Leigh, Brian Scott (2009) Electron Transfer through Organic and Biological Molecules. Dissertation (Ph.D.), California Institute of Technology. http://resolver.caltech.edu/CaltechETD:etd-08042008-115533
The function of solvent in facilitating long-range coupling in donor/bridge/acceptor complexes is not well understood. There are exceptional challenges inherent to the measurement of the electron transfer coupling properties of solvents. By immobilizing the donor and acceptor in a glass to eliminate the effects of diffusion, statistical methods of analysis can be employed to study electron transfer between randomly dispersed donor and acceptor molecules over long distances. Toluene and 2-methyltetrahydrofuran form glasses that can solubilize donor and acceptor molecules at 77 K. Exponential decay constant of 1.23 per angstrom, for electron tunneling through a frozen toluene glass, and 1.62 per angstrom through 2-methyltetrahydrofuran glass have been found. Identification of the electronic coupling sites on the surfaces of proteins is usually achieved by inspection of a crystal structure. These coupling spots have been experimentally observed by employing mixed self-assembled monolayer electrodes and a variety of mutants. The electron transport protein azurin has a well defined reduction potential on self-assembled monolayer electrodes (0.16 V vs. saturated Ag/AgCl). When a point mutation is made at position 48, electron transfer ceases. This disruption of electron transfer occurs because the mutation forces conformational changes that disrupt a critical hydrogen bond between asparagine-47 and cysteine-112. This hydrogen bond is a key element for electron transfer into and out of the protein.
|Item Type:||Thesis (Dissertation (Ph.D.))|
|Subject Keywords:||azurin; electron transfer; glass; tryptophan|
|Degree Grantor:||California Institute of Technology|
|Division:||Chemistry and Chemical Engineering|
|Thesis Availability:||Public (worldwide access)|
|Defense Date:||15 July 2008|
|Non-Caltech Author Email:||bleigh (AT) caltech.edu|
|Default Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Imported from ETD-db|
|Deposited On:||13 Aug 2008|
|Last Modified:||03 Feb 2017 23:31|
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