Local Structure and Dynamics of Exciton-Coupled Cyanine Dimers Labeled in DNA

Simple item page
dc.contributor.advisorCina, Jeffrey
dc.contributor.authorKringle, Loni
dc.date.accessioned2018-09-06T21:56:51Z
dc.date.available2018-09-06T21:56:51Z
dc.date.issued2018-09-06
dc.description.abstractUnderstanding the properties of electronically interacting molecular chromophores, which involve internally coupled electronic-vibrational motions, is important to the spectroscopy of many biological systems. Here we apply linear absorption, circular dichroism, and two-dimensional fluorescence spectroscopy to study the local structure and excited state dynamics of excitonically coupled cyanine dimers that are rigidly positioned within the sugar-phosphate backbones of the DNA. Dimer probes were positioned within the double-stranded DNA duplex and at the single-strand/double-stranded DNA junction to examine the positional dependence of the structural variation and fluctuations. We interpret spectroscopic measurements in terms of the Holstein vibronic dimer model, from which we obtain information about the local conformation of the dimer probe locally within their respective DNA environments. We show that the exciton-coupling strength of the dimer-DNA construct can be systematically varied with temperature below the double-stranded – single-strand DNA denaturation transition. Using time-resolve 2DFS measurements we observed long lived vibronic coherences in the system. The properties of the cyanine DNA construct we determine suggest that it may be employed as a useful model system to test fundamental concepts of protein DNA interactions and the role of electronic-vibrational coherence in electronic energy migration within exciton-coupled biomolecular arrays. This dissertation contains previously published and unpublished co-authored material.en_US
dc.identifier.urihttps://hdl.handle.net/1794/23749
dc.language.isoen_US
dc.publisherUniversity of Oregon
dc.rightsAll Rights Reserved.
dc.subjectCyanine Dyesen_US
dc.subjectExcited State Dynamicsen_US
dc.subjectMultidimensional Optical Spectroscopyen_US
dc.subjectVibronic Couplingen_US
dc.titleLocal Structure and Dynamics of Exciton-Coupled Cyanine Dimers Labeled in DNA
dc.typeElectronic Thesis or Dissertation
thesis.degree.disciplineDepartment of Chemistry and Biochemistry
thesis.degree.grantorUniversity of Oregon
thesis.degree.leveldoctoral
thesis.degree.namePh.D.

Files

Original bundle
Now showing 1 - 1 of 1
Thumbnail Image
Name:
Kringle_oregon_0171A_12173.pdf
Size:
8.47 MB
Format:
Adobe Portable Document Format
Download

Collections

Theses and Dissertations
Chemistry Theses and Dissertations