Transition Metal Chemistry,2010年35(6):731-736 ISSN：0340-4285
[Wu, Fu-Hai] School of Public Health, Guangdong Pharmaceutical University, Guangzhou 510006, China;[Zeng, Cheng-Hui; Liu, Yun-Jun; Li, Zheng-Zheng; Liang, Zhen-Hua] School of Pharmacy, Guangdong Pharmaceutical University, Guangzhou 510006, China;[Huang, Hong-Liang] School of Life Science and Biopharmaceutical, Guangdong Pharmaceutical University, Guangzhou 510006, China
The stability constants of the binary ML2+ and ternary M(ATP)L2- complexes, where L=Iq (isoquinoline) or BIm (benzimidazole) and M=Zn2+ or Cd2+, have been determined by potentiometric pH titration in aqueous solution at I=0.1 mol/L (NaClO4), T=25 degrees C. The stability of the ternary complexes characterized by Delta logK(M)=logK(M(ATP)L)(M(ATP))-logK(ML)(M) corresponding to the equilibrium M(ATP)(2-) + ML2+ = M(ATP)L2- + M2+ is higher than what would be expected on statistical grounds. The increase may be related to the stacking interaction between the aromatic ring of the ligands L and the purine moiety of ATP(4-). H-1 NMR studies of Zn2+/ATP(4-)/L confirm the presence of stacking in the ternary complexes. It is concluded that the strength of the intramolecular stacking interaction is dependent on the structure of the aromatic ring of the ligand L and the formation of a metal ion bridge. Possible implications are discussed briefly.
Ye, Xiaolan;Cao, Di;Zhao, Xin;Song, Fenyun;Huang, Qinghua;Fan, Guorong*;Wu, Fuhai*
Journal of chromatography. B, Analytical technologies in the biomedical and life sciences,2014年970:108-120 ISSN：1570-0232
Fan, Guorong;Wu, Fuhai
[Ye, Xiaolan; Huang, Qinghua; Cao, Di; Wu, Fuhai; Song, Fenyun] Department of Pharmaceutical Analysis, School of Pharmacy, Guangdong Pharmaceutical University, Guangzhou, China;[Ye, Xiaolan; Fan, Guorong; Cao, Di; Zhao, Xin] Shanghai Key Laboratory for Pharmaceutical Metabolite Research, No. 325 Guohe Road, Shanghai, China;[Ye, Xiaolan; Fan, Guorong; Cao, Di; Zhao, Xin] Department of Pharmaceutical Analysis, School of Pharmacy, Second Military Medical University, No. 325 Guohe Road, Shanghai, China;[Wu, Fuhai] School of Public Health, Guangdong Key Laboratory of Molecular Epidemiology, Guangdong Pharmaceutical University, Guangzhou, China
[Fan, Guorong] Shanghai Key Laboratory for Pharmaceutical Metabolite Research, No. 325 Guohe Road, Shanghai 200433, PR China. Electronic address:;[Wu, Fuhai] School of Public Health, Guangdong Key Laboratory of Molecular Epidemiology, Guangdong Pharmaceutical University, Guangzhou 510310, PR China. Electronic address:
Two Ru(II) complexes [Ru(dmb)2(dtmi)](ClO4)2 (1) (dmb = 4, 4'-dimethyl-2, 2'-bipyridine, dtmi = 3-(pyrazin-2-yl)-as-triazino[5, 6-f]-5-methoxylisatin) and [Ru(dmb)2(dtni)](ClO4)2 (2) (dtni = 3-(pyrazin-2-yl)-as-triazino[5, 6-f]-5-nitroisatin) have been synthesized and characterized by elemental analysis, ES-MS, and 1H NMR. DNA-binding behaviors of these complexes have been investigated by spectroscopic titration, viscosity measurements, and thermal denaturation. The results indicate that the two complexes interact with calf thymus DNA by intercalation.
A new ligand DBHIP and its two ruthenium(II) complexes [Ru(dmb)(2)(DBHIP)](ClO(4))(2) (1) and [Ru(dmp)(2)(DBHIP)](ClO(4))(2) (2) have been synthesized and characterized. The cytotoxicity of DBHIP and complexes 1 and 2 has been assessed by MTT assay. The apoptosis studies were carried out with acridine orange/ethidium bromide (AO/EB) staining methods. The binding behaviors of these complexes to calf thymus DNA (CT-DNA) were studied by absorption titration, viscosity measurements, thermal denaturation and photoactivated cleavage. The DNA-binding constants of complexes 1 and 2 were determined to be 8.64 +/- A 0.16 x 10(4) (s = 1.34) and 2.79 +/- A 0.21 x 10(4) (s = 2.17) M(-1). The results suggest that these complexes interact with DNA through intercalative mode. The studies on the mechanism of photocleavage demonstrate that superoxide anion radical (O(2) (aEuro cent aEuro")) and singlet oxygen ((1)O(2)) may play an important role in the DNA cleavage. The experiments on antioxidant activity show that these compounds also exhibit good antioxidant activity against hydroxyl radical (OH(aEuro cent)).
Many ruthenium(II) complexes show high antitumor activities, and the in vitro antitumor activities are usually related to DNA binding. We designed and synthesized two Ru(II) polypyridyl complexes, [Ru(dmp)(2)(fpp)](2+) (dmp=2,9-dimethyl-1,10-phenanthroline; fpp=2-[3,4-(difluoromethylenedioxy)-phenyl]imidazo[4,5-f] [1,10]phenanthroline and [Ru(phen)(2)(fpp)](2+) (phen=1,10-phenanthroline). The DNA-binding properties of these complexes have been investigated by spectroscopic titration. DNA melting experiments, viscosity measurements, and photoactivated cleavage. The mechanism studies of photocleavage revealed that singlet oxygen ((1)O(2)) and superoxide anion radical (O(2)(center dot-)) may play an important role in the photocleavage. The cytotoxicity of complexes 1 and 2 have been evaluated by MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-2H-tetrazolium bromide) method; complex 2 shows slightly higher anticancer potency than 1 does against all the cell lines screened.
The title compound, [Ru(C14H12N2)(2)(C18H14N4)](ClO4)(2)center dot-2H(2)O, consists of an Ru-II complex cation, two perchlorate anions and two uncoordinated water molecules. The Ru-II ion is chelated by a 10,11,12,13-tetrahydrodipyrido[3,2-a:2',3'-c]-phenazine ligand and two 2,9-dimethyl-1,10-phenanthroline ligands in a distorted octahedral geometry. The two uncoordinated water molecules are disordered over five positions, with an occupancy factor of about 0.4 for each site. A supramolecular structure is formed by weak pi-pi interactions between neighbouring molecules, with centroid-centroid distances of 3.618 (2)and 3.749 (2)angstrom.