This thesis discusses developing new tools to probe DNA damage resulting from photoinduced chemical processes and probing the initial excited-state structural dynamics of nucleic acids and sunscreen agents. The results of this thesis show that UV resonance Raman spectroscopy (UVRRS) is an information-rich probe of chemical compositions in in situ analysis of sunscreen formulations. The results indicate that 244-nm excited UV resonance Raman spectra can provide a limit of detection of 0.23% w/w of sunscreen active ingredients (AIs), far below typical active ingredient (AI) concentrations in sunscreen formulations.
UVRRS was used to probe the photostability of sunscreens, by determining the initial excited-state structural dynamics of Benzophenone-3 (BZ3), a common sunscreen active ingredient. Only minor excited-state structural distortions were obtained, based on the low displacement values, suggesting an inherently stable molecule. The largest structural change occurs along the carbonyl stretch, suggesting a strong interaction with the methanol solvent and a dissipative decay path for the molecule. Similarly, to gain an insight into how the structure of nucleic acids determine their photochemistry, UVRRS was used to probe the initial excited-state structural dynamics of 9-methyladenine (9-MeA). As for BZ3, the initial excited-state structural dynamics obtained for 9-MeA, are low, and much lower than for pyrimidine bases, providing a strong evidence for the photochemical stability of this purine base analog, compared to pyrimidines.
Since DNA does not exist in isolation in cells, the role of a UV-absorbing amino acid, tryptophan, in UV-induced DNA photodamage was explored using molecular beacons (MBs) to detect the damage. The results indicate that tryptophan protective effects on DNA far outweighs their photodamage potential.
However, MBs are expensive and they have some technical limitations, despite their exquisite sensitivity. Therefore, a new DNA damage detection method was developed based on smart probes (SPs). These probes are shown to be sensitive and sequence specific for detecting DNA photodamage.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:AEU.10048/1039 |
| Date | 06 1900 |
| Creators | Oladepo, Sulayman |
| Contributors | Loppnow, Glen (Chemistry), McDermott, Mark (Chemistry), Klassen, John (Chemistry), Lucy, Charles (Chemistry), Choi, Phillip (Chemical and Materials Engineering), Aroca, Ricardo (Chemistry and Biochemistry) University of Windsor |
| Source Sets | Library and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada |
| Language | English |
| Detected Language | English |
| Type | Thesis |
| Format | 1921023 bytes, application/pdf |
| Relation | Loppnow, Glen R., Billinghurst, Brant E., Oladepo, Sulayman A. (2008) Springer., Oladepo, Sulayman A., Loppnow, Glen R. (2008) Analytica Chimica Acta |
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