Local Conformations and Excited State Dynamics of Porphyrins and Nucleic Acids by 2-Dimensional Fluorescence Spectroscopy
| dc.contributor.advisor | von Hippel, Peter | en_US |
| dc.contributor.author | Widom, Julia | en_US |
| dc.date.accessioned | 2014-06-17T19:39:13Z | |
| dc.date.available | 2014-06-17T19:39:13Z | |
| dc.date.issued | 2014-06-17 | |
| dc.description.abstract | Biological systems present many challenges to researchers attempting to study them using spectroscopy. Low specificity, low sensitivity, and broad and overlapping lineshapes limit the amount of information that can be obtained in experiments. Two-dimensional fluorescence spectroscopy (2D FS) is a highly sensitive and information-rich spectroscopic technique that was developed to study the conformations and excited state dynamics of systems exhibiting exciton coupling. In this dissertation, I describe a variety of extensions of 2D FS that further increase its utility for the study of biological systems. I describe experiments on a dimer of zinc tetraphenylporphyrin embedded in a membrane, in which the signals from two conformational subpopulations were separated in order to study the thermodynamics of their interconversion. I present proof-of-principle experiments on nucleic acids that utilize fluorescence resonance energy transfer to separate signals from different subpopulations. I also describe experiments in which 2D FS was performed using ultraviolet excitation to determine the conformation of a dinucleotide of a fluorescent analogue of the nucleic acid base adenine. I discuss experiments on porphyrin dimers in which 2D FS was used as a probe of excited state dynamics. Finally, I present model calculations for a proposed variation of 2D FS in which entangled photons would be used as the excitation source. These calculations suggest that this approach has the potential to yield significantly narrower spectral lineshapes than conventional 2D FS. These experiments and calculations yield new insight into the systems investigated and establish a `toolbox' of variations of 2D FS that can be used to gain as much information as possible from experiments on challenging systems such as protein-DNA complexes. This dissertation contains previously published and unpublished co-authored material. | en_US |
| dc.identifier.uri | https://hdl.handle.net/1794/17885 | |
| dc.language.iso | en_US | en_US |
| dc.publisher | University of Oregon | en_US |
| dc.rights | All Rights Reserved. | en_US |
| dc.subject | 2D spectroscopy | en_US |
| dc.subject | DNA | en_US |
| dc.subject | Entanglement | en_US |
| dc.subject | Fluorescence | en_US |
| dc.subject | Porphyrin | en_US |
| dc.title | Local Conformations and Excited State Dynamics of Porphyrins and Nucleic Acids by 2-Dimensional Fluorescence Spectroscopy | en_US |
| dc.type | Electronic Thesis or Dissertation | en_US |
| thesis.degree.discipline | Department of Chemistry and Biochemistry | en_US |
| thesis.degree.grantor | University of Oregon | en_US |
| thesis.degree.level | doctoral | en_US |
| thesis.degree.name | Ph.D. | en_US |
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