Synthesis,characterization and DNA binding and photocleavage studies of [Ru(bpy)2BDPPZ]2+, [Ru(dmb)2BDPPZ]2+ and [Ru(phen)2BDPPZ]2+ complexes and their antimicrobial activity

Polypyridyl ligand 9a,13a‐dihydro‐4,5,9,14‐tetraaza‐benzo[b]triphenylene‐11‐yl)‐phenyl‐methanone (BDPPZ) and its complexes [Ru(bpy)₂BDPPZ]²⁺, [Ru(dmb)₂BDPPZ]²⁺ and [Ru(phen)₂BDPPZ]²⁺ (where bpy = 2,2′‐bipyridine, dmb = 4,4′‐dimethyl‐2,2′‐bipyridine, phen = 1,10‐phenanthroline) have been synthesized and characterized by elemental analysis, IR, UV–vis, ¹H‐NMR, ¹³C‐NMR and mass spectra. The DNA‐binding properties of the complexes were investigated by absorption, emission, melting temperature and viscosity measurements. Experimental results indicate that the three complexes can intercalate into DNA base pairs. Photo activated cleavage of pBR‐322 DNA by the three complexes was also studied. Further, all three Ru(II) complexes synthesized were screened for their antimicrobial activity. Copyright © 2009 John Wiley & Sons, Ltd.     

A dinuclear diamagnetic copper(II) complex [Cu2(ophen)2]Cl2 with hydroxylated phen

A dinuclear diamagnetic copper(II) complex, [Cu₂(ophen)₂]Cl₂ (Hophen = 2-hydroxy-1,10-phenanthroline), has been synthesized and characterized, providing good structural evidence for the long-debated Gillard mechanism.     

Effect of substituents on DNA-binding behaviors of ruthenium(II) complexes: [Ru(dmb)2(dtmi)]2+ and [Ru(dmb)2(dtni)]2+

Two Ru(II) complexes [Ru(dmb)₂(dtmi)](ClO₄)₂ (1) (dmb = 4, 4′-dimethyl-2, 2′-bipyridine, dtmi = 3-(pyrazin-2-yl)-as-triazino[5, 6-f]-5-methoxylisatin) and [Ru(dmb)₂(dtni)](ClO₄)₂ (2) (dtni = 3-(pyrazin-2-yl)-as-triazino[5, 6-f]-5-nitroisatin) have been synthesized and characterized by elemental analysis, ES-MS, and ¹H NMR. DNA-binding behaviors of these complexes have been investigated by spectroscopic titration, viscosity measurements, and thermal denaturation. The results indicate that the two complexes interact with calf thymus DNA by intercalation.     

Fe(phen)32+‐Modified Zeolite Particles and Their Energetic Studies

Chemically modified zeolite Y (NaY) particles and their resulting modified electrodes were prepared with acridinium (AcH+), iron(II) and 1,10‐phenanthroline (phen) for energetic studies. According to diffuse reflectance absorption spectroscopy and cyclic voltammetry, AcH⁺ and Fe(phen)₃²⁺ were successfully entrapped in the zeolite particles. Transient emission spectra measurements showed that the life time of AcH+* in the zeolite particles (to 35 ns; λ_ex 365 nm; λ_em 500 nm) was greatly reduced upon incorporating Fe(phen)₃²⁺ and Fe²⁺. The fast de cay of AcH+*(NaY) suggested that a reductive quench was likely to take place in the zeolite particle. Probably due to a size‐exclusion effect, the bulky electron donor, N, N‐diethyl‐2‐methyl‐1,4‐phenylenediamine (DEPD), revealed a difficulty in reaching the photosensitizer, AcH⁺, in side the zeolite particle. As a consequence, the in significant photocurrent for the oxidation of DEPD was from the NaY|AcH⁺ electrode. However, if Fe²⁺ and Fe(phen)₃²⁺ were incorporated, the photocurrent would become more significant. Closer examinations, in addition, showed that the photooxidaton of DEPD occurred more rapidly on the NaY|AcH⁺|Fe(phen)₃²⁺ electrode, compared to the NaY|AcH⁺|Fe²⁺ electrode. This difference apparently results from a greater gap in energetics between DEPD and Fe(phen)₃³⁺_(NaY) than that between DEPD and Fe³⁺_(NaY). Due to this effect, a greater amount of indophenol blue, derived from the coupling reaction of the oxidized DEPD with 1‐naphthol, was formed and de posited on the NaY|AcH⁺|Fe(phen)₃²⁺modified electrode. Thanks to this photo‐induced charge‐transfer reaction, the NaY|AcH⁺|Fe(phen)₃²⁺ particle showed an application potential in image recording.     

钌联吡啶单配体双取代基效应

对钌联吡啶配合物及其单配体的4,4′ 双取代衍生物, 用量子化学密度泛函(DFT)方法在B3LYP/LanL2DZ水平上进行计算.探讨一些强的推电子基团(如－OCH3)和强的拉电子基团(如－NO2)的取代基效应对配合物的电子结构与相关性质,如配位键长、光谱性质等的影响规律,为该类配合物的合成,光、电、催化和生化作用机理分析提供理论参考.     

Determination of Cu2+ in Drinking Water Based on Electrochemiluminescence of Ru(phen)32+ and Cyclam

A convenient and simple electrochemiluminescence (ECL) method was employed to detect trace amounts of Cu²⁺ in drinking water. This method is based on the inhibitory effect of Cu²⁺ on the ECL of Ru(phen)₃²⁺ and 1,4,8,11‐tetraazacyclotetradecane (cyclam) system. ECL intensity of Ru(phen)₃²⁺ was considerably enhanced by the addition of cyclam because of the ECL reaction between them. The ECL intensity of Ru(phen)₃²⁺/cyclam system rapidy decreased with the addition Cu²⁺ because of the formation of chelate complex [Cu(cyclam)]²⁺. Good linear response (R ²=0.9948) was obtained at Cu²⁺ concentration of 1.0×10⁻⁹−1.0×10⁻⁵ mol ⋅ L⁻¹ at glassy carbon electrode in 0.1 mol ⋅ L⁻¹ phosphate buffer (pH 9.0). Observed detection limit of 4.8×10⁻¹⁰ mol ⋅ L⁻¹ satisfied the maximum contaminant level goal (MCLG) for Cu²⁺ set by the US Environmental Protection Agency (US EPA). Applicability of the proposed method was verified by the good reproducibility and stability of the method when applied to determine Cu²⁺ in tap water and simulated wastewater. Thus, a novel ECL detection method was developed for Cu²⁺ detection.     

Synthesis,electrochemistry and fluorescence of four new Ru(phen)2/3+ derivatives

Four typical LB monolayer film materials, Ru(phen)2/3 ⁺ complexes with one ligand attached to different long chain alkyl amides, were designed and synthesized. Their chemical structures were identified by the techniques of FT-IR, ¹H NMR and ESI-MS. Also, UV-Vis, electrochemistry and fluorescence of these complexes are reported.     

M(bpy)2+3(M=Fe,Ru,Os)电子结构与相关性质

报导了对配合物Ｍ（ｂｐｙ）＾２＋３（Ｍ＝Ｆｅ,Ｒｕ,Ｏｓ）的量子化学密度泛函法研究的结果。Ｂ３ＬＹＰ／ＬａｎＬ２ＤＺ方法与基组的水平上进行计算,探讨Ｍ（ｂｐｙ）＾２＋３电子结构特征及相关性质,特别是中心原子对配合物的配位键长、光谱性质,电荷布局及化学稳定性等的影响规律,为该类配合物的合成,为分析光、电、催化作用机理提供理论参考。     

A DFT/TDDFT study on the structures, trend in DNA-binding and spectral properties of molecular “light switch” complexes [Ru(phen)2(L)](L = dppz, taptp, phehat)

Theoretical studies on a series of molecular “light switch” complexes [Ru(phen)₂L]²⁺ (phen = 1,10-phenanthroline; L: dppz = dipyrido [3,2-a:2′,3′-c]phenazine; taptp = 4,5,9,18-tetraazaphenanthreno-[9,10-b]triphenylene; phehat = 1,10-phenanthrolino[5,6-b]1,4,5,8,9,12-hexaazatriphenylene) 1-3 have been carried out applying DFT/TDDFT (density functional theory and time-dependent DFT) methods. The geometric and electric structure-characteristics of these complexes have been revealed, and the trend in their DNA-binding constants (K_b), i.e., K_b (2) < K_b (3) < K_b (1), which closely relates to the luminescence properties of the complexes in DNA, has been reasonably explained. The results show that simply increasing the planar area of intercalative ligand may be ineffective on improvement of DNA-binding of resulting complex because of going with the increase in the LUMO (and LUMO + x) energy, but introducing some heteroatoms (e.g., N atom) with stronger electronegativity into the ring skeleton of intercalative ligand should be effective because of the decrease in the LUMO (and LUMO + x) energy to a certain extent. In addition, the spectra of this series of complexes in vacuo are also computed, simulated, and minutely discussed by the DFT/TDDFT methods, and it is interesting to find that the symmetries of the excited and accepting orbitals of the transition with the largest f value are the same.     

Study on Triplex DNA by Use of Molecular “Light Switch“ Complex of Ru(phen)2(dppx)^2

A new method for the study of triplex DNA is established according the fluorescence enhancement of molecular “Light Switch“ complex of Ru(phen)2(dppx)^2 when it intercalate into triplex DNA.Because the fluorescence intensity of Ru(phen)2(dppx)^2 bonded to triplex DNA is in ths case higher than that bonded to duplex DNA in certain range of DNA concentration,the method is much more sensitive than other methods reported previously.     

Synthesis, electrochemistry and fluorescence of four new Ru(phen)_3~(2 ) derivatives

Four typical LB monolayer film materials, Ru(phen)32 complexes with one ligand attached to different long chain alkyl amides, were designed and synthesized. Their chemical structures were identified by the techniques of FT-IR, 1H NMR and ESI-MS. Also, UV-Vis, electrochemistry and fluorescence of these complexes are reported.     

配合物Ru(dcbpy)(phen)2(PF6)2的2D-NMR分析

用一维ＮＭＲ方法研究了新型电化学发光探针Ｒｕ（ｄｃｂｐｙ）（ｐｈｅｎ）２（ＰＦ６）２的立体结构,借助二维＾１Ｈ－＾１Ｈ ＣＯＳＹ和＾１Ｈ－＾１３Ｃ ＣＯＳＹ实验对其氢谱和碳谱进行了完全的归属,并给出了其氢谱和碳谱的化学位移值。     

Ru(phen)2dppx2+-SDBS-DNA体系共振瑞利散射光谱及其分析应用研究

在水溶液中,带正电荷的Ru(phen)2dppx2+在阴离子表面活性剂十二烷基苯磺酸钠(SDBS)的表面聚集后,产生很强的共振瑞利散射.由于Ru(phen)2dppx2+与DNA之间有较大的结合常数(KB≥106 L·5mol-1),DNA的加入会使体系中"光开关"与SDBS分离,散射光强度大大降低,且体系散射光的降低程度与DNA的浓度呈线性关系.据此建立了DNA的定量测定新方法.     

Ru(bpy)32+配合物及bpy上双取代基效应的DFT法研究

报道Ru(bpy)32+配合物取代基效应的量子化学密度泛函(DFT)法研究的结果。探讨Ru(bpy)32+的三个配体bpy(2,2′-联二吡啶)被取代基(-NH2,-OH,-NO2)对位双取代后对配合物电子结构及相关性质,如配位键长、光谱性质等的影响规律,为该类配合物的合成及性质分析提供理论参考。     

Synthesis, Electrochemistry, and Fluorescence of Two Ru(phen)_3~(2 )-based Surfactants

In1988.ZhangandBard'firstobservedtheelectrochemilurninescence(ECL)fromamonomolecularorganizedassemblylayerofaRu(bpy),= -basedsurfactantconfinedtothesurfaceofasolidelectrodebytheLangmuir-Blodgettmethod.Subsequently,theirgroup=furtherstudiedthiskindofmonolayermembranebythetechniqueofECLphotography.Zhaoetal.'havefoundECLefficiencyofRu(phen),",wherephenisl,10-phennanthroline,ismuchhigherthanthatofRu(bpy),' .InordertodevelophighefficientlyECLdevices,wedesignedandsynthesizedtwonewRu(phen),= …     

Synthesis and Characterization of Heteroleptic Ru(II) Complexes Based on 4,4′‐Bis((E)‐styryl)‐2,2′‐bipyridine as Ancillary Ligand and Application for Dye‐Sensitized Solar Cells

Heteroleptic Ru(II) complexes were designed based on 4,4′‐bis((E)‐styryl)‐2,2′‐bipyridine (bsbpy) as an ancillary ligand for dye‐sensitized solar cells (DSSCs), and those Ru(II) sensitizers, [Ru(L)(bsbpy)(NCS)₂][TBA] (TBA; tetrabutylammonium), were synthesized according to a typical one‐pot reaction of [RuCl₂(p‐cymene)]₂ with the corresponding anchoring ligands (where L = 4,4′‐dicarboxy‐2,2′‐bipyridine (dcbpy), 4,4′‐bis((E)‐carboxyvinyl)‐2,2′‐bipyridine (dcvbpy), 4,7‐dicarboxy‐1,10‐phenanthroline (dcphen), or 4,7‐bis((E)‐carboxyvinyl)‐1,10‐phenanthroline (dcvphen)). The new Ru(II) dyes, [Ru(L)(bsbpy)(NCS)₂][TBA] that incorporated vinyl spacer(s) into ancillary and/or anchoring ligand displayed red‐shifted bands over the overall UV/VIS region relative to the absorption spectra of N719 . A combination of bsbpy ancillary and dcphen anchoring ligand showed the best result for the overall power conversion efficiency (η); i.e., a DSSC fabricated with [Ru(dcphen)(bsbpy)(NCS)₂][TBA] exhibited a power conversion efficiency (η) of 2.98% (compare to N719 , 4.82%).     

DHP促进[Ru(bpy)_3]~(2+)介导鸟嘌呤的氧化

应用循环伏安法和微分脉冲伏安法研究了ITO电极上双十六烷基磷酸盐(DHP)和多壁碳纳米管(MWNTs)对[Ru(bpy)3]2+(bpy=2,2′-联吡啶)介导鸟嘌呤氧化的影响.结果表明,[Ru(bpy)3]2+能够介导鸟嘌呤氧化.在0.01至0.15 mmol.L-1DHP浓度范围内,[Ru(bpy)3]2+介导鸟嘌呤氧化峰电流随DHP浓度的增大而增大,阳离子表面活性剂HTAC则起抑制作用.讨论了DHP参与[Ru(bpy)3]2+介导鸟嘌呤氧化的可能电极过程机理.     

[Ru(bpy)2(phen)]^2+主配体上双取代效应DFT法研究

对钌联吡啶菲咯啉配合物[Ru(bpy)2(phen)]^2+及其主配体(phen)上5,6-双取代衍生物,用密度泛函(DFT)法在B3LYP/LanL2DZ水平上进行理论计算研究。探讨供电子基团(OH)和拉电子基团(F)在主配体上的取代对配合物的电子结构及相关性质,如配合物前沿分子轨道的能量、组成、光谱性质、原子的净电荷布居及配位键长键角等的影响规律。计算结果表明,取代基对该系列取代衍生物的电子结构,特别是第一激发态的电子云分布影响较大,拉电子基团(F)能活化主配体,钝化辅助配体;而代电子基团(OH)则相反。无认是供电子基团(OH),还是拉电子基团(F)都导致取代衍生物的电子基谱带红移。此外,用基于极性交替规律及极性叠加概念的多系列箭头的图示方法对主配体上的原子净电荷布居的特征作了讨论。计算结果能较好地解释有关的实验现象与规律。     

Syntheses and Crystal Structures of Copper(II) and Copper(I) dpp Complexes, [Cu(dpp)Br2] and [Cu(dpp)2][CuBr2] (dpp = 2,9‐diphenyl‐1,10‐phenanthroline)

The complexes [Cu(dpp)Br₂] ( 1 ) and [Cu(dpp)₂][CuBr₂] ( 2 ) (dpp = 2,9‐diphenyl‐1,10‐phenanthroline) were synthesized and characterized by single‐crystal X‐ray diffraction methods. Reaction of copper(II) bromide with the dpp ligand in dichloromethane at room temperature afforded 1 , which is a rare example of non‐square planar four‐coordinate copper(II) complexes. Complex 1 crystallizes in the monoclinic space group C2/c with a = 15.352(3), b = 13.192(3), c = 11.358(2) Å, β = 120.61(3)°, V = 1979.6(7) ų, Z = 4, D_calc = 1.865 g cm^?3. The coordination geometry about the copper center is distorted about halfway between square planar and tetrahedral. The Cu‐N distance is 2.032(2) Å and the Cu‐Br distance 2.3521(5) Å. Heating a CH₂Cl₂ or acetone solution of 1 resulted in complex 2 , which consists of a slightly distorted tetrahedral [Cu(dpp)₂]⁺ cation and a linear two‐coordinate [CuBr₂]^? anion. 2 crystallizes in the triclinic space group with a = 10.445(2), b = 11.009(2), c = 18.458(4) Å, α = 104.72(3), β = 94.71(3), γ = 103.50(3)°, V = 1973.3(7) ų, Z = 2, D_calc = 1.602 g cm^?3. The four Cu(1)‐N distances are between 2.042(3) and 2.067(3) Å, the distance of Cu(2)‐Br(1) 2.2268(8) Å, and the disordered Cu(3)‐Br(2) distances are 2.139(7) and 2.237(4) Å, respectively. Complex 2 could also be prepared by directly reacting CuBr with dpp in CH₂Cl₂.     

Chemiluminescence determination of barbituric acid using Ru(phen)(3)(2+)-Ce(IV) system

A chemiluminescence (CL) method for the determination of barbituric acid (BA) was proposed, which is based on the enhancement of BA to the CL intensity of Tris-(1,10-phenanthroline)ruthenium(II) (Ru(phen)₃²⁺)-cerium(IV) (Ce(IV)) system. The concentration of BA is proportional to the CL intensity in the range of 5.0×10⁻³-2.0 μg ml⁻¹. The detection limit is 6.9×10⁻⁴ μg ml⁻¹. The relative standard deviation (R.S.D.) of determining 11 samples containing 0.20 μg ml⁻¹ BA is 3.2%. This CL method has been successfully applied to the determination of BA in the synthetic samples. The mechanism of CL reaction was studied.