Nucleic Acids Research, Vol 24, Issue 4 676-682, Copyright © 1996 by Oxford University Press
H Robinson and AH Wang
The (dG)n.(dC)n-containing 34mer DNA duplex [d(A2G15C15T2)]2 can be
effectively converted from the B-DNA to the A-DNA conformation by neomycin,
spermine and Co(NH3)6(3+). Conversion is demonstrated by a characteristic
red shift in the circular dichroism spectra and dramatic NMR spectral
changes in chemical shifts. Additional support comes from the substantially
stronger CH6/GH8-H3'NOE intensities of the ligand-DNA complexes than those
from the native DNA duplex. Such changes are consistent with a deoxyribose
pucker transition from the predominate C2'-endo (S-type) to the C3'-endo
(N-type). The changes for all three ligand-DNA complexes are identical,
suggesting that those three complex cations share common structural motifs
for the B- to A-DNA conversion. The A-DNA structure of the 4:1 complex of
Co(NH3)6(3+)/d(ACCCGCGGGT) has been analyzed by NOE-restrained refinement.
The structural basis of the transition may be related to the closeness of
the two negatively charged sugar-phosphate backbones along the major groove
in A-DNA, which can be effectively neutralized by the multivalent
positively charged amine functions of these ligands. In addition, ligands
like spermine or Co(NH3)6(3+) can adhere to guanine bases in the deep major
groove of the double helix, as is evident from the significant direct NOE
cross-peaks from the protons of Co(NH3)6(3+) to GH8, GH1 (imino) and CH4
(amino) protons. Our results point to future directions in preparing more
potent derivatives of Co(NH3)6(3+) for RNA binding or the induction of
A-DNA.
ARTICLES
Neomycin, spermine and hexaamminecobalt (III) share common structural motifs in converting B- to A-DNA
Biophysics Division and Department of Cell and Structural Biology, University of Illinois at Urbana-Champaign, IL 61801, USA.
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