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https://hdl.handle.net/2440/75792
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Type: | Journal article |
Title: | Electrochemical and computational studies on intramolecular dissociative electron transfer in β‐peptides |
Other Titles: | Electrochemical and computational studies on intramolecular dissociative electron transfer in beta-peptides |
Author: | Yu, J. Huang, D. Shapter, J. Abell, A. |
Citation: | The Journal of Physical Chemistry C: Energy Conversion and Storage, Optical and Electronic Devices, Interfaces, Nanomaterials, and Hard Matter, 2012; 116(50):26608-26617 |
Publisher: | American Chemical Society |
Issue Date: | 2012 |
ISSN: | 1932-7447 1932-7455 |
Statement of Responsibility: | Jingxian Yu, David M. Huang, Joe G. Shapter, and Andrew D. Abell |
Abstract: | The preparation of the β-peptides PCB-β3Val- β3Ala-β3Leu-NHC(CH3) 2OOtBu and PCB-(β3Val-β3Ala- β3Leu)2-NHC(CH3)2OOtBu, with a specific donor and acceptor at each terminus, is described. Circular dichroism, 2D NMR, and density functional theory calculations confirmed that PCB-(β3Val-β3Ala-β3Leu) 2-NHC(CH3)2OOtBu adopts a 14-helix conformation, whereas PCB-β3Val-β3Ala- β3Leu-NHC(CH3)2OOtBu has an ill-defined secondary structure. The electron-transfer rate constants in the two peptides were found to be 2580 and 9.8 s-1 respectively. Computational simulations based on Marcus theory coupled to constrained density functional theory provide clear theoretical evidence that different electron-transport pathways occur in the two peptides due to their different conformations: sequential hopping within PCB-(β3Val-β3Ala- β3Leu)2-NHC(CH3)2OOtBu and superexchange within PCB-β3Val-β3Ala- β3Leu-NHC(CH3)2OOtBu. Electron population analysis provides the first clear theoretical evidence that amide groups can act as hopping sites in long-range electron transfer. © 2012 American Chemical Society. |
Rights: | © 2012 American Chemical Society |
DOI: | 10.1021/jp3082563 |
Grant ID: | http://purl.org/au-research/grants/arc/DP0985176 http://purl.org/au-research/grants/arc/DP0985176 |
Published version: | http://dx.doi.org/10.1021/jp3082563 |
Appears in Collections: | Aurora harvest 7 IPAS publications |
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