Premium
Effect of Electronic Structures of Enantiomers of Ruthenium(II) Polypyridyl Complexes on DNA Binding Behaviors
Author(s) -
Luo Haimei,
Xiao Jie,
Chen Jincan,
Xu Hong,
Lu Jun,
Liu Zhigang,
Chen Siping,
Tong Mingliang,
Zheng Kangcheng,
Ji Liangnian
Publication year - 2010
Publication title -
chinese journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.28
H-Index - 41
eISSN - 1614-7065
pISSN - 1001-604X
DOI - 10.1002/cjoc.201090226
Subject(s) - chemistry , enantiomer , ruthenium , density functional theory , titration , stereoselectivity , dna , crystallography , electrochemistry , electronic structure , crystal structure , stereochemistry , bipyridine , computational chemistry , inorganic chemistry , organic chemistry , catalysis , biochemistry , electrode
A pair of Ru(II) complex enantiomers, Δ ‐ and Λ ‐[Ru(bpy) 2 ( p ‐mpip)] 2+ {bpy=2,2′‐bipyridine, p ‐mpip=2‐(4‐methylphenyl)imidazo[4,5‐f]‐1,10‐phenanthroline} have been synthesized and structurally characterized. Both experimental results from crystallography, NMR, electrochemistry and theoretical calculations applying the density functional theory (DFT) method based on their crystal structures show that small difference in geometric structure existed can cause a considerable difference in electronic structure between enantiomers. In addition, the binding of the two enantiomers to calf thymus DNA (CT DNA) has been investigated with UV spectroscopy titration and viscosity measurements. It is very rare that the Λ enantiomer binds to DNA more strongly than the Δ enantiomer, which can be reasonably explained by their different electronic structures for the first time, suggesting that the dominant factor governing the stereoselectivity of DNA binding of Ru(II) complex may be the different electronic structures of its enantiomers.