Structure of a copper-mediated base pair in DNA.

Stable and selective DNA base pairing by metal coordination was recently demonstrated with nucleotides containing complementary pyridine-2,6-dicarboxylate (Dipic) and pyridine (Py) bases (Meggers, E.; Holland, P. L.; Tolman; W. B.; Romesberg, F. E.; Schultz, P. G. J. Am. Chem. Soc. 2000, 122, 10714-10715). To understand the structural consequences of introducing this novel base pair into DNA we have solved the crystal structure of a duplex containing the metallo-base pair. The structure shows that the bases pair as designed, but in a Z-DNA conformation. The structure also provides a structural explanation for the B- to Z-DNA transition in this duplex. Further solution studies demonstrate that the metallo-base pair is compatible with Z- or B-DNA conformations, depending on the duplex sequence.

Electron transfer in DNA from guanine and 8-oxoguanine to a radical cation of the carbohydrate backbone.

Photolysis of a 4'-pivaloyl-substituted nucleotide in single- and double-stranded DNA (1) generated an enol ether radical cation 4 that was reduced to enol ether 17 by electron transfer from the nearest guanoside (G). Variation of the nucleotide sequence demonstrated a strong distance dependence of this electron-transfer rate with beta = 1.0 +/- 0.1 A(-1). When 8-oxoguanosine (G(oxo)) was used as the electron donor, the rate of the electron transfer increased by a factor of 4 but the distance dependence of the transfer remained unchanged within experimental error. In single strands, the number of intervening A, T, and C nucleotides had a much smaller effect; the rate remained nearly constant for two, three, or four intervening nucleotides. This is explained by the flexibility of the single-stranded oligonucleotides.