A solid-state 2H NMR investigation of purine motion in a 12 base pair RNA duplex.
Solid-state 2H NMR spectroscopy has been used to investigate the base dynamics of a RNA oligonucleotide with a defined sequence, [r(CGCGAAUUCGCG)]2, which contains the RNA analogue of the EcoRI binding site. The C8 protons of all purines in the self-complementary dodecamer were exchanged for deuterons. The quadrupole-echo lineshapes and spin-lattice relaxation times as a function of hydration for the sample in the form of the Na salt have previously been reported. In that study the 2H NMR lineshapes and T1 values of [r(CG*CG*A*A*UUCG*CG*)]2 were compared with those of the analogously labeled DNA sequence, [(CG*CG*A*A*TTCG*CG*)]2 (Wang et al., J. Am. Chem. Soc. 114, 6583, 1992). It was concluded that the amplitudes of purine motion for DNA and RNA are similar at all hydration levels; however, the rate difference observed at low-hydration levels may or may not persist at high hydration. Here the internal motions of the purine bases in the RNA oligomer have been thoroughly investigated. Three models were used to simulate the motion: (1) two-site jump, (2) diffusion in a cone, and (3) restricted diffusion on the surface of a cone. The purine motion is best simulated by the restricted-diffusion on a cone model with an amplitude of +/- 9.5 degrees and a rate between 8.0 x 10(6) rad/s at 90% RH and 8.4 x 10(8) rad/s at 0% RH. This small amplitude and fast rate of purine motion for RNA are similar to previous results obtained for DNA purines.
Wang
A C
AC
Department of Biochemistry, University of Washington, Seattle 98195.
Kennedy
M A
MA
Reid
B R
BR
Drobny
G P
GP
D001483:Base Sequence; D009682:Magnetic Resonance Spectroscopy; D009690:Nucleic Acid Conformation; D011687:Purines / Q000737:chemistry*; D012313:RNA / Q000737:chemistry*
D011687:Purines; D012313:RNA