A novel, yet effective method for identifying DNA-binding modes of [Ru(bpy)2dmt]2+ (where bpy = 2,2′-bipyridine and dmt = 2,3-dimethyl-1,4,8,9-tetra-aza-triphenylene) on an indium tin oxide electrode has been successfully developed by introducing Cu2+ ion and ethylenediaminetetraacetic acid. The results from emission spectra and fluorescence microscopic images suggested that [Ru(bpy)2dmt]2+ not only associates with Cu2+ ion in both the absence and presence of DNA but also shows strong affinity with DNA in the presence of Cu2+. Evidence for the strong binding of [Ru(bpy)2dmt]2+ to DNA was determined from the interface studies using electrochemical methods. The present study suggests that a combination of photoluminescence measurement with electrochemical methods identifies the DNA-binding behavior of luminescent molecules with redox activities. [Ru(bpy)2dmt]2+ binds to DNA via an intercalative mode.
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References
1.
AmbrosekD., LoosP.F., AssfeldX., DanielC.2010. A theoretical study of Ru(II) polypyridyl DNA intercalators: structure and electronic absorption spectroscopy of [Ru(phen)2(dppz)]2+ and [Ru(tap)2(dppz)]2+ complexes intercalated in guanine–cytosine base pairs. J Inorg Biochem, 104:893–901.
2.
ArkinM.R., StempE.D.A., BartonJ.K., HörmannA., OlsonE.J.C., BarbaraP.F.1996. Rates of DNA-mediated electron transfer between metallointercalators. Science, 273:475–479.
3.
BandoT., SugiyamaH.2006. Synthesis and biological properties of sequence-specific DNA-alkylating pyrrole-imidazole polyamides. Acc Chem Res, 39:935–944.
4.
BartonJ.K., DanishefskyA., GoldbergJ.1984. Tris(phenanthroline)ruthenium(II): stereoselectivity in binding to DNA. J Am Chem Soc, 106:2172–2176.
5.
ChenP.L., ChaoH., XuJ., WangL., LiH.2009. Luminescence properties of a di-ruthenium(II) complex with an intramolecular hydrogen bond modulated by DNA and copper(II) ion. Transition Met Chem, 34:773–778.
6.
CoatesC.G., JacquetL., McGarveyJ.J., BellS.E.J., Al-ObaidiA.H.R., KellyJ.M.1997. Resonance Raman probing of the interaction between dipyridophenazine complexes of Ru(II) and DNA. J Am Chem Soc, 119:7130–7136.
7.
DupureurC.M., BartonJ.K.1997. Structural studies of Λ- and Δ- [Ru(phen)2dppz]2+ bound to d(GTCGAC)2: characterization of enantioselective intercalation. Inorg Chem, 36:33–43.
8.
ErikssonM., LeijonM., HiortC., NordenB., GraeslundA.1992. Minor groove binding of [Ru(phen)3]2+ to [d(CGCGATCGCG)]2 evidenced by two-dimensional NMR. J Am Chem Soc, 114:4933–4934.
9.
GaoY.A., LiN., ZhengL.Q., ZhaoX.Y., ZhangS.H., HanB.X., HouW.G., LiG.Z.2006. A cyclic voltammetric technique for the detection of micro-regions of bmimPF6/Tween 20/H2O microemulsions and their performance characterization by UV–vis spectroscopy. Green Chem, 8:43–49.
10.
HanM.J., GaoL.H., LüY.Y., WangK.Z.2006. Ruthenium(II) complex of hbopip: Synthesis, characterization, pH-induced luminescence “off−on−off” switch, and avid binding to DNA. J Phys Chem B, 110:2364–2371.
11.
HiortC., NordenB., RodgerA.1990. Enantiopreferential DNA binding of [ruthenium(II)(1,10-phenanthroline)3]2+ studied with linear and circular dichroism. J Am Chem Soc, 112:1971–1982.
12.
LiH., LiuY.J., XuJ., XuZ.H., JiL.N., LiW.S., ChenH.Y.2007. DNA-enhanced assembly of [Ru(bpy)2ITATP]3+/2+ on an ITO electrode. Electrochim Acta, 52:4956–4961.
13.
LiJ., XuL.C., ChenJ.C., ZhengK.C., JiL.N.2006. Density functional theory/time-dependent DFT studies on the structures, trend in DNA-binding affinities, and spectral properties of complexes [Ru(bpy)2(p-R-pip)]2+ (R = −OH, −CH3, −H, −NO2)J Phys Chem A, 110:8174–8180.
14.
LimM.H., SongH., OlmonE.D., DervanE.E., BartonJ.K.2009. Sensitivity of [Ru(bpy)2dppz]2+ luminescence to DNA defects. Inorg Chem, 48:5392–5397.
15.
LiuJ.G., ZhangQ.L., ShiX.F., JiL.N.2001. Interaction of [Ru(dmp)2(dppz)]2+ and [Ru(dmb)2(dppz)]2+ with DNA: effects of the ancillary ligands on the DNA-binding behaviors. Inorg Chem, 40:5045–5050.
16.
LiuX.W., LuJ.L., ChenY.D., LiL., ZhangD.S.2010. A novel DNA light switch [Ru(bpy)2pzip]2+ activated by cobalt(II) ion. Inorg Chem Commun, 13:449–451.
17.
LiuY., ChouaiA., DegtyarevaN.N., LuttermanD.A., DunbarK.R., TurroC.2005. Chemical control of the DNA light switch: cycling the switch on and off. J Am Chem Soc, 127:10796–10797.
18.
LiuY.J., WeiX.Y., WuF.H., MeiW.J., HeL.X.2008. Interaction studies of DNA binding of ruthenium(II) mixed-ligand complexes: [Ru(phen)2(dtmi)]2+ and [Ru(phen)2(dtni)]2+Spectrochim Acta A, 70:171–176.
19.
MarmurJ.1961. A procedure for the isolation of deoxyribonucleic acid from micro-organisms. J Mol Biol, 3:208–218.
20.
MihailovicA., VladescuI., McCauleyM., LyE., WilliamsM.C., SpainE.M., NuñezM.E.2006. Exploring the interaction of ruthenium(II) polypyridyl complexes with DNA using single-molecule techniques. Langmuir, 22:4699–4709.
21.
NakabayashiY., WatanabeY., NakaoT., YamauchiO.2004. Interactions of mixed ligand ruthenium(II) complexes containing an amino acid and 1,10-phenanthroline with DNA. Inorg Chim Acta, 357:2553–2560.
22.
ReichmannM.E., RiceS.A., ThomasC.A., DotyP.1954. A further examination of the molecular weight and size of desoxypentose nucleic acid. J Am Chem Soc, 76:3047–3053.
23.
SatyanarayanaS., DabrowiakJ.C., ChairesJ.B.1992. Neither Δ- nor Λ- tris(phenanthroline)ruthenium(II) binds to DNA by classical intercalation. Biochemistry, 31:9319–9324.
24.
ShiS., XieT., YaoT.M., WangC.R., GengX.T., YangD.J., HanL.J., JiL.N.2009. Synthesis, characterization, DNA-binding and DNA-photocleavage studies of [Ru(bpy)2(pmip)]2+ and [Ru(phen)2(pmip)]2+ (pmip = 2-(2′-pyrimidyl)imidazo [4,5-f][1,10]phenanthroline. Polyhedron, 28:1355–1361.
25.
ShinoharaK., NaritaA., OyoshiT., BandoT., TeraokaH., SugiyamaH.2004. Sequence-specific gene silencing in mammalian cells by alkylating pyrrole-imidazole polyamides. J Am Chem Soc, 126:5113–5118.
26.
SpillaneC.B., DaboM.N.V., FletcherN.C., MorganJ.L., KeeneF. R., HaqI., BuurmaN.J.2008. The dichotomy in the DNA-binding behaviour of ruthenium(II) complexes bearing benzoxazole and benzothiazole groups. J Inorg Biochem, 102:673–683.
27.
SunY.J., LuttermanD.A., TurroC.2008. Role of electronic structure on DNA light-switch behavior of Ru(II) intercalators. Inorg Chem, 47:6427–6434.
28.
TanL.F., ChaoH., LiH., LiuY.J., SunB., WeiW., JiL.N.2005. Synthesis, characterization, DNA-binding and photocleavage studies of [Ru(bpy)2(PPIP)]2+ and [Ru(phen)2(PPIP)]2+J Inorg Biochem, 99:513–520.
29.
TuiteE., LincolnP., NordénB.1997. Photophysical evidence that Δ- and Λ-[Ru(phen)2(dppz)]2+ intercalate DNA from the minor groove. J Am Chem Soc, 119:239–240.
30.
TysoeS.A., KopelmanR., SchelzigD.1999. Flipping the molecular light switch off: formation of DNA-bound heterobimetallic complexes using Ru(bpy)2tpphz2+ and transition metal ions. Inorg Chem, 38:5196–5197.
WangX.h., RenJ.S., QuX.G.2008. Biophysical studies on the full-length human cyclin A2: protein stability and folding/unfolding thermodynamics. J Phys Chem B, 112:8346–8353.
33.
WilliamsR.L., ToftH.N., WinkelB., BrewerK.J.2003. Synthesis, characterization, and DNA binding properties of a series of Ru, Pt mixed-metal complexes. Inorg Chem, 42:4394–4400.
34.
YanX.X., LiH., XuZ.H., LiW.S.2009. Electrocatalytic activity of [Ru(bpy)3]2+ for hypoxanthine oxidation studied by rotating electrode methods. Bioelectrochemistry, 74:310–314.
35.
YangH.H., LiuH.P., KangH.Z., TanW.H.2008. Engineering target-responsive hydrogels based on aptamer-target interactions. J Am Chem Soc, 130:6320–6321.
36.
YaoS., LiH., GuoQ.Y., XuZ.H., JiL.N.2008. DNA-promoted electrochemical assembly of [Ru(bpy)2dpp]3+/2+ on the ITO electrode by introducing copper(II) ion. Electrochim Acta, 53:5169–5173.
37.
YunB.H., KimJ.O., LeeB.W., LincolnP., NordénB., KimJ.M., KimS.K.2003. Simultaneous binding of ruthenium(II) [(1,10-Phenanthroline)2 dipyridophenazine]2+ and minor groove binder 4',6-diamidino-2-phenylindole to poly[d(A−T)2] at high binding densities: observation of fluorescence resonance energy transfer across the DNA stem. J Phys Chem B, 107:9858–9864.
38.
ZhangX.R., LiY., SuH.R., ZhangS.S.2010. Highly sensitive and selective detection of Hg2+ using mismatched DNA and a molecular light switch complex in aqueous solution. Biosens Bioelectron, 25:1338–1343.
39.
ZhangZ.Q., LiH., XuJ., YaoS., XuZ.H., LiuJ.G., JiL.N.2007. DNA intercalating studies of [Ru(bpy)2HPIP]2+ with intramolecular hydrogen bond ligand based on introduction of copper ion. Transition Met Chem, 32:776–780.
40.
ZhenQ.X., YeB.H., LiuJ.G., JiL.N., WangL.1999. Synthesis of ruthenium polypyridyl complexes and the steric influence of the intercalated ligand on DNA binding. Chem Res Chin U, 20:1661–1666.
41.
ZouX.H., YeB.H., LiH., ZhangQ.L., ChaoH., LiuJ.G., JiL.N., LiX.Y.2001. The design of new molecular “light switches” for DNA. J Biol Inorg Chem, 6:143–150.
