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The electrochemistry of thiols on gold would be significantly complicated by the ease of S-Au bond formation. For an extensive review of thiol/ transition metal bonds, see: Love, J. C, Estroff, L. A, Kriebel, J. K, Nuzzo, R. G, Whitesides, G. M. Chem. Rev. 2005, 105, 1103
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The electrochemistry of thiols on gold would be significantly complicated by the ease of S-Au bond formation. For an extensive review of thiol/ transition metal bonds, see: Love, J. C.; Estroff, L. A.; Kriebel, J. K.; Nuzzo, R. G.; Whitesides, G. M. Chem. Rev. 2005, 105, 1103.
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The 5′ C6 thiol modifier S-S phosphoramidites and 3′ C3 thiol modifier S-S CPG were purchased from Glen Research, mass spectrometry, UV-visible spectroscopy, and HPLC
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The 5′ C6 thiol modifier S-S phosphoramidites and 3′ C3 thiol modifier S-S CPG were purchased from Glen Research. All DNA synthesized was confirmed by MALDI-TOF mass spectrometry, UV-visible spectroscopy, and HPLC.
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All DNA synthesized was confirmed by MALDI-TOF
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In an aerobic buffer for duplex DNA, a disulfide bond is formed between two contiguous thiols incorporated within the DNA backbone in quantitative yields. The reaction is templated by the complementary strand and occurs in negligible yields for the single strands
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In an aerobic buffer for duplex DNA, a disulfide bond is formed between two contiguous thiols incorporated within the DNA backbone in quantitative yields. The reaction is templated by the complementary strand and occurs in negligible yields for the single strands.
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XPS measurements on DNA monolayers featuring thiols incorporated into the sugar-phosphate backbone exhibit a broad S2p peak centered at 164 eV Supporting Information, The signal observed is fully consistent with previous XPS measurements of polymer films on gold featuring bound thiols. See for example: Johnson, P. A, Levicky, R. Langmuir 2004, 20, 9621
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XPS measurements on DNA monolayers featuring thiols incorporated into the sugar-phosphate backbone exhibit a broad S2p peak centered at 164 eV (Supporting Information). The signal observed is fully consistent with previous XPS measurements of polymer films on gold featuring bound thiols. See for example: Johnson, P. A.; Levicky, R. Langmuir 2004, 20, 9621.
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We have previously found that trace amounts of oxygen are necessary for disulfide bond formation see ref 6, All experiments were carried out under similarly low oxygen concentrations. Small signals due to oxygen at ca, 200 mV are observed for well matched DNA featuring one thiol or no thiols, but this peak is obscured by the much larger disulfide reduction peaks
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We have previously found that trace amounts of oxygen are necessary for disulfide bond formation (see ref 6). All experiments were carried out under similarly low oxygen concentrations. Small signals due to oxygen at ca. -200 mV are observed for well matched DNA featuring one thiol or no thiols, but this peak is obscured by the much larger disulfide reduction peaks.
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Two separate one-electron reduction steps have been previously observed for the electrochemistry of the cysteine active site of thioredoxins at similar potentials. See Salamon, Z, Tollin, G, Hirasawa, M, Gardet-Salvi, L, Stritt-Etter, A.-L, Knaff, D. B, Schurmann, P. Biochim. Biophys. Acta 1995, 1230, 114
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Two separate one-electron reduction steps have been previously observed for the electrochemistry of the cysteine active site of thioredoxins at similar potentials. See Salamon, Z.; Tollin, G.; Hirasawa, M.; Gardet-Salvi, L.; Stritt-Etter, A.-L.; Knaff, D. B.; Schurmann, P. Biochim. Biophys. Acta 1995, 1230, 114.
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See also
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See also: Johnson, D. L.; Polyak, S. W.; Wallace, J. C.; Martin, L. L. Lett. Pept. Sci. 2004, 10, 495.
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(2004)
Lett. Pept. Sci
, vol.10
, pp. 495
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Johnson, D.L.1
Polyak, S.W.2
Wallace, J.C.3
Martin, L.L.4
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37
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0037415009
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A slope of 59 mV per pH unit is expected for the proton-coupled transfer of one electron. Similar nonidealized pH responses have been previously observed for DNA polyion films on graphite. See Munge, B.; Estavillo, C.; Schenkman, J. B.; Rusling, J. F. ChemBioChem 2003, 4, 82.
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A slope of 59 mV per pH unit is expected for the proton-coupled transfer of one electron. Similar nonidealized pH responses have been previously observed for DNA polyion films on graphite. See Munge, B.; Estavillo, C.; Schenkman, J. B.; Rusling, J. F. ChemBioChem 2003, 4, 82.
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An anionic radical intermediate has been observed spectroscopically for small molecules in Goebl, M, Bonifacic, M, Asmus, K.-D. J. Am. Chem. Soc. 1984, 106, 5984
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An anionic radical intermediate has been observed spectroscopically for small molecules in Goebl, M.; Bonifacic, M.; Asmus, K.-D. J. Am. Chem. Soc. 1984, 106, 5984.
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42
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For thioredoxins in El Hanine, see: Lmoumene, C.; Conte, D.; Jacquot, J.-P.; Houee-Levin, C. Biochemistry 2000, 39, 9295. See also reference 23.
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For thioredoxins in El Hanine, see: Lmoumene, C.; Conte, D.; Jacquot, J.-P.; Houee-Levin, C. Biochemistry 2000, 39, 9295. See also reference 23.
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