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Intercalative Stacking: A Critical Feature of DNA Charge-Transport Electrochemistry

Boon, Elizabeth M. and Jackson, Nicole M. and Wightman, Matthew D. and Kelley, Shana O. and Hill, Michael G. and Barton, Jacqueline K. (2003) Intercalative Stacking: A Critical Feature of DNA Charge-Transport Electrochemistry. Journal of Physical Chemistry B, 107 (42). pp. 11805-11812. ISSN 1520-6106. doi:10.1021/jp030753i.

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In electrochemistry experiments on DNA-modified electrodes, features of the redox probe that determine efficient charge transport through DNA-modified surfaces have been explored using methylene blue (MB^+) and Ru(NH_3)_6^(3+) as DNA-binding redox probes. The electrochemistry of these molecules is studied as a function of ionic strength to determine the necessity of tight binding to DNA and the number of electrons involved in the redox reaction; on the DNA surface, MB^+ displays 2e^-/1H^+ electrochemistry (pH 7) and Ru(NH^3)_6^(3+) displays 1e^- electrochemistry. We examine also the effect of electrode surface passivation and the effect of the mode (intercalation or electrostatic) of MB^+ and Ru(NH_3)_6^(3+) binding to DNA to highlight the importance of intercalation for reduction by a DNA-mediated charge-transport pathway. Furthermore, in experiments in which MB^+ is covalently linked to the DNA through a σ-bonded tether and the ionic strength is varied, it is demonstrated that intercalative stacking rather than covalent σ-bonding is essential for efficient reduction of MB^+. The results presented here therefore establish that efficient charge transport to the DNA-binding moiety in DNA films requires intercalative stacking and is mediated by the DNA base pair array.

Item Type:Article
Related URLs:
URLURL TypeDescription
Boon, Elizabeth M.0000-0003-1891-839X
Kelley, Shana O.0000-0003-3360-5359
Barton, Jacqueline K.0000-0001-9883-1600
Additional Information:© 2003 American Chemical Society. Received 13 June 2003. Published online 2 October 2003. Published in print 1 October 2003. We are grateful to the National Institutes of Health (Grant GM61077) for their financial support of this research. In addition, we thank the Parsons Foundation for fellowship support (E.M.B.)
Funding AgencyGrant Number
Ralph M. Parsons FoundationUNSPECIFIED
Issue or Number:42
Record Number:CaltechAUTHORS:20170523-145321462
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Official Citation:Intercalative Stacking:  A Critical Feature of DNA Charge-Transport Electrochemistry Elizabeth M. Boon, Nicole M. Jackson, Matthew D. Wightman, Shana O. Kelley, Michael G. Hill, and Jacqueline K. Barton The Journal of Physical Chemistry B 2003 107 (42), 11805-11812 DOI: 10.1021/jp030753i
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:77668
Deposited By: Ruth Sustaita
Deposited On:23 May 2017 23:46
Last Modified:15 Nov 2021 17:33

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