Long-Range Electron Transfer Across Peptide Bridges:  The Transition from Electron Superexchange to Hopping

• Abstract
• Full Text HTML
• Hi-Res PDF[47 KB]
• PDF w/ Links[97 KB]

• Figures
• Citing Articles

Your current credentials do not allow retrieval of the full text.

Purchase the full-text

• PDF/HTML,
  figures/images,
  references and tables,
  (where available)

Abstract

Long-range electron transfer rate constants for complexes of the type [(bpy)₂Ru^IIL−Pro_n−apyRu^III)(NH₃)₅]⁵⁺⁺ proline residues (n) varying from 0 to 9 were determined by complementary electron pulse radiolysis and flash photolysis techniques from the picosecond to the millisecond time scales. The activationless k_max values from both techniques coalesce into one data set. The distance dependence of the reactions is consistent with a smooth transition from a superexchange mechanism with attenuation constant β = 1.4 Å^-1 to a hopping mechanism with attenuation constant β = 0.17 Å^-1. The transition occurs between n = 3 and 4 prolines, and the virtual hopping rate constant at the shortest distance is about 1 x 10⁶ times slower than that observed for the superexchange value.

Citing Articles

View all 66 citing articles

Citation data is made available by participants in CrossRef's Cited-by Linking service. For a more comprehensive list of citations to this article, users are encouraged to perform a search in SciFinder.

This article has been cited by 28 ACS Journal articles (5 most recent appear below).

• 

  Charge Transfer in Model Peptides: Obtaining Marcus Parameters from Molecular Simulation

  Alexander Heck, P. Benjamin Woiczikowski, Tomáš Kubař, Bernd Giese, Marcus Elstner, and Thomas B. Steinbrecher
  The Journal of Physical Chemistry B2012 Article ASAP

  • Charge Transfer in Model Peptides: Obtaining Marcus Parameters from Molecular Simulation

    Alexander Heck, P. Benjamin Woiczikowski, Tomáš Kubař, Bernd Giese, Marcus Elstner, and Thomas B. Steinbrecher
    The Journal of Physical Chemistry B2012 Article ASAP

    Charge transfer within and between biomolecules remains a highly active field of biophysics. Due to the complexities of real systems, model compounds are a useful alternative to study the mechanistic fundamentals of charge transfer. In recent years, such ...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  Long-Range Electron Transfer in Biomolecules. Tunneling or Hopping?

  Alexander A. Voityuk
  The Journal of Physical Chemistry B2011 115 (42), 12202-12207

  • Long-Range Electron Transfer in Biomolecules. Tunneling or Hopping?

    Alexander A. Voityuk
    The Journal of Physical Chemistry B2011 115 (42), 12202-12207

    Two competing mechanisms are relevant for long-range electron transfer (ET) in biomolecules: direct electron tunneling between donor (D) and acceptor (A), D → A, and multistep hopping D → X → A, where an electron or an electron hole is transiently ...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  Tunneling versus Hopping in Mixed-Valence Oligo-p-phenylenevinylene Polychlorinated Bis(triphenylmethyl) Radical Anions

  Vega Lloveras, José Vidal-Gancedo, Teresa M. Figueira-Duarte, Jean-François Nierengarten, Juan J. Novoa, Fernando Mota, Nora Ventosa, Concepció Rovira, and Jaume Veciana
  Journal of the American Chemical Society2011 133 (15), 5818-5833

  • Tunneling versus Hopping in Mixed-Valence Oligo-p-phenylenevinylene Polychlorinated Bis(triphenylmethyl) Radical Anions

    Vega Lloveras, José Vidal-Gancedo, Teresa M. Figueira-Duarte, Jean-François Nierengarten, Juan J. Novoa, Fernando Mota, Nora Ventosa, Concepció Rovira, and Jaume Veciana
    Journal of the American Chemical Society2011 133 (15), 5818-5833

    Radical anions 1−•−5−•, showing different lengths and incorporating up to five p-phenylenevinylene (PPV) bridges between two polychlorinated triphenylmethyl units, have been prepared by chemical or electrochemical reductions from the corresponding ...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  Charge Mapping in 3₁₀-Helical Peptide Chains by Oxidation of the Terminal Ferrocenyl Group

  Alessandro Donoli, Vanessa Marcuzzo, Alessandro Moretto, Claudio Toniolo, Roberta Cardena, Annalisa Bisello, and Saverio Santi
  Organic Letters2011 13 (6), 1282-1285

  • Charge Mapping in 3₁₀-Helical Peptide Chains by Oxidation of the Terminal Ferrocenyl Group

    Alessandro Donoli, Vanessa Marcuzzo, Alessandro Moretto, Claudio Toniolo, Roberta Cardena, Annalisa Bisello, and Saverio Santi
    Organic Letters2011 13 (6), 1282-1285

    Two series of 310-helical peptides of different lengths and rigidity, based on the strongly foldameric α-aminoisobutyric acid and containing a terminal ferrocenyl unit, have been synthesized. Oxidation-state sensitive spectroscopic tags of helical ...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
• 

  Ultra-Long-Range Electron Transfer through a Self-Assembled Monolayer on Gold Composed of 120-Å-Long α-Helices

  Yoko Arikuma, Hidenori Nakayama, Tomoyuki Morita, and Shunsaku Kimura
  Langmuir2011 27 (4), 1530-1535

  • Ultra-Long-Range Electron Transfer through a Self-Assembled Monolayer on Gold Composed of 120-Å-Long α-Helices

    Yoko Arikuma, Hidenori Nakayama, Tomoyuki Morita, and Shunsaku Kimura
    Langmuir2011 27 (4), 1530-1535

    Electron transfer through α-helices has attracted much attention from the viewpoints of their contributions to efficient long-range electron transfer occurring in biological systems and their utility as molecular-electronics elements. In this study, we ...

    Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links

SciFinder Links

• Get Reference Detail
• Get Substances
• Get Cited
• Get Citing