Blasius Romain, Nierengarten Hélène, Luhmer Michel, Constant Jean-François, Defrancq Eric, Dumy Pascal, van Dorsselaer Alain, Moucheron Cécile, Kirsch-Demesmaeker Andrée
Université Libre de Bruxelles, Chimie Organique et Photochime, Brussels, Belgium.
Chemistry. 2005 Feb 18;11(5):1507-17. doi: 10.1002/chem.200400591.
[Ru(hat)2phen]2+ (HAT=1,4,5,8,9,12-hexaazatriphenylene, phen=1,10-phenanthroline) interacts with a good affinity with polynucleotides and DNA by intercalation, despite the presence of a second voluminous ancillary HAT ligand. It photoreacts with guanosine-5'-monophosphate (GMP). From HPLC, ESMS and NMR analyses, it can be concluded that this complex forms photoadducts with GMP. In contrast to the photoadducts isolated with Ru-TAP complexes (TAP=1,4,5,8-tetraazaphenanthrene), the photoadducts with [Ru(hat)2phen]2+ contain a covalent link between the oxygen atom of the guanine unit and a HAT ligand. Formation of oxidised photoadducts and compounds resulting from the addition of two GMP entities to the complex are also detected as side products. In the presence of oligo- and polynucleotides, [Ru(hat)2phen]2+ yields photoadducts when guanine bases are present.
[Ru(hat)2phen]2+(HAT = 1,4,5,8,9,12 - 六氮杂三亚苯,phen = 1,10 - 菲咯啉)尽管存在第二个体积较大的辅助HAT配体,但仍通过嵌入与多核苷酸和DNA以良好的亲和力相互作用。它与5'-鸟苷单磷酸(GMP)发生光反应。通过高效液相色谱(HPLC)、电喷雾质谱(ESMS)和核磁共振(NMR)分析,可以得出该配合物与GMP形成了光加合物。与用Ru - TAP配合物(TAP = 1,4,5,8 - 四氮杂菲咯啉)分离得到的光加合物不同,[Ru(hat)2phen]2+的光加合物在鸟嘌呤单元的氧原子和一个HAT配体之间含有一个共价键。氧化光加合物以及由两个GMP实体加成到配合物上产生的化合物也作为副产物被检测到。在寡核苷酸和多核苷酸存在的情况下,当存在鸟嘌呤碱基时,[Ru(hat)2phen]2+会产生光加合物。