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Heterogeneous Electron Transfer of Supramolecular Assemblies

Wei, Jianjun (2005) Heterogeneous Electron Transfer of Supramolecular Assemblies. Doctoral Dissertation, University of Pittsburgh. (Unpublished)

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Heterogeneous electron transfer of protein, porphyrins through self-assembled monolayer (SAM) at gold electrodes was studied. The SAM was characterized by electrochemistry, thickness measurement, contact angle, scanning tunneling microscopy (STM) and others. The electron transfer rate constants of cytochrome c immobilized on a SAM by directly ¡°wiring¡± its heme through a variety of nitrogen ligands (pyridine, imidazole or nitrilE) were measured by cyclic voltammetry. The electron transfer mechanism was explored by changing the distance between the electrode and protein, the composition of the SAM chains, the type of cytochrome c (horse heart cytochrome, rat cytochrome c and its mutants), and the conditions of electrolyte solutions. The results were compared to those of cytochrome c electrostatically adsorbed at carboxylic acid terminated SAMs, distinguishing the electron transfer mechanism and electron transfer pathways. A unified theoretical model, i.e. a gradual transition of the mechanism from a friction controlled reaction at short distance to tunneling controlled reaction at long distance, was applied to these ¡°heme-wired¡± systems. In a study of photo-induced electron transfer of porphyrins through SAMs with chiral structure, an asymmetrical effect on the efficiency of electron transfer through these chiral chain structures was found. Induced circular dichroism of porphyrin aggregates, orbital angular momentum interaction in electronic coupling, are proposed as possible mechanisms for the asymmetry of electronic tunneling.


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Item Type: University of Pittsburgh ETD
Status: Unpublished
CreatorsEmailPitt UsernameORCID
Wei, Jianjunjaw27@pitt.eduJAW27
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee ChairWaldeck, David Hdave@pitt.eduDAVE
Committee MemberArmitage, Bruce
Committee MemberWalker, Gilbertgilbertw@pitt.eduGILBERTW
Committee MemberAmemiya, Shigeruamemiya@pitt.eduAMEMIYA
Date: 1 February 2005
Date Type: Completion
Defense Date: 23 November 2004
Approval Date: 1 February 2005
Submission Date: 1 December 2004
Access Restriction: No restriction; Release the ETD for access worldwide immediately.
Institution: University of Pittsburgh
Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
Degree: PhD - Doctor of Philosophy
Thesis Type: Doctoral Dissertation
Refereed: Yes
Uncontrolled Keywords: Cytochrome c; Electron transfer; Porphyrins; Electrochemistry; Self-assembled Monolayers
Other ID:, etd-12012004-172612
Date Deposited: 10 Nov 2011 20:07
Last Modified: 15 Nov 2016 13:52


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