RESUMEN
This paper first reports on the condensation of DNA to a tightly packed state induced by a V-shaped di-ruthenium(II) complex [Ru2(bpy)4(mbpibH2)]Cl4 (bpy=2,2'-bipyridine and mbpibH2=1,3-bis([1,10]phenanthroline[5,6-d]imidazol-2-yl)benzene), which binds to the groove of herring sperm DNA (hsDNA) with the binding constant of 2.0×10(7)M(-1) (0.05M NaCl, pH7.2). The di-Ru(II) complex is found to induce the condensation of both hsDNA to long chain-like particle clusters and originally circular plasmid pBR322 DNA to particulate structure under neutral conditions. More interestingly, the presence of NaCl has a significant impact on the condensation and decondensation of DNA upon incorporation of [Ru2(bpy)4(mbpibH2)](4+), representing tunable luminescence characteristics by NaCl. High salt concentration facilitates the decondensation of DNA-[Ru2(bpy)4(mbpibH2)](4+) adducts. The results from this study offer an effective method to control the condensation and decondensation of DNA upon incorporation of luminescent concentrators.
Asunto(s)
ADN/química , Plásmidos/química , Compuestos de Rutenio/química , Cloruro de Sodio/química , Animales , Peces , Mediciones LuminiscentesRESUMEN
An imidazophenanthroline-containing ruthenium(II) complex [Ru(bpy)(2)(mbpibH2)](2+) (bpy=2,2'-bipyridine, mbpibH2=1,3-bis([1,10]phenanthroline[5,6-d]imidazol-2-yl)benzene) can bind DNA through groove-binding and/or non-classical intercalation modes, revealed by spectrophotometric methods, viscosity measurements and variable ionic strength experiments. On the basis of binding interactions between cationic [Ru(bpy)(2)(mbpibH2)](2+) and anionic DNA at a molar ratio of 1:1, a yellow transparent cast film has been assembled on an indium-tin oxide (ITO) surface using a solution-based self-standing method. The prepared DNA-[Ru(bpy)(2)(mbpibH2)](2+) film shows a bi-exponential luminescence decay with τ(1)=62.1 ns (8.0%) and τ(2)=594.5 ns (92.0%), whose lifetimes become much shorter than those of DNA-bound [Ru(bpy)(2)(mbpibH2)](2+) in buffer solutions. The Ru(II) complex with a free bi-dentate coordination site in the DNA cast film shows tunable luminescence, quenched dynamically by Cu(2+) and restored by using EDTA to eliminate two modes of Cu(2+)-binding. The results from this study provide a significant foundation for better understanding the fabrication and modulation of a DNA-based solid luminescence device using the Ru(II) complexes as DNA-concentrating and signal-sensing agents.