Skip to main content
Journal cover image

Charge transfer in dynamical biosystems, or the treachery of (static) images.

Publication ,  Journal Article
Beratan, DN; Liu, C; Migliore, A; Polizzi, NF; Skourtis, SS; Zhang, P; Zhang, Y
Published in: Accounts of chemical research
February 2015

CONSPECTUS: The image is not the thing. Just as a pipe rendered in an oil painting cannot be smoked, quantum mechanical coupling pathways rendered on LCDs do not convey electrons. The aim of this Account is to examine some of our recent discoveries regarding biological electron transfer (ET) and transport mechanisms that emerge when one moves beyond treacherous static views to dynamical frameworks. Studies over the last two decades introduced both atomistic detail and macromolecule dynamics to the description of biological ET. The first model to move beyond the structureless square-barrier tunneling description is the Pathway model, which predicts how protein secondary motifs and folding-induced through-bond and through-space tunneling gaps influence kinetics. Explicit electronic structure theory is applied routinely now to elucidate ET mechanisms, to capture pathway interferences, and to treat redox cofactor electronic structure effects. Importantly, structural sampling of proteins provides an understanding of how dynamics may change the mechanisms of biological ET, as ET rates are exponentially sensitive to structure. Does protein motion average out tunneling pathways? Do conformational fluctuations gate biological ET? Are transient multistate resonances produced by energy gap fluctuations? These questions are becoming accessible as the static view of biological ET recedes and dynamical viewpoints take center stage. This Account introduces ET reactions at the core of bioenergetics, summarizes our team's progress toward arriving at an atomistic-level description, examines how thermal fluctuations influence ET, presents metrics that characterize dynamical effects on ET, and discusses applications in very long (micrometer scale) bacterial nanowires. The persistence of structural effects on the ET rates in the face of thermal fluctuations is considered. Finally, the flickering resonance (FR) view of charge transfer is presented to examine how fluctuations control low-barrier transport among multiple groups in van der Waals contact. FR produces exponential distance dependence in the absence of tunneling; the exponential character emerges from the probability of matching multiple vibronically broadened electronic energies within a tolerance defined by the rms coupling among interacting groups. FR thus produces band like coherent transport on the nanometer length scale, enabled by conformational fluctuations. Taken as a whole, the emerging context for ET in dynamical biomolecules provides a robust framework to design and interpret the inner workings of bioenergetics from the molecular to the cellular scale and beyond, with applications in biomedicine, biocatalysis, and energy science.

Duke Scholars

Altmetric Attention Stats
Dimensions Citation Stats

Published In

Accounts of chemical research

DOI

EISSN

1520-4898

ISSN

0001-4842

Publication Date

February 2015

Volume

48

Issue

2

Start / End Page

474 / 481

Related Subject Headings

  • Water
  • Temperature
  • Macromolecular Substances
  • General Chemistry
  • Electron Transport
  • 34 Chemical sciences
  • 03 Chemical Sciences
 

Citation

APA
Chicago
ICMJE
MLA
NLM
Beratan, D. N., Liu, C., Migliore, A., Polizzi, N. F., Skourtis, S. S., Zhang, P., & Zhang, Y. (2015). Charge transfer in dynamical biosystems, or the treachery of (static) images. Accounts of Chemical Research, 48(2), 474–481. https://doi.org/10.1021/ar500271d
Beratan, David N., Chaoren Liu, Agostino Migliore, Nicholas F. Polizzi, Spiros S. Skourtis, Peng Zhang, and Yuqi Zhang. “Charge transfer in dynamical biosystems, or the treachery of (static) images.Accounts of Chemical Research 48, no. 2 (February 2015): 474–81. https://doi.org/10.1021/ar500271d.
Beratan DN, Liu C, Migliore A, Polizzi NF, Skourtis SS, Zhang P, et al. Charge transfer in dynamical biosystems, or the treachery of (static) images. Accounts of chemical research. 2015 Feb;48(2):474–81.
Beratan, David N., et al. “Charge transfer in dynamical biosystems, or the treachery of (static) images.Accounts of Chemical Research, vol. 48, no. 2, Feb. 2015, pp. 474–81. Epmc, doi:10.1021/ar500271d.
Beratan DN, Liu C, Migliore A, Polizzi NF, Skourtis SS, Zhang P, Zhang Y. Charge transfer in dynamical biosystems, or the treachery of (static) images. Accounts of chemical research. 2015 Feb;48(2):474–481.
Journal cover image

Published In

Accounts of chemical research

DOI

EISSN

1520-4898

ISSN

0001-4842

Publication Date

February 2015

Volume

48

Issue

2

Start / End Page

474 / 481

Related Subject Headings

  • Water
  • Temperature
  • Macromolecular Substances
  • General Chemistry
  • Electron Transport
  • 34 Chemical sciences
  • 03 Chemical Sciences