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.     

DNA binding by Ru(II)–bis(bipyridine)–pteridinyl complexes

The interactions of five bis(bipyridyl) Ru(II) complexes of pteridinyl-phenanthroline ligands with calf thymus DNA have been studied. The pteridinyl extensions were selected to provide hydrogen-bonding patterns complementary to the purine and pyrimidine bases of DNA and RNA. The study includes three new complexes [Ru(bpy)(2)(L-pterin)](2+), [Ru(bpy)(2)(L-amino)](2+), and [Ru(bpy)(2)(L-diamino)](2+) (bpy is 2,2'-bipyridine and L-pterin, L-amino, and L-diamino are phenanthroline fused to pterin, 4-aminopteridine, and 2,4-diaminopteridine), two previously reported complexes [Ru(bpy)(2)(L-allox)](2+) and [Ru(bpy)(2)(L-Me(2)allox)](2+) (L-allox and L-Me(2)allox are phenanthroline fused to alloxazine and 1,3-dimethyalloxazine), the well-known DNA intercalator [Ru(bpy)(2)(dppz)](2+) (dppz is dipyridophenazine), and the negative control [Ru(bpy)(3)](2+). Reported are the syntheses of the three new Ru-pteridinyl complexes and the results of calf thymus DNA binding experiments as probed by absorption and fluorescence spectroscopy, viscometry, and thermal denaturation titrations. All Ru-pteridine complexes bind to DNA via an intercalative mode of comparable strength. Two of these four complexes-[Ru(bpy)(2)(L-pterin)](2+) and [Ru(bpy)(2)(L-allox)](2+)-exhibit biphasic DNA melting curves interpreted as reflecting exceptionally stable surface binding. Three new complexes-[Ru(bpy)(2)(L-diamino)](2+), [Ru(bpy)(2)(L-amino)](2) and [Ru(bpy)(2)(L-pterin)](2+)-behave as DNA molecular "light switches."     

Interactions of the antibiotics neomycin B and chlortetracycline with the hammerhead ribozyme as studied by Zn2+-dependent RNA cleavage

We have investigated the interactions of two antibiotics, neomycin B and chlortetracycline (CTC), with the hammerhead ribozyme using two Zn(2+) cleavage sites at U4 and A9 in its catalytic core. CTC-dependent inhibition of Zn(2+) cleavage was observed in all cases. In contrast, we unexpectedly observed acceleration of A9 cleavage by neomycin under low ionic strength conditions similar to those used to study inhibition of hammerhead substrate cleavage by this antibiotic. This result provides evidence that the inhibitory mechanism of neomycin does not include competition with the metal ion bound to the A9/G10.1 metal-ion binding site, as previously proposed. Under high ionic strength conditions, optimized for Zn(2+)-dependent cleavage, we observed neomycin-dependent inhibition of cleavage at both A9 and U4. The ability of neomycin to both inhibit and accelerate Zn(2+) cleavage suggests that there is either more than one neomycin binding site or multiple binding modes at a single site in the hammerhead ribozyme. Furthermore, the accessibilities and/or affinities of disparate neomycin binding sites or binding modes are dependent on the ionic strength and the pH of the medium.     

Synthesis, characterization, and DNA-binding of chiral complexes delta- and lambda-[Ru(bpy)2(pyip)]2+

New chiral Ru(II) complexes delta and lambda-[Ru(bpy)(2)(pyip)](PF(6))(2) [(bpy = 2,2'-bipyridine; pyip = (2-(1-pyrenyl)-1H-imidazo[4,5-f] [1,10]phenanthroline] were synthesized and characterized by elemental analysis, (1)H NMR, ESI-MS, IR, and CD spectra. Their DNA-binding properties were studied by means of UV-vis, emission spectra, CD spectra and viscosity measurements. A subtle but detectable difference was observed in the interaction of both enantiomer with CT-DNA. Spectroscopy experiments indicated that each of these complexes could interact with the DNA. The DNA-binding of the Delta-enantiomer was stronger than that of Lambda-enantiomer. DNA-viscosity experiments provided evidence that both Delta- and Lambda-[Ru(bpy)(2)(pyip)](PF(6))(2) bound to DNA by intercalation. At the same time, the DNA-photocleavage properties of the complexes were investigated too. Under irradiation with UV light, Ru(II) complexes showed different efficiency of cleaving DNA.     

One-step electrochemically co-assembled redox-active [Ru(bpy)(2)(tatp)](2+)-BSA-SWCNTs hybrid film for non-redox protein biosensors

A redox-active [Ru(bpy)(2)(tatp)](2+)-BSA-SWCNTs (bpy=2,2'-bipyridine, tatp=1,4,8,9-tetra-aza-triphenylene, BSA=bovine serum albumin, SWCNTs=single-walled carbon nanotubes) hybrid film is fabricated on an indium-tin oxide (ITO) electrode via one-step electrochemical co-assembly approach. BSA is inherently dispersive and therefore served as the linking mediator of SWCNTs, which facilitate the redox reactions of [Ru(bpy)(2)(tatp)](2+) employed as a reporter of BSA. The evidences from differential pulse voltammetry, cyclic voltammetry, scanning electron microscope, emission spectroscopy and fluorescence microscope reveal that the [Ru(bpy)(2)(tatp)](2+)-BSA-SWCNTs hybrid can be electrochemically co-assembled on the ITO electrode, showing two pairs of well-defined Ru(II)-based redox waves. Furthermore, the electrochemical co-assembly of the [Ru(bpy)(2)(tatp)](2+)-BSA-SWCNTs hybrid is found to be strongly dependent on the simultaneous presence of BSA and SWCNTs, indicating a good linear response to BSA in the range from 6 to 50mgL(-1). The results from this study provide an electrochemical co-assembly method for the development of non-redox protein biosensors.     

DNA-binding and photoactivated enantiospecific cleavage of chiral polypyridyl ruthenium(II) complexes

A series of enantiomeric polypyridyl ruthenium(II) complexes Delta- and Lambda-[Ru(bpy)2CNOIP](PF6)2 (Delta-1 and Lambda-1; BPY=2,2'-bipyridine, CNOIP=2-(2-chloro-5-nitrophenyl)imidazo[4,5-f][1,10]phenanthroline), Delta- and Lambda-[Ru(bpy)2HPIP](PF6)2 (Delta-2 and Lambda-2; HPIP=2-(2-hydroxyphenyl)imidazo[4,5-f][1,10]phenanthroline), Delta- and Lambda-[Ru(bpy)2DPPZ](PF6)2 (Delta-3 and Lambda-3; DPPZ=dipyrido[3,2:a-2',3':c]-phenazine), Delta- and Lambda-[Ru(bpy)2TAPTP](PF6)2 (Delta-4 and Lambda-4; TAPTP=4,5,9,18-tetraazaphenanthreno[9,10-b] triphenylene) have been synthesized. Binding of these chiral complexes to calf thymus DNA has been studied by spectroscopic methods, viscosity, and equilibrium dialysis. The experimental results indicated that all the enantiomers of these complexes bound to DNA through an intercalative mode, but the binding affinity of each chiral complex to DNA was different due to the different shape and planarity of the intercalative ligand. After binding to DNA, the luminescence property of complex 1 was distinctly different from complexes 2 to 4. Upon irradiation at 302 nm, complexes 2-4 were found to promote the cleavage of plasmid pBR 322 DNA from supercoiled form I to nicked form II, and obvious enantioselectively was observed on DNA cleavage for the enantiomers of complexes 2 and 4. The mechanisms for DNA cleavage by these enantiomeric complexes were also proposed.     

Interaction of Lambda- and Delta-[Ru(bpy)2(pbmz)](PF6)2 with the oligonucleotide duplex d(CGCGAATTCGCG)2

The interaction of the enantiomeric complexes Lambda- and Delta-[Ru(bpy)(2)(pbmz)](PF(6))(2) (bpy=2,2'-bipyridine, pbmz=2-(2'-pyridyl)benzimidazole) with the DNA duplex d(CGCGAATTCGCG)(2) was investigated by means of 2D NMR techniques. The synthesis of the enantiomers was based on the optically pure complexes Lambda- and Delta-[Ru(bpy)(2)(py)(2)](2+) and were characterized by CD and NMR spectroscopy. NMR data indicate that both enantiomers bind weakly to the oligonucleotide, approaching from the minor groove at the centre of the helix. The perturbation of the B-DNA conformation is minor with an apparent absence of enantioselectivity. Molecular modelling calculations in conjunction with the NOE data support the suggestion that more than one binding modes are present. The imidazole amine group of the pbmz ligand is probably hydrogen bonded to the DNA phosphodiesteric backbone at the AATT step, and this may provide an explanation for the diminished enantioselectivity observed.     

Optically active molecule-based magnets: enantioselective self-assembling, optical, and magnetic properties.

In this short communication we describe the synthesis and the optical and magnetic properties of optically active three dimensional (3D) bimetallic [Cr-Mn] networks [[Delta Cr(III) Delta Mn(II)(ox)(3)][Delta Ru(II)(bpy)(3)]ClO(4)](n)1 - Delta, [[Lambda Cr(III)Lambda Mn(II)(ox)(3)][Lambda Ru(II) (bpy)(3)]ClO(4)](n) 1 - Lambda and [[Delta Cr(III)Delta Mn(II)(ox)(3)][Delta Ru(II)(bpy)(2)p p y]](n) 2 - Delta,[[Lambda Cr(III)Lambda Mn(II)(ox)(3)][Lambda Ru(II)(bpy)(2)ppy]](n) 2 - Lambda (ox = oxalate, bpy = bipyridine, ppy = phenyl-pyridine).     

Highly efficient supramolecular photocatalysts for CO2 reduction using visible light.

We report the most efficient homogeneous photocatalyst yet for CO(2) reduction using a wide range of visible-light wavelength. We synthesized new Ru(II)-Re(I) binuclear complexes with 1,3-bis(4'-methyl-[2,2']bipyridinyl-4-yl)-propan-2-ol (bpyC3bpy) as a bridge ligand, specifically [Ru-ReP(OEt)(3)](3+) and [Ru-Repy](3+) where a P(OEt)(3) or pyridine ligand coordinates on the Re site. Their photocatalytic activities were compared with [Ru-ReCl](2+), which has a Cl(-) ligand on the Re site and has recently been reported as a much better photocatalyst (Phi = 0.12, TN(CO) = 160) than a 1:1 mixed system of the corresponding Ru(II) and Re(I) mononuclear complexes. The best photocatalyst was [Ru-ReP(OEt)(3)](3+), for which Phi = 0.21 and TN(CO) = 232. A mechanistic study clearly showed that [Ru-ReP(OEt)(3)](3+) is rapidly converted into the solvento complex [Ru-ReSol](3+), (Sol = DMF or TEOA) which is the actual photocatalyst. Although similar rapid ligand substitution occurs with other supramolecules, the pyridine and Cl(-) anions accelerate the decomposition of the supramolecular photocatalysts.     

Photoelectron transfer processes with ruthenium(II) polypyridyl complexes and Cu/Zn superoxide dismutase

The processes that are photoinduced by [Ru(bpz)(3)](2+) (bpz = 2,2'-bipyrazyl) in the presence of Cu/Zn superoxide dismutase (Cu/Zn SOD) are investigated by laser flash photolysis and electron paramagnetic resonance (EPR) spectroscopy; they are compared to those of the system [Ru(bpy)(3)(2+)-Cu/Zn SOD]. Although the mechanism is complicated, primary and secondary reactions can be evidenced. First, the excited [Ru(bpz)(3)](2+) complex is quenched reductively by Cu/Zn SOD with the production of a reduced complex and an oxidized enzyme. The oxidation site of Cu/Zn SOD is proposed to correspond to amino acids located on the surface of the protein. Afterward and only when this reductive electron transfer to the excited complex has produced enough oxidized protein, another electron-transfer process can be evidenced. In this case, however, the charge-transfer process takes place in the other direction, i.e., from the excited complex to the Cu(II) center of the SOD with the formation of Ru(III) and Cu(I) species. This proposed mechanism is supported by the fact that [Ru(bpy)(3)](2+), which is less photo-oxidizing than [Ru(bpz)(3)](2+), exhibits no photoreaction with Cu/Zn SOD. Because Ru(III) species are generated as intermediates with [Ru(bpz)(3)](2+), they are proposed to be responsible for the enhancement of [poly(dG-dC)](2) and [poly(dA-dT)](2) oxidation observed when Cu/Zn SOD is added to the [Ru(bpz)(3)](2+)-DNA system.     

Chiral ruthenium complexes induce apoptosis of tumor cell and interact with bovine serum albumin

In this study, two isomeric ruthenium(II) complexes [Ru(bpy)(2)(p-mopip)](2+) (1) and [Ru(bpy)(2)(o-mopip)](2+) (2) (bpy = 2, 2-bipyridine; L: p-mopip = 2-(4-methoxylphenyl) imidazo [4,5-f][1,10]phenanthroline, o-mopip = 2-(2-methoxylphenyl) imidazo[4,5-f][1,10] phenan-throline) contained -OCH(3) at different positions on the phenyl ring and their enantiomers Λ-1, -2 and Δ-1, -2 displayed different properties. The cell viability of these ruthenium(II) complexes was evaluated by MTT, and complex Λ-1 has shown significant higher anticancer potency than Δ-1 against all the cell lines screened. Fluorescence microscopy and flow cytometric analyses demonstrated that complex Λ-1 was able to induce apoptosis. The interactions of complexes Λ-1, 1, and Δ-1 with bovine serum albumin (BSA) were investigated by fluorescence and circular dichroism (CD) measurements. The fluorescence quenching mechanism of BSA by complexes Λ-1, 1, and Δ-1 was determined to be a static process, and the apparent binding constant K(a) values is as follows: Λ-1 >1 > Δ-1. The number of binding sites n for all these complexes was 1. The result of CD showed that the secondary structure of BSA molecules was changed in the presence of the ruthenium(II) complex.     

Interaction of polypyridyl ruthenium (II) complex containing asymmetric ligand with DNA

A novel asymmetric bidentate ruthenium (II) complex, [Ru(bpy)(2)(PYNI)](2+) (bpy=2,2'-bipyridine, PYNI=2-(2'-pyridyl)naphthoimidazole), has been synthesized and characterized by elemental analysis, ES-MS (electrospray mass spectra) and (1)H NMR. The electrochemical behaviors of this complex were studied by cyclic voltammetry. DNA interaction studies suggest that [Ru(bpy)(2)(PYNI)](2+) binds to calf thymus DNA (CT-DNA) in an intercalative mode. Interestingly, this new Ru(II) complex has also been found to promote cleavage of plasmid pBR 322 DNA from the supercoiled form I to the open circular form II upon irradiation.     

Nucleic acid binding behaviors and cytotoxic properties of a Ru(II) complex

The interactions of complex [Ru(bpy)(2)(hnip)](2+) (1) {bpy?=?2,2'-bipyridine, hnip?=?2-(2-hydroxy-1-naphthyl)imidazo[4,5-f][1,10]phenanthroline} with calf thymus DNA and yeast tRNA were investigated by UV-vis spectroscopy, fluorescence spectroscopy, viscosity, equilibrium dialysis, and circular dichroism. In addition, the antitumor activities of complex 1 were evaluated with MTT method. These results indicate that the structures of DNA and RNA have significant effects on the binding behaviors of complex 1. Further, complex 1 demonstrates different antitumor activities against selected cancer cell lines in vitro.     

The DNA and RNA specificity of eilatin Ru(II) complexes as compared to eilatin and ethidium bromide

Eilatin-containing ruthenium complexes bind to a broad range of different nucleic acids including: calf thymus (CT) DNA, tRNA(Phe), polymeric RNAs and DNAs, and viral RNAs including the HIV-1 RRE and TAR. The nucleic acid specificity of Lambda- and Delta-[Ru(bpy)2eilatin]2+ have been compared to that of the 'free' eilatin ligand, and to the classic intercalating agent ethidium bromide. Interestingly, all four compounds appear to bind to nucleic acids by intercalation, but the trends in nucleic acid binding specificity are highly diverse. Unlike ethidium bromide, both eilatin and the eilatin-containing coordination complexes bind to certain single-stranded RNAs with high affinity (K(d) < or = 1 microM). Eilatin itself is selective for electron-poor polymeric purines, while the eilatin-coordination complexes exhibit preference for the polypyrimidine r(U). These results show how the binding specificity of an intercalating ligand can change upon its incorporation into an octahedral metal complex.     

Cytotoxicity, apoptosis, cellular uptake, cell cycle distribution, and DNA-binding investigation of ruthenium complexes

Three new ruthenium(II) polypyridyl complexes [Ru(bpy)(2)(BHIP)](2+) 1, [Ru(phen)(2)(BHIP)](2+) 2, and [Ru(dip)(2)(BHIP)](2+) 3 were synthesized and characterized. The cytotoxicity of the three complexes was evaluated by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. The apoptosis induced by the complexes was studied by cell morphology and flow cytometry. The results showed that the percentage of apoptotic cells is 7.19%, 75.58%, and 3.51% in the presence of complexes 1, 2, and 3, respectively. The cellular uptakes were also performed and the results indicated that complexes 1, 2, and 3 can enter into the cytoplasm and also into the nucleus. The studies on antiproliferative mechanism showed the induction of S-phase arrest by complexes 1, 2, and 3. DNA-binding constants of these complexes with calf thymus DNA (CT-DNA) were determined to be 1.07 (± 0.47) × 10(5) M(-1) (s = 2.04), 1.21 (± 0.32) × 10(5) M(-1) (s = 1.88), and 2.75 (± 0.27) × 10(5) M(-1) (s = 2.17), respectively. Upon irradiation at 365 nm, complexes 1, 2, and 3 can induce cleavage of pBR322 DNA.     

Fluorescence-based methods for evaluating the RNA affinity and specificity of HIV-1 Rev-RRE inhibitors

RNA plays a pivotal role in the replication of all organisms, including viral and bacterial pathogens. The development of small molecules that selectively interfere with undesired RNA activity is a promising new direction for drug design. Currently, there are no anti-HIV treatments that target nucleic acids. This article presents the HIV-1 Rev response element (RRE) as an important focus for the development of antiviral agents that target RNA. The Rev binding site on the RRE is highly conserved, even between different groups of HIV-1 isolates. Compounds that inhibit HIV replication by binding to the RRE and displacing Rev are therefore expected to retain activity across groups of genetically diverse HIV infections. Systematic evaluations of both the RRE affinity and specificity of numerous small molecule inhibitors are essential for deciphering the parameters that govern effective RRE recognition. This article discusses fluorescence-based techniques that are useful for probing a small molecule's RRE affinity and its ability to inhibit Rev-RRE binding. Rev displacement experiments can be conducted by observing the fluorescence anisotropy of a fluorescein-labeled Rev peptide, or by quantifying its displacement from a solid-phase immobilized RRE. Experiments conducted in the presence of competing nucleic acids are useful for evaluating the RRE specificity of Rev-RRE inhibitors. The discovery and characterization of new RRE ligands are described. Eilatin is a polycyclic aromatic heterocycle that has at least one binding site on the RRE (apparent Kd is approximately 0.13 microM), but it does not displace Rev upon binding the RRE (IC50 > 3 microM). In contrast, ethidium bromide and two eilatin-containing metal complexes show better consistency between their RRE affinity and their ability to displace a fluorescent Rev peptide from the RRE. These results highlight the importance of conducting orthogonal binding assays that establish both the RNA affinity of a small molecule and its ability to inhibit the function of the RNA target. Some Rev-RRE inhibitors, including ethidium bromide, Lambda-[Ru(bpy)(2)eilatin]2+, and Delta-[Ru(bpy)(2)eilatin]2+ also inhibit HIV-1 gene expression in cell cultures (IC50 = 0.2-3 microM). These (and similar) results should facilitate the future discovery and implementation of anti-HIV drugs that are targeted to viral RNA sites. In addition, a deeper general understanding of RNA-small molecule recognition will assist in the effective targeting of other therapeutically important RNA sites.     

Metal ion requirements for structure and catalysis of an RNA ligase ribozyme

The class I ligase, a ribozyme previously isolated from random sequence, catalyzes a reaction similar to RNA polymerization, positioning its 5'-nucleotide via a Watson-Crick base pair, forming a 3',5'-phosphodiester bond between its 5'-nucleotide and the substrate, and releasing pyrophosphate. Like most ribozymes, it requires metal ions for structure and catalysis. Here, we report the ionic requirements of this self-ligating ribozyme. The ligase requires at least five Mg(2+) for activity and has a [Mg(2+)](1/2) of 70-100 mM. It has an unusual specificity for Mg(2+); there is only marginal activity in Mn(2+) and no detectable activity in Ca(2+), Sr(2+), Ba(2+), Zn(2+), Co(2+), Cd(2+), Pb(2+), Co(NH(3))(6)(3+), or spermine. All tested cations other than Mg(2+), including Mn(2+), inhibit the ribozyme. Hill analysis in the presence of inhibitory cations suggested that Ca(2+) and Co(NH(3))(6)(3+) inhibit by binding at least two sites, but they appear to productively fill a subset of the required sites. Inhibition is not the result of a significant structural change, since the ribozyme assumes a nativelike structure when folded in the presence of Ca(2+) or Co(NH(3))(6)(3+), as observed by hydroxyl-radical mapping. As further support for a nativelike fold in Ca(2+), ribozyme that has been prefolded in Ca(2+) can carry out the self-ligation very quickly upon the addition of Mg(2+). Ligation rates of the prefolded ribozyme were directly measured and proceed at 800 min(-1) at pH 9.0.     

Luminescent pH sensing and DNA binding properties of a novel ruthenium(II) complex

A new Ru(II) complex, [Ru(bpy)(2)(dhipH3)](ClO4)(2) (in which bpy=2,2'-bipyridine, dhipH(3)=3,4-dihydroxy-imidado[4,5-f][1,10]-phenanthroline), was synthesized and characterized, and the pH effect on the emission spectra of the complex was studied. The interaction of the complex with calf thymus DNA was investigated by UV-visible and emission spectroscopy, and viscosity measurements. The results suggest that the complex acted as a sensitive luminescent pH sensor and a strong ct-DNA intercalator with an intrinsic binding constant of (4.0+/-0.7) x 10(5) M(-1) in buffered 50 mM NaCl.     

Developing red-emissive ruthenium(II) complex-based luminescent probes for cellular imaging

Ruthenium(II) complexes have rich photophysical attributes, which enable novel design of responsive luminescence probes to selectively quantify biochemical analytes. In this work, we developed a systematic series of Ru(II)-bipyrindine complex derivatives, [Ru(bpy)(3-n)(DNP-bpy)(n)](PF(6))(2) (n = 1, 2, 3; bpy, 2,2'-bipyridine; DNP-bpy, 4-(4-(2,4-dinitrophenoxy)phenyl)-2,2'-bipyridine), as luminescent probes for highly selective and sensitive detection of thiophenol in aqueous solutions. The specific reaction between the probes and thiophenol triggers the cleavage of the electron acceptor group, 2,4-dinitrophenyl, eliminating the photoinduced electron transfer (PET) process, so that the luminescence of on-state complexes, [Ru(bpy)(3-n)(HP-bpy)(n)](2+) (n = 1, 2, 3; HP-bpy, 4-(4-hydroxyphenyl)-2,2'-bipyridine), is turned on. We found that the complex [Ru(bpy)(DNP-bpy)(2)](2+) remarkably enhanced the on-to-off contrast ratio compared to the other two (37.8 compared to 21 and 18.7). This reveals a new strategy to obtain the best Ru(II) complex luminescence probe via the most asymmetric structure. Moreover, we demonstrated the practical utility of the complex as a cell-membrane permeable probe for quantitative luminescence imaging of the dynamic intracellular process of thiophenol in living cells. The results suggest that the new probe could be a very useful tool for luminescence imaging analysis of the toxic thiophenol in intact cells.     

SERRS study of the DNA binding by Ru(II) tris-(Bipyridyl) complexes bearing one carboxylic group

Surface enhanced resonance Raman scattering (SERRS) is shown to be a satisfying method to study the interaction between DNA and ruthenium complexes [Ru(bpy)(2)(Hcmbpy)][PF(6)](2), where Hcmbpy = 4-carboxy-4'-methyl-2,2'-bipyridine. Such metallic complexes are known for their fluorescence properties. To validate this spectroscopic approach we have checked that i) at a given lambda(ex), silver colloidal SERRS spectra of Ru complexes closely resemble resonance Raman spectra in aqueous solutions, intensity excepted, and ii) the DNA fragments are not altered when they are adsorbed on the Ag nanoparticles surface. This investigation shows that the intensity of the Ru complexes SERRS spectra is reduced in the presence of DNA, in particular for the specific bands assigned to the Hcmbpy ligand. This collapse demonstrates that the Ru complexes bind DNA through the Hcmbpy moiety, and intercalation is suggested as the binding mode. The DNA binding by the enantiopure Ru complexes (Delta or Lambda) is more efficient than by the racemic complexes.