Electrochemical and computational studies on intramolecular dissociative electron transfer in β-peptides

Jingxian Yu; David Huang; Joseph Shapter; Andrew Abell

doi:10.1021/jp3082563

Electrochemical and computational studies on intramolecular dissociative electron transfer in β-peptides

Jingxian Yu, David Huang, Joseph Shapter, Andrew Abell

Research output: Contribution to journal › Article › peer-review

24 Citations (Scopus)

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.

Original language	English
Pages (from-to)	26608-26617
Number of pages	10
Journal	Journal of Physical Chemistry C
Volume	116
Issue number	50
DOIs	https://doi.org/10.1021/jp3082563
Publication status	Published - 20 Dec 2012

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@article{7403a6d90f714c6bb35ca2625a524b4a,

title = "Electrochemical and computational studies on intramolecular dissociative electron transfer in β-peptides",

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.",

author = "Jingxian Yu and David Huang and Joseph Shapter and Andrew Abell",

year = "2012",

month = dec,

day = "20",

doi = "10.1021/jp3082563",

language = "English",

volume = "116",

pages = "26608--26617",

journal = "Journal of Physical Chemistry C",

issn = "1932-7447",

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T1 - Electrochemical and computational studies on intramolecular dissociative electron transfer in β-peptides

AU - Yu, Jingxian

AU - Huang, David

AU - Shapter, Joseph

AU - Abell, Andrew

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N2 - 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.

AB - 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.

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Electrochemical and computational studies on intramolecular dissociative electron transfer in β-peptides

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