期刊
JOURNAL OF BIOLOGICAL INORGANIC CHEMISTRY
卷 14, 期 3, 页码 401-407出版社
SPRINGER
DOI: 10.1007/s00775-008-0457-5
关键词
Circular dichroism; End-stacking; Guanine quadruplex; Mass spectrometry; Zinc porphyrin
资金
- New Century Excellent Talents in University [07-0134]
- National Natural Science Foundation of China [20603003]
- Doctoral Program of Higher Education [20070141071]
- Science Research Foundation of Dalian University of Technology [07014]
The interaction between small molecules and telomeric quadruplex DNA has received great attention because of its importance in molecular recognition and anticancer drug design. Using UV/vis absorption titration, thermal melting, circular dichroism spectroscopy, and electrospray ionization mass spectrometry, we examined the formation of lead ion induced guanine quadruplexes (Pb-G4) from oligonucleotide AG(3)(T(2)AG(3))(3) and their interaction with a zinc derivative of 5,10,15,20-tetrakis(N-methyl-4-pyridyl)porphyrin (Zn-TMPyP). The binding of lead ion to the oligonucleotide was found to have an unusually high affinity and followed a 1:1 stoichiometry, and the resultant Pb-G4 structure was stabilized by Zn-TMPyP binding. Owing to the steric hindrance of the axial ligand of zinc and also the relatively rigid structure of Pb-G4, intercalation of Zn-TMPyP between adjacent guanine quartets is precluded, thus allowing the end-stacking binding mode to be characterized exclusively. In conjunction with a big redshift (more than 8 nm) in the absorption spectrum, we demonstrate that a conservative induced circular dichroism is an important signature for end-stacking of porphyrins on guanine quadruplexes.
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