Polaronic semiconductor behavior of long-range charge transfer in DNA oligomers in solution: controlling barriers to long-distance radical cation migration in DNA with thymine analogs.
A series of anthraquinone-linked DNA oligonucleotides was prepared and the efficiency of long-distance radical cation migration was measured. In one set of oligonucleotides, two GG steps are separated by either a TATA or an ATAT bridge. In these two compounds, the efficiency of radical cation migration from GG to GG differs by more than an order of magnitude. Replacement of the thymines in the TATA or ATAT bridges with 3-methyl-2-pyridone (t, a thymine analog) results in the much more efficient radical cation migration across the bridge in both cases. This is attributed to a decrease in the oxidation potential of t to a value below that of A. In contrast, replacement of the thymines in the TATA or ATAT bridges with difluorotoluene (f, a thymine analog with high oxidation potential) does not measurably affect radical cation migration. These findings are readily accommodated by the phonon-assisted polaron-hopping mechanism for long-distance charge transfer in duplex DNA and indicate that DNA in solution behaves as a polaronic semiconductor.
Joy
Abraham
A
School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332, USA.
Guler
Gozde
G
Ahmed
Shahadat
S
McLaughlin
Larry W
LW
Schuster
Gary B
GB
D002412:Cations / Q000737:chemistry*; D004247:DNA / Q000737:chemistry*; D004058:Diffusion; D004559:Electric Wiring; D004563:Electrochemistry / Q000379:methods*; D004579:Electron Transport; D009841:Oligonucleotides / Q000032:analysis / Q000737:chemistry*; D012666:Semiconductors; D012996:Solutions; D055672:Static Electricity; D013941:Thymine / Q000031:analogs & derivatives*
D002412:Cations; D009841:Oligonucleotides; D012996:Solutions; D004247:DNA; D013941:Thymine