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Electrochemistry of Methylene Blue Bound to a DNA-Modified Electrode

Kelley, Shana O. and Barton, Jacqueline K. and Jackson, Nicole M. and Hill, Michael G. (1997) Electrochemistry of Methylene Blue Bound to a DNA-Modified Electrode. Bioconjugate Chemistry, 8 (1). pp. 31-37. ISSN 1043-1802. https://resolver.caltech.edu/CaltechAUTHORS:20160405-110030531

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Abstract

Gold surfaces have been derivatized with 15-base-pair double-stranded DNA oligonucleotides containing a pendant 5‘ hexanethiol linker. The electrochemistry of intercalated methylene blue has been investigated at these modified electrodes. Chronocoulometry, cyclic voltammetry, ellipsometry, and quantitation via ^(32)P labeling are all consistent with a surface coverage of ≥ 75% with the DNA helices stacked at an angle from the electrode surface. Cyclic voltammetry at low methylene blue/duplex stoichiometries yields well-behaved surface waves with E° = −0.25 V (vs SCE), a value 0.03 V negative of that in aqueous solution. A binding isotherm for methylene blue at an electrode derivatized with the double-stranded sequence 5‘ SH-(CH_2)_6-p-AGTACAGTCATCGCG 3‘ was obtained from coulometric titrations and gave an affinity constant equal to 3.8(5) × 10^6 M^(-1) with a saturation value of 1.4(2) methylene blue intercalators per DNA duplex. Taken together, these experiments support a model for the surface morphology in which DNA duplexes are densely packed; methylene blue therefore reversibly binds to sites in the DNA that are close to the bulk solution. Electrochemistry at DNA-derivatized electrodes provides a valuable methodology to examine DNA-bound redox reactions and may offer new insight into DNA-mediated electron transfers.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/bc960070oDOIArticle
http://pubs.acs.org/doi/abs/10.1021/bc960070oPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/bc960070oRelated ItemSupporting Information
ORCID:
AuthorORCID
Kelley, Shana O.0000-0003-3360-5359
Barton, Jacqueline K.0000-0001-9883-1600
Additional Information:© 1997 American Chemical Society. Received August 1, 1996. Publication Date (Web): January 29, 1997. We are grateful to the NIH (GM49216 to J.K.B.), the Research Corporation (M.G.H.), the Camille and Henry Dreyfus Foundation (M.G.H.), and the NSF (DUE-9551647 to M.G.H.) for their financial support. In addition, we thank Ashish Bansal for assistance with the ellipsometry experiments and Professor F. C. Anson for helpful discussions.
Funders:
Funding AgencyGrant Number
NIHGM49216
Research CorporationUNSPECIFIED
Camille and Henry Dreyfus FoundationUNSPECIFIED
NSFDUE-9551647
Issue or Number:1
Record Number:CaltechAUTHORS:20160405-110030531
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20160405-110030531
Official Citation:Electrochemistry of Methylene Blue Bound to a DNA-Modified Electrode Shana O. Kelley and, Jacqueline K. Barton, Nicole M. Jackson and, and Michael G. Hill Bioconjugate Chemistry 1997 8 (1), 31-37 DOI: 10.1021/bc960070o
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:65929
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:06 Apr 2016 18:48
Last Modified:03 Oct 2019 09:51

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