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1.
Previous studies have suggested that tris(4,7-diphenyl-1,10-phenanthrolinedisulfonate)ruthenium(II) (Ru(BPS)34−) has great potential as a chemiluminescence reagent in acidic aqueous solution. We have evaluated four different samples of this reagent (two commercially available and two synthesised in our laboratory) in comparison with tris(2,2′-bipyridine)ruthenium(II) (Ru(bipy)32+) and tris(1,10-phenanthroline)ruthenium(II) (Ru(phen)32+), using a range of structurally diverse analytes. In general, Ru(BPS)34− produced more intense chemiluminescence, but the oxidised Ru(BPS)33− species is less stable in aqueous solution than Ru(bipy)33+ and produced a greater blank signal than Ru(bipy)33+ or Ru(phen)33+, which had a detrimental effect on sensitivity. Although the complex is often depicted with the sulfonate groups of the BPS ligand in the para position on the phenyl rings, NMR characterisation revealed that the commercially available BPS material used in this study was predominantly the meta isomer.  相似文献   

2.
Ruthenium complexes containing 4,7-diphenyl-1,10-phenanthroline disulfonate (bathophenanthroline disulfonate; BPS) ligands, Ru(BPS)34−, Ru(BPS)2(bipy)2− and Ru(BPS)(bipy)2, were compared to tris(2,2′-bipyridine)ruthenium(II) (Ru(bipy)32+), including examination of the wavelengths of maximum absorption and corrected emission intensity, photoluminescence quantum yield, stability of their oxidised ruthenium(III) form, and relative chemiluminescence intensities and signal-to-blank ratios with cerium(IV) sulfate and six analytes (codeine, morphine cocaine, potassium oxalate, furosemide and hydrochlorothiazide) in acidic aqueous solution. The presence of BPS ligands in the complex increased the photoluminescence quantum yield, but decreased the stability of the oxidised form of the reagent. In contrast to previous evidence showing much greater electrochemiluminescence intensities using Ru(BPS)2(bipy)2− and Ru(BPS)(bipy)2, these complexes did not provide superior chemiluminescence signals than their homoleptic analogues.  相似文献   

3.
Due to the highly sensitive electrochemiluminescence (ECL), tris(2,2′-bipyridyl) ruthenium(II) (Ru(bpy)32+) is often used in the field of bioarrays with the help of co-reactants. However, the generally used co-reactant, tripropylamine (TPA), is toxic, corrosive and volatile. Therefore, the search for safe, sensitive and economical co-reactants is critical. Herein, three aminocarboxylic acids, ethylenediamine-tetraacetic acid (EDTA), nitrilotriacetic acid (NTA), and 2-hydroxyethylethylene diaminetriacetic ac...  相似文献   

4.
《Analytical letters》2012,45(8):1381-1391
A novel and simple method for detection of choline in milk powder using electrogenerated chemiluminescence (ECL) without prior separation was developed and its mechanism was studied thoroughly. Choline could not strengthen ECL signals of tris(2,2′-bipyridine)ruthenium(II) (Ru(bpy)32+) to be detected. Heated to its melting point, choline decomposed into two new compounds, trimethylamine and N,N-dimethyl-2-aminoethanol. Both of them were tertiary amines and could act as ECL co-reactants to strengthen the ECL signals of Ru(bpy)32+ sharply. The detection method overcame the defects of the commonly used method based on enzyme procedures and liquid chromatography-mass spectrometric technique.  相似文献   

5.
Electrochemiluminescence (ECL) of ruthenium complexes has broad applications and the immobilization of Ru(bpy)32+ has received extensive attention. In comparison with Ru(bpy)32+, Ru(phen)32+ can be immobilized more easily because of its better adsorbability. In this study, immobilization of Ru(phen)32+ for ECL analysis has been demonstrated for the first time by using graphene oxide (GO) as an immobilization matrix. The immobilization of Ru(phen)32+ is achieved easily by mixing Ru(phen)32+ with GO without using any ion exchange polymer or covalent method. The strong binding of Ru(phen)32+ with GO is attributed to both the π–π stacking interaction and the electrostatic interaction. The Ru(phen)32+/GO modified electrode was characterized by using tripropylamine (TPA) as the coreactant. The linear range of TPA is from 3 × 10−7 to 3 × 10−2 mol L−1 with the detection limit of 3 × 10−7 mol L−1. The ECL sensor demonstrates outstanding long-term stability. After the storage in the ambient environment for 90 days, the ECL response remains comparable with its original signal.  相似文献   

6.
Li Y  Zhang Z  Li J  Li H  Chen Y  Liu Z 《Talanta》2011,84(3):690-695
A simple, stable and sensitive electrogenerated chemiluminescence (ECL) detector was developed. It was based on tris(2,2-bipyridyl)ruthenium(II) (Ru(bpy)32+) immobilized on the surface of a Pt wire with Nepem-105D ion exchange solution. The detector was prepared by inserting a Pt wire with immobilized Ru(bpy)32+ (working electrode) into a capillary tube, followed by inserting another Pt wire (counter electrode) in this tube and sealing. ECL behavior was investigated using ofloxacin as an analyte. Under optimal conditions, stable ECL intensity was obtained. This detector has been used in HPLC-ECL for the determination of multiple target fluoroquinolone residues in milk. There is no post column reagent addition, which would dilute the analytes, potentially leading to chromatographic band-broadening. The system is very simple with low dead volume, low baseline and background noise, together with high sensitivity and stability. The as-prepared ECL detector, when was used for the determination of ofloxacin, pefloxacin, enrofloxacin and difloxacin in milk, demonstrated adequate sensitivity to allow quantification of trace FQ levels in commercial milk samples. One or more of the target FQ analytes were present at levels above the LOD of the new ECL detector in each and every one of the 22 milk samples analysed.  相似文献   

7.
《Electroanalysis》2004,16(17):1401-1405
The immobilization of tris(2,2′‐bipyridyl)ruthenium(II), Ru(bpy)32+, at a glassy carbon electrode was achieved by entrapping the Ru(bpy)32+ in a vapor deposited titania sol‐gel membrane. The electrogenerated chemiluminescence (ECL) of the immobilized Ru(bpy)32+ was studied. The Ru(bpy)32+ modified electrode showed a fast ECL response to both oxalate and proline. The ECL intensity was linearly related to concentrations of oxalate and proline over the ranges from 20 to 700 μmol L?1 and 20 to 600 μmol L?1, respectively. The detection limits for oxalate and proline at 3σ were 5.0 μmol L?1 and 4.0 μmol L?1, respectively. This electrode possessed good precision and stability for oxalate and proline determinations. The electrogenerated chemiluminescence mechanism of proline system was discussed. This work provided a new way for the immobilization of Ru(bpy)32+ and the application of titania sol‐gel membrane in electrogenerated chemiluminescence.  相似文献   

8.
A series of mono- and binuclear ruthenium(II) tris-bipyridine complexes tethered to oligothienylenevinylenes have been synthesized and characterized by 1H NMR, 13C NMR and TOF-MS spectrometry. Photophysics, electrochemistry and electrogenerated chemiluminescence (ECL) properties of these complexes are investigated. The electronic absorption spectra of the mononuclear ruthenium complexes show a significant red shift both at MLCT (metal-to-ligand charge transfer) and π-π transitions of oligothienylenevinylenes with increase in the number of thiophenyl-2-yl-vinyl unit. For the binuclear complexes these two absorption bands are overlapped. All the metal complexes have very weak emission compared to that of the reference complex Ru(bpy)2+3. The first reduction potentials of all mononuclear ruthenium complexes are less negative than that of Ru(bpy)2+3, due to the moderate electron-withdrawing effect of oligothienylenevinylenes. For binuclear ruthenium complexes, only one Ru(II/III) oxidation peak (E1/2 = 0.96 V vs. Ag/Ag+) was observed, suggesting a weak interaction between two metal centers. Three successive reduction processes of bipyridine ligands are similar among all ruthenium complexes except for RuTRu, which has a very sharp peak owing to the accumulation of neutral product on the electrode surface. All these ruthenium complexes exhibited different ECL property in CH3CN solution without any additional reductant or oxidant. For three mononuclear ruthenium complexes, the ECL intensity strengthens with increase in the number of thiophene-2-yl-vinyl unit. However, the ECL efficiency dramatically decreased in the binuclear ruthenium complexes. The ECL efficiencies of all the reported complexes do not exceed that of Ru(bpy)2+3, where the ECL efficiency decreases in the order of RuTRu > Ru3T > Ru2T > RuT > Ru2TRu (RuT,bis-2,2′-bipyridyl-(4-methyl-4′-(2-thienylethenyl)-2,2′-bipyridine) ruthenium dihexafluorophosphate; Ru2T, bis-2,2′-bipyridyl-(4-methyl-4′-{(E)-2-[5-((E)-2-thienylethenyl)-thienylethenyl]}-2,2′-bipyridine) ruthenium dihexafluorophosphate; Ru3T, bis-2,2′-bipyridyl-(4-methyl-4′-{(E)-2-{(E)-2-[5-((E)-2-thienylethenyl)-thienylethenyl]}}-2,2′-bipyridine) ruthenium dihexafluorophosphate; RuTRu, bis-2,2′-bipyridyl-ruthenium-bis-[2-((E)-4′-methyl-2, 2′-bipyridinyl-4)-ethenyl]-thienyl-bis-2,2′-bipyridyl-ruthenium tetrahexafluorophosphate; Ru2TRu, bis-2,2′-bipyridyl-ruthenium-(E)-1,2-bis-{2-[2-((E)-4′-methyl-2,2′-bipyridinyl-4)-ethenyl]-thienyl}-ethenyl-bis-2,2′-bipyridyl-ruthenium tetrahexafluorophosphate).  相似文献   

9.
Ru(bpy) 3 2+ electrogenerated chemiluminescence (CL) has rapidly gained importance as a sensitive and selective detection method in analytical science. The Ru(bpy) 3 2+ ECL is observed when Ru(bpy) 3 3+ reacts with Ru(bpy) 3 + and yields an excited state Ru(bpy) 3 2+* . ECL emission can also be obtained when a variety of oxidants and reductants react with the reduced or oxidized forms of Ru(bpy) 3 2+ . Either the reductant or the oxidant can be treated as an analyte. The Ru(bpy) 3 2+ ECL is used as a detection method for the determination of oxalate and a variety of amine-containing analytes without derivatization in flowing streams such as flow injection and HPLC. When the ECL format is used as a detector for HPLC, unstable post-column reagent addition can often be eliminated and, the problems of both sample dilution and band broadening can be avoided because the Ru(bpy) 3 3+ species are generatedin situ in the reaction/observation flow cell. Since NADH is sensitively detected with the Ru(bpy) 3 2+ ECL, many clinically important analytes can be detected by coupling them to dehydrogenase enzymes that utilize -nicotinamide adenine cofactors to convert NAD+ to NADH. Ru(bpy) 3 2+ -derivatives are used as CL labels for immunoassay and PCR assay with Ru(bpy) 3 2+ /tripropylamine ECL system. The Ru(bpy) 3 2+ ECL label can be sensitively determined at subpicomolar concentrations, along with an extremely wide dynamic range of greater than six orders of magnitude. Furthermore, it can eliminate disposal and lifetime problems inherent in radio immunoassays. In this paper, basic principles of the Ru(bpy) 3 2+ ECL are discussed. In addition, analytical applications of the Ru(bpy) 3 2+ ECL are illustrated with examples.  相似文献   

10.
Summary Using 1,2-naphthoquinone-1-oxime (HL) as the principal ligand, four mixed-ligand ruthenium oximate complexes - namely [Ru(bipy)2(L)]ClO4, [Ru(pap)2(L)]-ClO4, [Ru(bipy)(L)2] and [Ru(PPh3)2(L)2], where bipy = 2,2′-bipyridine and pap = 2-(phenylazo)pyridine- have been synthesized and characterized. In all these complexes, Ru exists in the +2 state. They are diamagnetic and, in solution, show several intense metal-to-ligand charge transfer (MLCT) transitions in the vis. region. In MeCN solution, all four complexes show a reversible RuII-RuIII oxidation on the positive side of a standard calomel electrode (s.c.e.), the potential of which varies with the compositions of the complexes. Reductions of the coordinated co-ligands (bipy or pap) are also observed.  相似文献   

11.
Summary Reactions of ruthenium carbonyl complexes of the type [RuX2(CO)(Ph2RAs)3] (X=Cl or Br; R=Me or Et) with 2,2-bipyridyl (bipy) and 1,10-phenanthroline (phen) in alcohol produce orange red cationic products of the formula [RuX(CO)(N-N)(Ph2RAs)2]ClO4 (N-N=bipy or phen). Likewise, the hydridocarbonyls of ruthenium and osmium of the type [MHX(CO)(Ph2RAs)3] (M=Ru or Os) react with bipy and phen to yield yellow cationic complexes of the composition [(MH(CO)(N-N)(Ph2RAs)2]ClO4. Structures have been assigned to all the complexes on the basis of i.r. and1 H n.m.r. spectral data.  相似文献   

12.
Several dendritic bridging ligands were designed and synthesized to develop more sensitive and efficient electrochemiluminescent (ECL) polynuclear Ru(II) complexes. Various types of novel two-armed, four-armed and six-armed tris(bipyridyl)ruthenium core dendrimers were synthesized by coordinating dendritic polybipyridyl ligands with Ru(II) complexes, and the effect of the ligand and the dendritic network on the ECL characteristics were studied. Their electrochemical redox potentials, UV, photoluminescence (PL), and relative ECL intensities were also investigated in detail. The synthesized metallodendrimers exhibited strong metal-to-ligand charge transfer (MLCT) absorption at 428-451 nm and emission at 591-601 nm. Most of the newly synthesized metallodendrimers showed enhanced ECL intensities compared to the reference complex, [Ru(o-phen)3](PF6)2. In particular, the ECL intensities of the six-armed heptanuclear ruthenium complexes were almost four times greater than that of [Ru(o-phen)3]2+. These metallodendrimers could be utilized as efficient ECL materials and light emitting devices.  相似文献   

13.
A novel electrogenerated chemiluminescence (ECL) sensor based on natural clay and ionic liquid was fabricated. Tris(2,2′‐bipyridine)ruthenium(II) (Ru(bpy)32+) was immobilized on natural clay surface through simple adsorption. An ECL sensor was prepared by mixing Ru(bpy)32+‐incorporated clay, graphite powder and an ionic liquid (1‐butyl‐3‐methylimidazolium hexafluorophosphate) as the binder. The electrochemical behavior and ECL of the immobilized Ru(bpy)32+ was investigated. It was observed that the ECL of immobilized Ru(bpy)32+ was activated by the ionic liquid. The proposed ECL sensor showed high sensitivity to tri‐n‐propylamine (TPrA) and the detection limit was found to be 20 pM. In addition, the ECL sensor displayed good stability for TPrA detection and long‐term storage stability.  相似文献   

14.
Two polypyridyl ligands 6-fluro-3-(1H-imidazo [4,5-f] [1,10]-phenanthroline-2-yl)-4H-chromen-4-one (FIPC), 6-chloro-3-(1H-imidazo [4,5-f] [1,10]-phenanthroline-2-yl)-4H-chromen-4-one (ClIPC) polypyridyl ligands and their Ru(II) complexes [Ru(bipy)2FIPC]2+(1), [Ru(dmb)2FIPC]2+(2), [Ru(phen)2FIPC]2+(3), [Ru(bipy)2ClIPC]2+(4), [Ru(dmb)2ClIPC]2+(5) and [Ru(phen)2ClIPC]2+(6) ((bipy = 2,2′-bipyridine, dmb = 4,4′-dimethyl-2,2′-bipyridine and phen = 1,10-phenanthroline) have been synthesised and characterised by elemental analysis, Mass spectra, IR, 1H and 13C-NMR. The DNA-binding of the six complexes to calf-thymus DNA (CT-DNA) has been investigated by different spectrophotometric, fluorescence and viscosity measurements. The results suggest that 1–6 complexes bind to CT-DNA through intercalation. The variation in binding affinities of these complexes is rationalised by a consideration of electrostatic, steric factors and nature of ancillary ligands. Under irradiation at 365 nm, the three complexes have also been found to promote the photocleavage of plasmid pBR 322 DNA. Inhibitor studies suggest that singlet oxygen (1O2) plays a significant role in the cleavage mechanism of Ru(II) complexes. Thereby, under comparable experimental conditions [Ru(phen)2FIPC]2+(3), [Ru(phen)2ClIPC]2+(6) cleaves DNA more effectively than 1, 2, 4 and 5 complexes do. The Ru(II) polypyridyl complexes (1–6) have been screened for antimicrobial activities.  相似文献   

15.
DNA-binding properties of a number of ruthenium complexes with different polypyridine ligands are reported. The new polypyridine ligand BFIP (=2-benzo[b] furan-2-yl-1H-imidazo[4,5-f][1,10]phenanthroline) and its ruthenium complexes [Ru(bpy)2BFIP]2+ (bpy = 2,2′-bipyridine), [Ru(dmb)2BFIP]2+ (dmb = 4,4′-dimethyl-2,2′-bipyridine), and [Ru(phen)2BFIP]2+ (phen = 1,10-phenanthroline) have been synthesized and characterized by elemental analysis, mass spectra, IR, UV-Vis, 1H- and 13C-NMR, and cyclic voltammetry. The DNA binding of these complexes to calf-thymus DNA (CT-DNA) was investigated by spectrophotometric, fluorescence, and viscosity measurements. The results suggest that ruthenium(II) complexes bind to CT-DNA through intercalation. Photocleavage of pBR 322 DNA by these complexes was also studied, and [Ru(phen)2BFIP]2+ was found to be a much better photocleavage agent than the other two complexes.  相似文献   

16.
多吡啶钌(Ⅱ)配合物化学发光性质研究   总被引:3,自引:0,他引:3  
韩鹤友  何治柯  曾云鹗 《化学学报》2001,59(9):1513-1518
详细研究了Ru(bpy)3^2+,Ru(bpy)2(dppx)^2+,Ru(bpy)2(dppz)^2+,Ru(phen)3^2+,Ru(phen)2(dppx)^2+和Ru(phen)2(dppz)^2+六个多吡啶钌(Ⅱ)配合物的化学发光性质,筛选出Ru(bpy)3^2+和Ru(phen)3^2+两种性能优良的化学发光试剂;并探讨了它们发光的可能机理和影响因素,为钌(Ⅱ)配合物在化学发光分析中的应用提供了可供参考的理论依据。  相似文献   

17.
Semi-automated flow injection instrumentation, incorporating a small anion exchange column coupled with tris(2,2′-bipyridyl)ruthenium(II) (Ru(bipy)32+) chemiluminescence detection, was configured and utilised to develop rapid methodology for the determination of sodium oxalate in Bayer liquors. The elimination of both negative and positive interferences from aluminium(III) and, as yet, unknown concomitant organic species, respectively are discussed. The robustness of the methodology was considerably enhanced by using the temporally stable form of the chemiluminescence reagent, tris(2,2′-bipyridyl)ruthenium(III) perchlorate in dry acetonitrile. Real Bayer process samples were analysed and the results obtained compared well with those performed using standard methods within industrial laboratories.  相似文献   

18.
A highly sensitive and stable tris(2,2′-bipyridyl)ruthenium(II) (Ru(bpy)32+) electrogenerated chemiluminescence (ECL) sensor was developed based on carbon nanotube (CNT) dispersed in mesoporous composite films of sol-gel titania and perfluorosulfonated ionomer (Nafion). Single-wall (SWCNT) and multi-wall carbon nanotubes (MWCNT) can be easily dispersed in the titania-Nafion composite solution. The hydrophobic CNT in the titania-Nafion composite films coated on a glassy carbon electrode certainly increased the amount of Ru(bpy)32+ immobilized in the ECL sensor by adsorption of Ru(bpy)32+ onto CNT surface, the electrocatalytic activity towards the oxidation of hydrophobic analytes, and the electronic conductivity of the composite films. Therefore, the present ECL sensor based on the CNT-titania-Nafion showed improved ECL sensitivity for tripropylamine (TPA) compared to the ECL sensors based on both titania-Nafion composite films without CNT and pure Nafion films. The present Ru(bpy)32+ ECL sensor based on the MWCNT-titania--Nafion composite gave a linear response (R2 = 0.999) for TPA concentration from 50 nM to 1.0 mM with a remarkable detection limit (S/N = 3) of 10 nM while the ECL sensors based on titania-Nafion composite without MWCNT, pure Nafion films, and MWCNT-Nafion composite gave a detection limit of 0.1 μM, 1 μM, and 50 nM, respectively. The present ECL sensor showed outstanding long-term stability (no signal loss for 4 months).  相似文献   

19.
A series of new ruthenium(II) complexes containing 1,3-dihydro-1,1,3,3-tetramethyl-7,8-diazacyclopenta[1]phenanthren-2-one (DTDP) ligand, such as [Ru(DTDP)n(L)3−n]2+ (L = 2,2′-bipyridyl (bpy), 4,4′-dimethyl-2,2′-bipyridyl (dmbpy), o-phenanthroline (o-phen), 5-chloro-o-phenanthroline (o-phen-Cl), 2,2′-bipyridine-4,4′-dicarboxaldehyde (bpy-(CHO)2), n = 1, 2, 3) were synthesized and examined as ECL materials. All the complexes were characterized in terms of electrochemical redox potential and relative ECL intensity, and were compared to the well-known tris(o-phenanthroline) ruthenium(II) complex. Most of the synthesized Ru(II) complexes containing the DTDP ligand exhibited more intense ECL emissions than [Ru(o-phen)3]2+. In particular, the ECL intensities of [Ru(DTDP)(o-phen)2]2+ and [Ru(DTDP)(bpy-(CHO)2)2]2+ were observed to be as high as 9-fold and 20-fold greater, respectively, than the ECL intensity of [Ru(o-phen)3]2+.  相似文献   

20.
陈晓彤  董彬  崔孟超  王科志  金林培 《化学学报》2007,65(12):1181-1184
比较研究了以C2O42-为共反应物时5个结构相关的Ru(II)配合物[Ru(bpy)2L1]2+, [Ru(bpy)2L2]2+, [Ru(bpy)2L3]2+, [Ru(phen)2L1]2+和[Ru(phen)2L2]2+(其中bpy=2,2′-联吡啶, phen=1,10-邻菲啰啉, L1=4-羧基苯基咪唑[4,5-f][1,10]邻菲啰啉, L2=3-羧基-4-羟基苯基咪唑[4,5-f][1,10]邻菲啰啉, L3=3,4-二羟基苯基咪唑[4,5-f][1,10]邻菲啰啉)的电致化学发光(ECL)性质. 结果表明, 酚羟基的存在能有效地淬灭Ru(II)配合物[Ru(bpy)2L2]2+, [Ru(bpy)2L3]2+和[Ru(phen)2L2]2+的ECL, 其它Ru(II)配合物的ECL量子效率与[Ru(bpy)3]2+相差不大.  相似文献   

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