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For examples of studies of DNA-modified surfaces, see: (a) Herne, T. M.; Tarlov, M. J. J. Am. Chem. Soc. 1997, 119, 8916. (b) Kelley, S. O.; Jackson, N. M.; Hill, M. G.; Barton, J. K. Angew. Chem., Int. Ed. 1999, 38, 941. (c) Yu, C. J.; Wan, Y. J.; Yowanto, H.; Li, J.; Tao, C. L.; James, M. D.; Tan, C. L.; Blackburn, G. F.; Meade, T. J. J. Am. Chem. Soc. 2001, 123, 11155. (d) Kertesz, V.; Whittemore, N. A.; Chambers, J. Q.; McKinney, M. S.: Baker, D. C. J. Electroanal. Chem. 2000, 493, 28. (e) Hartwich, G.; Caruana, D. J.; de Lumley-Woodyear, T.; Wu, Y. B.; Campbell, C. N.; Heller, A. J. Am. Chem. Soc. 1999, 121, 10803. (f) Pike, A. R.; Lie, L. H.; Eagling, R. A.; Ryder, L. C.; Patole, S. N.; Connolly, B. A.; Horrocks, B. R.; Houlton, A. Angew. Chem., Int. Ed. 2002, 41, 615.
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For examples of studies of DNA-modified surfaces, see: (a) Herne, T. M.; Tarlov, M. J. J. Am. Chem. Soc. 1997, 119, 8916. (b) Kelley, S. O.; Jackson, N. M.; Hill, M. G.; Barton, J. K. Angew. Chem., Int. Ed. 1999, 38, 941. (c) Yu, C. J.; Wan, Y. J.; Yowanto, H.; Li, J.; Tao, C. L.; James, M. D.; Tan, C. L.; Blackburn, G. F.; Meade, T. J. J. Am. Chem. Soc. 2001, 123, 11155. (d) Kertesz, V.; Whittemore, N. A.; Chambers, J. Q.; McKinney, M. S.: Baker, D. C. J. Electroanal. Chem. 2000, 493, 28. (e) Hartwich, G.; Caruana, D. J.; de Lumley-Woodyear, T.; Wu, Y. B.; Campbell, C. N.; Heller, A. J. Am. Chem. Soc. 1999, 121, 10803. (f) Pike, A. R.; Lie, L. H.; Eagling, R. A.; Ryder, L. C.; Patole, S. N.; Connolly, B. A.; Horrocks, B. R.; Houlton, A. Angew. Chem., Int. Ed. 2002, 41, 615.
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For examples of studies of DNA-modified surfaces, see: (a) Herne, T. M.; Tarlov, M. J. J. Am. Chem. Soc. 1997, 119, 8916. (b) Kelley, S. O.; Jackson, N. M.; Hill, M. G.; Barton, J. K. Angew. Chem., Int. Ed. 1999, 38, 941. (c) Yu, C. J.; Wan, Y. J.; Yowanto, H.; Li, J.; Tao, C. L.; James, M. D.; Tan, C. L.; Blackburn, G. F.; Meade, T. J. J. Am. Chem. Soc. 2001, 123, 11155. (d) Kertesz, V.; Whittemore, N. A.; Chambers, J. Q.; McKinney, M. S.: Baker, D. C. J. Electroanal. Chem. 2000, 493, 28. (e) Hartwich, G.; Caruana, D. J.; de Lumley-Woodyear, T.; Wu, Y. B.; Campbell, C. N.; Heller, A. J. Am. Chem. Soc. 1999, 121, 10803. (f) Pike, A. R.; Lie, L. H.; Eagling, R. A.; Ryder, L. C.; Patole, S. N.; Connolly, B. A.; Horrocks, B. R.; Houlton, A. Angew. Chem., Int. Ed. 2002, 41, 615.
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For examples of studies of DNA-modified surfaces, see: (a) Herne, T. M.; Tarlov, M. J. J. Am. Chem. Soc. 1997, 119, 8916. (b) Kelley, S. O.; Jackson, N. M.; Hill, M. G.; Barton, J. K. Angew. Chem., Int. Ed. 1999, 38, 941. (c) Yu, C. J.; Wan, Y. J.; Yowanto, H.; Li, J.; Tao, C. L.; James, M. D.; Tan, C. L.; Blackburn, G. F.; Meade, T. J. J. Am. Chem. Soc. 2001, 123, 11155. (d) Kertesz, V.; Whittemore, N. A.; Chambers, J. Q.; McKinney, M. S.: Baker, D. C. J. Electroanal. Chem. 2000, 493, 28. (e) Hartwich, G.; Caruana, D. J.; de Lumley-Woodyear, T.; Wu, Y. B.; Campbell, C. N.; Heller, A. J. Am. Chem. Soc. 1999, 121, 10803. (f) Pike, A. R.; Lie, L. H.; Eagling, R. A.; Ryder, L. C.; Patole, S. N.; Connolly, B. A.; Horrocks, B. R.; Houlton, A. Angew. Chem., Int. Ed. 2002, 41, 615.
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2), which would exhibit a considerably lower hybridization ratio as result of spatial hindrance. The other method, as demonstrated in this work (see also ref 3b), is to prepare a dsDNA-modified surface first and then remove the complementary strand, which naturally produces an ssDNA-modified surface with optimal surface coverage for hybridization.
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37
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note
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To be more accurate, at these relatively high concentrations (Figure 2), the area of the left half of the peak (with negligible contribution from the diffusing peaks) was measured and multiplied by 2.
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38
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note
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2), within the experimental uncertainties. This could be due to incomplete heterogeneous denaturation of the duplex or to imperfect hybridization when the duplex was prepared in solution before self-assembly on the electrode surfaces. These are challenging topics in DNA chip technology for which further investigations are in progress in our laboratory.
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In the determination of adsorbed reactants by chronocoulometry, reactants arrive at the diffusion-limited rate: Anson, F. C.; Osteryoung, R. A. J. Chem. Educ. 1083, 60, 293. Heterogeneous kinetic data can be obtained by using a step potential that is insufficiently extreme to enforce diffusion-controlled electrolysis throughout the experimental time domain and analyzed by appropriate theoretical considerations: Christie, J. H.; Lauer, G.; Osteryoung, R. J. Electroanal. Chem. 1064, 7, 60. It is not easy to measure kinetic parameters of the adsorbed reactant in the presence of diffusing reactants at concentrations high enough to contribute significantly to the measured charges.
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