Selectively 13C-enriched DNA: dynamics of the C1'-H1' vector in d(CGCAAATTTGCG)2

In order to examine the internal dynamic processes of the dodecamer d(CGCAAATTTGCG)2, the 13C-enriched oligonucleotide has been synthesized. The three central thymines were selectively 13C-labeled at the C1' position and their spin-lattice relaxation parameters R(CZ), R(CX,Y), R(HZ-->CZ), R(2HZCZ), R(2HZCX,Y) and R(HZC) were measured. Density functions were computed for two models of internal motions. Comparisons of the experimental data were made with spin-lattice relaxation rates rather than with the density functions, whose values were altered by accumulation of the uncertainties of each relaxation rate measurement. The spin-lattice relaxation rates were computed with respect to the motions of the sugar around the C1'-N1 bond. A two-state jump model between the anti- and syn-conformations with P(anti)/P(syn) = 91/9 or a restricted rotation model with delta chi = 28 degrees and an internal diffusion coefficient of 30 x 10(7) s-1 gave a good fit with the experimental data. Twist, tilt or roll base motions have little effect on 13C1' NMR relaxation. Simulation of spin-relaxation rates with the data obtained at several temperatures between 7 and 32 degrees C, where the dodecamer is double stranded, shows that the internal motion amplitude is independent of the temperature within this range, as expected for internal motion. Using the strong correlation which exists in a B-DNA structure between the chi and delta angle, we suggest that the change in the glycosidic angle value should be indicative of a sugar puckering between the C1'-exo and C2'-endo conformations.