DNA fragment conformations. A 1H-NMR conformational analysis of the d(G-G)-chelated platinum-oligonucleotide d(A-T-G-G)cisPt

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Abstract
The conformation of d(A‐T‐G‐G) and d(A‐T‐G‐G)cisPt has been investigated by 1H‐NMR at 500 MHz and 90 MHz under various experimental conditions of temperature and concentration. Analysis of the coupling constants between the deoxyribose protons shows that all the sugar rings of d(A‐T‐G‐G) adopt the S(C2′‐endo) conformation most of the time. By contrast, in the platinated tetramer, d(A‐T‐G‐C)cisPt, the N(C3′‐endo) conformation is highly predominant for the internal dG residue while the S(C2′‐endo) conformation is largely favoured for the other residues as in the case of the unplatinated compound. The relaxation time and nuclear Overhauser effect measurements indicate that the orientation of the two guanines of d(A‐T‐G‐G)cisPt is anti in agreement with the previous results obtained for the dimers: r(G‐G)cisPt, d(G‐G)cisPt. On lowering the temperature from 80° to 20 °C, several proton resonances of d(A‐T‐G‐G)cisPt exhibit large chemical shift and linewidth variations. The most spectacular temperature effect was observed for the internal dG(H1′) and dT(H4′) protons. All the Δ=f(t) curves display a sigimoid form with the same mid‐point temperature of 44 ± 2 °C. This mid‐point temperature together with the observed chemical shift and linewidth variations were found to be independent of the d(A‐T‐G‐G)cisPt concentration. These results suggest that d(A‐T‐G‐G)cisPt can adopt two different conformations depending on the temperature. The enthalpy for the transition between the high and low temperature conformations is about 84 kJ/mol.

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