Exchange rate determination allows precise modeling of chemical systems, and allows one to infer properties relevant to tumor biology such as enzyme activity and pH. Current exchange rate determination methods found via Contrast Enhanced Saturation Transfer agents are not effective for fast exchanging protons and use non-linear models. A comparison of their effectiveness has not been performed. In this thesis, I compare the effectiveness of current exchange rate measurement methods. I also develop exchange rate measurement methods that are effective for fast exchanging CEST agents and use linear models instead of non-linear models. In chapter 1 I review current exchange rate measurement methods. In chapter 2 I compare several of the current methods of exchange rate measurement, along with several techniques we develop. In chapter 3 I linearize the Quantifying Exchange through Saturation Transfer (QUEST) measurement method analogously to the Omega Plot method, and compare its effectiveness to the QUEST method. In chapter 4, I compare the effectiveness of current exchange rate theories (Transition State Theory and Landau-Zener theory) in the moderate coupling regime, and propose our own combined Eyring-Landau-Zener theory for this intermediate regime. In chapter 5 I discuss future directions for method development and experiments involving exchange rate determination.
| Identifer | oai:union.ndltd.org:arizona.edu/oai:arizona.openrepository.com:10150/314652 |
| Date | January 2013 |
| Creators | Randtke, Edward Alexander |
| Contributors | Corrales, Louis Rene, Pagel, Mark D., Kuo, Phillip, Cárdenas-Rodríguez, Julio, Pagel, Mark D., Corrales, Louis Rene |
| Publisher | The University of Arizona. |
| Source Sets | University of Arizona |
| Language | en_US |
| Detected Language | English |
| Type | text, Electronic Dissertation |
| Rights | Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author. |
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