Synthesis, spectroscopic studies of new water-soluble Co(II) and Cu(II) macrocyclic complexes of 4,15-bis(2-hydroxyethyl)-2,4,6,13,15,17-hexaazatricyclodocosane:: their interaction studies with calf thymus DNA and guanosine 5′ monophosphate

被引:47
|
作者
Arjmand, Farukh [1 ]
Aziz, Mubashira [1 ]
Chauhan, Mala [1 ]
机构
[1] Aligarh Muslim Univ, Dept Chem, Aligarh 202002, Uttar Pradesh, India
关键词
binding studies; CT-DNA; 5'GMP binding studies; NMR and UV/vis; fluorescence; macrocyclic complexes;
D O I
10.1007/s10847-008-9417-5
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
New water soluble Co(II) 1, Ni(II) 2 and Cu(II) 3 complexes of 4,15-bis(2-hydroxyethyl)-2,4,6,13,15,17-hexaazatricyclodocosane Co(II) were synthesized and characterized by various techniques, viz. elemental analysis, conductivity measurements, infrared, electronic, ESI-MS, H-1 and C-13 NMR spectroscopy. Molar conductance measurements in aqueous solution showed that complexes 1, 2 and 3 are ionic in nature. On the basis of spectroscopic data, a square planar geometry was assigned to the complexes involving four N-atoms of the two cyclohexane moieties. Interaction studies of 1 and 3 with CT-DNA were carried using UV/Visible absorption spectroscopy, fluorescence spectrophotometry, cyclic voltammetry and viscosity measurements. Absorption spectral traces reveal 27.7 and 23.3% hyperchromism for complexes 1 and 3, respectively indicative of strong binding to CT-DNA. These results were authenticated by fluorescence quenching experiments and viscosity measurements. The intrinsic binding constants K-b of 1 and 3 are 2.94 x 10(4) and 2.71 x 10(4) M-1, respectively. Early transition metals show preference for O6 position while later ones copper and cobalt prefer N7 position of DNA base guanine. To validate this hypothesis, interaction studies of copper (II) and cobalt (II) complexes were carried out with 5'GMP, which revealed electrostatic interactions are more favored along with hydrogen bonding than coordinate covalent interaction to N7 position of guanine.
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页码:265 / 278
页数:14
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