The dichotomy in the DNA-binding behaviour of ruthenium(II) complexes bearing benzoxazole and benzothiazole groups.
The substituted tris(bipyridine)ruthenium(II) complexes {[Ru(bpy)(2)(4,4'-bbob)](2+) and [Ru(bpy)(2)(5,5'-bbob)](2+) [where bpy=2,2'-bipyridine and bbob=bis(benzoxazol-2-yl)-2,2'-bipyridine] have been prepared and compared to the previously studied complex [Ru(bpy)(2)(4,4'-bbtb)](2+) [where bbtb=bis(benzothiazol-2-yl)-2,2'-bipyridine]. From the UV/VIS titration studies, Delta-[Ru(bpy)(2)(4,4'-bbob)](2+) displays a stronger association than the Lambda-isomer with calf-thymus DNA (ct-DNA). For [Ru(bpy)(2)(5,5'-bbob)](2+), there appears to be minimal interaction with ct-DNA. The results of fluorescence titration studies suggest that [Ru(bpy)(2)(4,4'-bbob)](2+) gives an increase in emission intensity with increasing ct-DNA concentrations, with an enantiopreference for the Delta isomer, confirmed by membrane dialysis studies. The fluorescent intercalation displacement studies revealed that [Ru(bpy)(2)(4,4'-bbob)](2+) and [Ru(bpy)(2)(5,5'-bbob)](2+) display a preference for more open DNA structures such as bulge and hairpin sequences. While Lambda-[Ru(bpy)(2)(4,4'-bbtb)](2+) has shown the most significant affinity for all the oligonucleotides sequences screened in previous studies, it is the Delta isomer of the comparable benzoxazole ruthenium(II) complex (Delta-[Ru(bpy)(2)(4,4'-bbob)](2+)) that preferentially binds to DNA.
Spillane
Catriona B
CB
The School of Chemistry and Chemical Engineering, Queen's University Belfast, Belfast BT9 5AG, Northern Ireland, United Kingdom.
Dabo
Marième N V
MN
Fletcher
Nicholas C
NC
Morgan
Joy L
JL
Keene
F Richard
FR
Haq
Ihtshamul
I
Buurma
Niklaas J
NJ
D000818:Animals; D052160:Benzothiazoles / Q000737:chemistry*; D001583:Benzoxazoles / Q000737:chemistry*; D002417:Cattle; D004247:DNA / Q000737:chemistry*; D017975:Ruthenium Compounds / Q000737:chemistry*; D013057:Spectrum Analysis
D052160:Benzothiazoles; D001583:Benzoxazoles; D017975:Ruthenium Compounds; D004247:DNA; C005465:benzothiazole