期刊
JOURNAL OF INORGANIC BIOCHEMISTRY
卷 103, 期 5, 页码 827-832出版社
ELSEVIER SCIENCE INC
DOI: 10.1016/j.jinorgbio.2009.02.006
关键词
Mismatched DNA; Cobalt(III) complex; DNA recognition; NMR; Molecular modeling
资金
- National Natural Science Foundation of China [20601018]
- Shanxi Provincial Natural Science Foundation for Youth
The binding of a Co(III) complex to the decanucleotide d(CCGAATGAGG)(2) containing two pairs of G:A mismatches was studied by 2D-NMR, UV absorption, and molecular modeling. NMR investigations indicate that racemic [Co(phen)(2)(HPIP)]Cl-3 [HPIP = 2-(2-hydroxyphenyl) imidazo [4,5-f][1, 10] phenanthroline] binds the decanucleotide by intercalation: the HPIP ligand selectively inserts between the stacked bases from the minor groove at the terminal regions and from the major groove at the sheared region. Further, molecular modeling revealed that the recognition shows strong enantioselectivity; the Delta-isomer preferentially intercalates into the T(6)G(7):A(5)A(4) region from the DNA major groove, while Delta-isomer favors t he terminal C(1)C(2:)G(10)G(9) region and intercalates from the minor groove. Detailed energy analysis suggests that the steric interaction, especially the electrostatic effect, is the primary determinants of the recognition event. Melting experiments indicate that binding stabilizes the DNA duplex and increases the melting temperature by 9.5 degrees C. The intrinsic binding constant of the complex to t he mismatched duplex was determined to be 3.5 x 105 M-1.
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