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A Mechanistic Study of Electron Transfer from the Distal Termini of Electrode-Bound, Single-Stranded DNAs

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Department of Chemistry and Biochemistry, Interdepartmental Program in Biomolecular Science and Engineering, University of California, Santa Barbara, California 93106, and Department of Chemistry and Biochemistry, The University of Texas, Austin, Texas 78712
[email protected]
†Present address: Biochemistry lab, Riken, Wako 351-0198, Japan.
‡Department of Chemistry and Biochemistry, University of California.
§Interdepartmental Program in Biomolecular Science and Engineering, University of California.
∥The University of Texas.
Cite this: J. Am. Chem. Soc. 2010, 132, 45, 16120–16126
Publication Date (Web):October 21, 2010
https://doi.org/10.1021/ja106345d
Copyright © 2010 American Chemical Society
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    Abstract

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    Electrode-bound, redox-reporter-modified oligonucleotides play roles in the functioning of a number of electrochemical biosensors, and thus the question of electron transfer through or from such molecules has proven of significant interest. In response, we have experimentally characterized the rate with which electrons are transferred between a methylene blue moiety on the distal end of a short, single-stranded polythymine DNA to a monolayer-coated gold electrode to which the other end of the DNA is site-specifically attached. We find that this rate scales with oligonucleotide length to the −1.16 ± 0.09 power. This weak, approximately inverse length dependence differs dramatically from the much stronger dependencies observed for the rates of end-to-end collisions in single-stranded DNA and through-oligonucleotide electron hopping. It instead coincides with the expected length dependence of a reaction-limited process in which the overall rate is proportional to the equilibrium probability that the end of the oligonucleotide chain approaches the surface. Studies of the ionic strength and viscosity dependencies of electron transfer further support this “chain-flexibility” mechanism, and studies of the electron transfer rate of methylene blue attached to the hexanethiol monolayer suggest that heterogeneous electron transfer through the monolayer is rate limiting. Thus, under the circumstances we have employed, the flexibility (i.e., the equilibrium statistical properties) of the oligonucleotide chain defines the rate with which an attached redox reporter transfers electrons to an underlying electrode, an observation that may be of utility in the design of new biosensor architectures.

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