Abstract
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Reports of transition metal complexes containing Ru(II) with {dollar}\alpha{dollar}-diimine ligands have appeared in the literature within the last 20 years concerning their usefulness as a light sensitizers in photochemical processes, as well as a photocatalysts in electron transfer reactions. More recently, reports have appeared concerning the usefulness of Ru(II) complexes as spectroscopic probes of nucleic acid structure. Perturbations of the spectroscopic properties of Ru(II) complexes in the presence of a nucleic acid are indicative of the conformation or conformations existing in the DNA or RNA, as well as an indication of the binding characteristics of the metal complex to the nucleic acid.;Much attention has been given to transition metal complexes and their interaction with double-stranded DNA in the B-Form. Several Ru(II) complexes are known to bind to this conformation of DNA in an intercalative fashion, where a planar aromatic ligand can slip between two base pairs within the major groove. Some have also been shown to cleave DNA photolytically. Upon binding to DNA, effects on the optical spectra can lead to knowledge of the binding characteristics of the metal complex, and therefore serve as a probe of DNA structure.;Several metal complexes of the type Ru(bpy){dollar}\sb2{dollar}L{dollar}\sp{lcub}2+{rcub}{dollar} or Ru(phen){dollar}\sb2{dollar}L{dollar}\sp{lcub}2+{rcub}{dollar}, where L is a bis-chelate ligand, have been shown by our laboratories to bind to double-stranded DNA in aqueous solution. Binding is largely affected by the shape and charge of the ligands surrounding the metal, so these parameters have been varied for each complex studied.;Optical isomers of the complex Ru(bpy){dollar}\sb2{dollar}ppz{dollar}\sp{lcub}2+{rcub}{dollar}, which have been characterized in this work, exhibit differential binding to DNA. The differential binding is probed by several spectroscopic techniques, all which support intercalation of the ppz ligand of both enantiomeric complexes into the major groove of B-DNA, however the effect is more pronounced for the {dollar}\Delta{dollar} isomer. This is believed to be caused by the opposing (non-intercalating) bpy ligands which sterically interact with the sugar-phosphate backbone of DNA differently for each enantiomer. DNA binding of several other non-resolved Ru(II) complexes are also investigated in this work.
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Type
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dissertation
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Source
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PQT Legacy CUNY.xlsx
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degree
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Ph.D.
