A pair
of ruthenium(II) complex enantiomers, Δ- and Λ-[Ru(bpy)2MBIP]2+ (bpy = 2,2′-bipyridine,
MBIP = 2-(3-bromophenyl)imidazo[5,6-f]phenanthroline),
were designed, synthesized, and characterized.
Comparative studies between the enantiomers on their binding behaviors
to calf thymus DNA (CT-DNA) were conducted using UV−visible,
fluorescence, and circular dichroism spectroscopies, viscosity measurements,
isothermal titration calorimetry, a photocleavage experiment, and
molecular simulation. The experimental results indicated that both
the enantiomers spontaneously bound to CT-DNA through intercalation
stabilized by the van der Waals force or the hydrogen bond and driven
by enthalpy and that Δ-[Ru(bpy)2MBIP]2+ intercalated into DNA more deeply than Λ-[Ru(bpy)2MBIP]2+ did and exhibited
a better DNA photocleavage ability. Molecular simulation further indicated
that Δ-[Ru(bpy)2MBIP]2+ more preferentially intercalated between the base pairs of CT-DNA
to the major groove, and Λ-[Ru(bpy)2MBIP]2+ more favorably intercalated to the minor groove.
These research findings should be very helpful to the understanding
of the stereoselectivity mechanism of DNA-bindings of metal complexes,
and be useful for the design of novel metal-complex-based antitumor
drugs with higher efficacy and lower toxicity.