Tris(tetramethylphenanthroline)ruthenium(II): a chiral probe that cleaves A-DNA conformations.
lambda-Tris(3,4,7,8-tetramethyl-1,10-phenanthroline)ruthenium(II) [lambda-Ru(TMP)2+3] was found to be a distinctive molecular tool to examine the local variations in conformation along the strand. The metal complex binds cooperatively to A-form helices of various base sequences under conditions where little or no binding was found to analogous B-form DNAs. Photoactivated DNA cleavage may be coupled to this conformation-specific binding by taking advantage of the photophysical properties of ruthenium(II) complexes. lambda-Ru(TMP)2+3 cleaves preferentially 3H-labeled A-form polynucleotides upon irradiation with visible light. The photoinduced DNA strand scission is likely to be mediated by singlet oxygen, which leads to a preferential cleavage of guanine residues. Comparative mapping of cleavage sites on a linear pBR322 fragment for tris(phenanthroline)ruthenium(II), which binds to B-DNA and cleaves also by sensitization of singlet oxygen, and for Ru(TMP)2+3 shows the selective binding of lambda-Ru(TMP)2+3 to conformationally distinct sites along the fragment. These sites correspond to 5- to 13-base-pair homopyrimidine stretches.
Mei
H Y
HY
Department of Chemistry, Columbia University, New York, NY 10027.
Barton
J K
JK
D055598:Chemical Phenomena; D002621:Chemistry; D004247:DNA; D009690:Nucleic Acid Conformation; D009942:Organometallic Compounds; D010618:Phenanthrolines; D011119:Polynucleotides; D012428:Ruthenium
D009942:Organometallic Compounds; D010618:Phenanthrolines; D011119:Polynucleotides; C055043:tris(3,4,7,8-tetramethyl-1,10-phenanthroline)ruthenium(II); D012428:Ruthenium; D004247:DNA