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Synthesis,Characterization, and DNA‐Binding Properties of the Chiral Ruthenium(II) Complexes Δ‐ and Λ‐[Ru(bpy)2(dmppd)]2+ (dmppd = 10,12‐Dimethylpteridino[6,7‐f] [1,10]phenanthroline‐11,13(10H,12H)‐dione; bpy = 2,2′‐Bipyridine)
Authors:Feng Gao  Hui Chao  Feng Zhou  Lian‐Cai Xu  Kang‐Cheng Zheng  Liang‐Nian Ji
Institution:1. Key Laboratory of Bioinorganic and Synthetic Chemistry of the Ministry of Education, School of Chemistry and Chemical Engineering, Sun Yat‐Sen University, Guangzhou 510275, P.?R. China, (fax: 86‐20‐84035497);2. Department of Chemistry, Tongji University, Shanghai 200092, P.?R. China;3. State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, P.?R. China
Abstract:Two novel chiral ruthenium(II) complexes, Δ‐Ru(bpy)2(dmppd)]2+ and Λ‐Ru(bpy)2(dmppd)]2+ (dmppd = 10,12‐dimethylpteridino6,7‐f] 1,10]phenanthroline‐11,13(10H,12H)‐dione, bpy = 2,2′‐bipyridine), were synthesized and characterized by elemental analysis, 1H‐NMR and ES‐MS. The DNA‐binding behaviors of both complexes were studied by UV/VIS absorption titration, competitive binding experiments, viscosity measurements, thermal DNA denaturation, and circular‐dichroism spectra. The results indicate that both chiral complexes bind to calf‐thymus DNA in an intercalative mode, and the Δ enantiomer shows larger DNA affinity than the Λ enantiomer does. Theoretical‐calculation studies for the DNA‐binding behaviors of these complexes were carried out by the density‐functional‐theory method. The mechanism involved in the regulating and controlling of the DNA‐binding abilities of the complexes was further explored by the comparative studies of Ru(bpy)2(dmppd)]2+ and of its parent complex Ru(bpy)2(ppd)]2+ (ppd = pteridino6,7‐f] 1,10]phenanthroline‐11,13 (10H,12H)‐dione).
Keywords:Ruthenium complexes  2  2′  ‐Bipyridine complexes  Polypyridine ligands  DNA  Chiral complexes
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