Unique electrochemiluminescence behavior of Ru(bpy)3 in a gold/Nafion/Ru(bpy)3 composite

The unique electrochemiluminescence (ECL) behavior of tris(bipyridine) ruthenium(II) (Ru(bpy)₃²⁺) immobilized in a gold/Nafion/Ru(bpy)₃²⁺ composite material was investigated. In this composite, the Ru(bpy)₃²⁺ ECL was found mainly occurred at 0-0.4 V during the cathodic scan process and the ECL peak was at about 0.1 V, which was quite different to the reported Ru(bpy)₃²⁺ ECL. Similar to the generally observed Ru(bpy)₃²⁺ ECL, the present ECL also could be enhanced by tri-n-propylamine (TPA). It is also unique that in the presence of TPA, another ECL peak at about 0.38 V occurred. These two ECL peak potentials all could be used as characteristic potential for the ECL determination of TPA.     

Luminescent supramolecular microstructures containing Ru(bpy)3(2+): solution-based self-assembly preparation and solid-state electrochemiluminescence detection application

In this correspondence, we report on the first preparation of novel, robust Ru(bpy)32+-containing supramolecular microstructures via a solution-based self-assembly strategy, carried out by directly mixing H2PtCl6 and Ru(bpy)3Cl2 aqueous solutions at room temperature. It reveals that both the molar ratio and concentration of reactants have a heavy influence on the morphologies of such microstructures. The electrochemical behavior of the Ru(bpy)32+ components contained in the solid film of the microstructures formed on the electrode surface is also studied and found to exhibit a diffusion-controlled voltammetric feature. Most importantly, such microstructures exhibit excellent electrochemiluminescence (ECL) behaviors and therefore hold great promise as new luminescent materials for solid-state ECL detection in capillary electrophoresis (CE) or CE microchip.     

Scanning electrochemical microscopy. 56. Probing outside and inside single giant liposomes containing Ru(bpy)32+

Giant liposomes containing Ru(bpy)(3)(2+) (bpy = 2,2'-bipyridine) were prepared as model systems for biomembranes and cells and studied by scanning electrochemical microscopy (SECM). Conical carbon fiber tips of submicrometer size were used to approach, image, and puncture individual liposomes immobilized on glass substrates. SECM images of the liposomes were obtained, and the leakage of Ru(bpy)(3)(2+) through the lipid membrane was probed. The tip was also pushed into liposomes and characteristic breakthrough transients, corresponding to liposomes with different compartmental configurations, were obtained. Voltammograms were obtained with the tip inside a single liposome after breaking through the membrane, and the influx of mediator and efflux of encapsulant after puncture could be observed.     

Electrogenerated chemiluminescence sensors using Ru(bpy)3(2+) doped in silica nanoparticles

A novel electrogenerated chemiluminescence (ECL) sensor based on Ru(bpy)3(2+)-doped silica (RuDS) nanoparticles conjugated with a biopolymer chitosan membrane was developed. These uniform RuDS nanoparticles (approximately 40 nm) were prepared by a water-in-oil microemulsion method and were characterized by electrochemical and transmission electron microscopy technology. The Ru(bpy)3(2+)-doped interior maintained its high ECL efficiency, while the exterior nanosilica prevented the luminophor from leaching out into the aqueous solution due to the electrostatic interaction. This is the first attempt to branch out the application of RuDS nanoparticles into the field of ECL, and since a large amount of Ru(bpy)3(2+) was immobilized three-dimensionally on the electrode, the Ru(bpy)3(2+) ECL signal could be enhanced greatly, which finally resulted in the increased sensitivity. This sensor shows a detection limit of 2.8 nM for tripropylamine, which is 3 orders of magnitude lower than that observed at a Nafion-based ECL sensor. Furthermore, the present ECL sensor displays outstanding long-term stability.     

Method for effective immobilization of Ru(bpy)(3)2+ on an electrode surface for solid-state electrochemiluminescene detection

A novel method for effective immobilization of Ru(bpy)3(2+) on an electrode surface is developed. The whole process involves two steps: the electrostatic interactions between citrate-capped gold nanoparticles (AuNPs) and Ru(bpy)3Cl2 in aqueous medium were used to fabricate Ru(bpy)(3)2+-AuNP aggregates (Ru-AuNPs) first, and then the Au-S interactions between as-formed Ru-AuNPs and sulfhydryl groups were used to effectively immobilize the Ru-AuNPs on a sulfhydryl-derivated indium tin oxide (ITO) electrode surface. As-prepared ITO electrode shows excellent stability, and the ECL active species Ru(bpy)3(2+) contained therein exhibit excellent ECL behaviors.     

Pt nanoparticles: Heat treatment-based preparation and Ru(bpy)(3)2+-mediated formation of aggregates that can form stable films on bare solid electrode surfaces for solid-state electrochemiluminescence detection

A simple thermal process for the preparation of small Pt nanoparticles is presented, carried out by heating a H2PtCl6/3-thiophenemalonic acid aqueous solution. The following treatment of such colloidal Pt solution with Ru(bpy)(3)2+ causes the assembly of Pt nanoparticles into aggregates. Most importantly, directly placing such aggregates on bare solid electrode surfaces can produce very stable films exhibiting excellent electrochemiluminescence behaviors.     

Spectroscopic Probing of Mixed-Mode Adsorption of Ru(bpy)(3)(2+) to Silica

Evanescent wave excitation of fluorescence was used to study the adsorption of Ru(bpy)(3)(2+) from aqueous solution to three types of surfaces: bare silica, a dimethylethylsiloxane (C(2)) monolayer on silica, and a dimethyloctadecylsiloxane (C(18)) monolayer on silica. The solution pH was varied to investigate the nonpolar and electrostatic contributions to the free energy of adsorption for each surface. The pH dependence of the adsorption showed that the pK(a) is the same for each of the three surfaces, consistent with earlier conclusions that the acidity of derivatized silica surfaces is due to areas of exposed silica. The free energies of adsorption for the bare silica surface, -26.2(±0.2) kJ/mol at pH 8, was attributed to electrostatic interactions alone. The free energy of adsorption for the C(2) and C(18) surfaces, -28.5(±0.1) and -31.5(±0.1) kJ/mol, respectively, were found to have both electrostatic and nonpolar contributions, with the latter being larger by 50% for the C(2) surface and 100% for the C(18) surface. Using Gouy-Chapman theory, the surface charge densities on each of the three surfaces, calculated from the electrostatic interaction energy of Ru(bpy)(3)(2+), were found to be within the range of literature values: 8.8(±0.1) × 10(-)(7) mol/m(2) for bare silica and 1.7(±0.1) × 10(-)(7) mol/m(2) for both the C(18) and C(2) surfaces. The results demonstrate that a cationic dye can be used to probe the silanol activity of chemically modified silica surfaces. The results support the picture that these chemically modified silica surfaces are acidic due to molecular-scale areas of contact between the bare silica substrate and the aqueous phase.     

Electrogenerated chemiluminescence. 80. C-reactive protein determination at high amplification with [Ru(bpy)3]2+-containing microspheres

Biotinylated anti-C-reactive protein (CRP) species were attached to the surface of streptavidin-coated magnetic beads (MB) and avidin-coated polystyrene microspheres/beads (PSB) entrapping a large number of electrogenerated chemiluminescence (ECL) labels ( approximately 10(9) Ru(bpy)(3)[B(C(6)F(5))(4)](2)/bead) to form anti-CRP<-->MB and Ru(II) subsetPSB/avidin<-->anti-CRP conjugates, respectively. Sandwich-type Ru(II) subsetPSB/avidin<-->anti-CRP CRP anti-CRP<-->MB aggregates were formed when Ru(II) subsetPSB/avidin<-->anti-CRP was mixed with anti-CRP<-->MB conjugates in the presence of analyte CRP. The newly formed aggregates were magnetically separated from the reaction media and dissolved in MeCN containing tri-n-propylamine as an ECL coreactant. ECL was carried out with a potential scan from 0 to 2.8 V vs Ag/Ag(+), and the ECL intensity was found to be proportional to the analyte CRP concentration over the range of 0.010-10 mug/mL. The CRP concentration of an unknown human plasma specimen was measured by the standard addition method based on this technique. Elimination of the nonspecific adsorption of the CRP system with several different blocking agents was also studied, and 2.0% bovine serum albumin was found to be best.     

Electrostatic Interactions between Ru(bpy)(3)(2+) and Chromatographic Surfaces

In HPLC, the zones of organic bases tail when silica-based stationary phases are used because the analytes and the surface are oppositely charged. In developing new stationary phases to achieve lower surface charge, a measure of surface charge is needed. The choice of a suitable analyte to quantitate electrostatic interactions is complicated by the acid-base equilibrium of the analyte itself and by nonelectrostatic interactions between the analyte and the surface, which alter the charge-induced tailing. This paper describes the study of the pH dependence of adsorption to isolate electrostatic interaction and the use of a cationic probe, tris(2,2'-bipyridine)ruthenium chloride (Ru(bpy)(3)(2+)), to sense surface charge without the complication of the probe's acid-base equilibria. The paper further describes the application of Gouy-Chapman theory to reveal the surface charge density. The results confirm that type A silica is considerably more acidic than type B silica and that horizontal polymerization makes type A silica perform as well as type B silica.     

Electrogenerated chemiluminescence. 77. DNA hybridization detection at high amplification with [Ru(bpy)3]2+-containing microspheres

An ultrasensitive DNA hybridization detection method based on electrogenerated chemiluminescence (ECL) using polystyrene microspheres/beads (PSB) as the carrier of the ECL labels, namely, tris(2,2'-bipyridyl)ruthenium(II) tetrakis(pentafluorophenyl)borate (Ru(bpy)3[B(C6F5)4]2), is reported. Probe single-stranded DNA (p-ssDNA) was attached to the surface of magnetic beads (MB) and hybridized with target-ssDNA (t-ssDNA) with immobilized PSB containing a large number of water insoluble Ru(bpy)3[B(C6F5)4]2 species (approximately 7.5 x 10(9) molecules/bead). With this approach a large amplification factor of Ru(bpy)3[B(C6F5)4]2 molecules for each t-ssDNA can be achieved, when each PSB is attached to a limited number of t-ssDNA. The p-ssDNA-MB <--> t-ssDNA-PSB/Ru(bpy)3(2+) conjugates formed were magnetically separated from the reaction media and dissolved in MeCN containing tri-n-propylamine (TPrA) as an ECL coreactant. ECL was produced with a potential scan from 0 to 3.0 V versus Ag/Ag+, and the integrated ECL intensity was found to be linearly proportional to the t-ssDNA concentration in a range of 1.0 fM to 10 nM under optimized conditions. ECL signals associated with two base pair mismatched ssDNA and noncomplementary ssDNA can be distinguished well from the ECL signal related to the complementary DNA hybridization. A Poisson distribution is followed when a large number of MB reacts with PSB, and the minimum number of 1.0- and 2.8-microm diameter MB required to bind and magnetically separate a single 10-microm diameter PSB from the reaction solution was estimated to be three and one, respectively. The principle described in this paper could be also applied to many other ECL analyses, such as immunoassays.     

新型材料用于固定联吡啶钌电致化学发光的研究进展

固定联吡啶钌电致化学发光体系因其灵敏度高、可以连续测试、装置简单等优点被广泛应用于分子生物学、化学、药学等领域.各种新材料的运用克服了原有方法稳定性差、重现性差等缺点,拓宽了固定化联吡啶钌电致化学发光的应用范围.介绍了近几年来一些用于固定联吡啶钌新的材料、固定方法及其相关的应用.     

Research Progress of New Materials Applied in Ru(bpy)32+ Immobilized Electrochemiluminescence System

固定联吡啶钌电致化学发光体系因其灵敏度高、可以连续测试、装置简单等优点被广泛应用于分子生物学、化学、药学等领域.各种新材料的运用克服了原有方法稳定性差、重现性差等缺点,拓宽了固定化联吡啶钌电致化学发光的应用范围.介绍了近几年来一些用于固定联吡啶钌新的材料、固定方法及其相关的应用.     

Analysis of the photodecomposition products of Ru(bpy)3(2+) in various buffers and upon zeolite encapsulation

The photodecomposition products of Ru(bpy)3(2+) in water, in aqueous buffered solutions and encapsulated in zeolite-Y have been analyzed by chromatography and UV-visible spectroscopy. The chromatographic method is found to be capable of separating species with the same charge but slightly different ligands as well as geometrical isomers. In all the systems investigated, photodecomposition proceeded via photoaquation resulting in the formation of cis- and trans-Ru(bpy)2(OH2)2(2+). In the case of acetate and phthalate buffers, a third species, Ru(bpy)2(L)(OH2)+, where L is the buffer anion, was found to be the dominant product. For a given pH, the extent of decomposition was found to be dependent on both the buffer anion, following the trend, phosphate < acetate < phthalate and buffer concentration. The presence of the electron-transfer quenching agent, N,N'-dimethyl-4,4'-bipyridinium ion in the medium led to a decrease of the photodecomposition and closely followed the quenching efficiency as measured by intensity and lifetime quenching studies. Encapsulation of Ru(bpy)3(2+) in the supercages of zeolite-Y did not lead to a substantial decrease in photodecomposition as compared to an aqueous solution, suggesting that the expected enhanced stability of Ru(bpy)3(2+*) due to the destabilization of 3dd orbitals and the cage effect was being negated by the close proximity and intrazeolite packing of H2O molecules around the Ru center.     

Ru(bpy)32+-sensitized{001}facets LiCoO2 nanosheets catalyzed CO2 reduction reaction with 100% carbonaceous products

Photosensitized heterogeneous CO₂ reduction(PHCR)has emerged as a promising means to convert CO₂ into valuable chemicals,however,challenged by the relatively low carbonaceous product selectivity caused by the competing hydrogen evolution reaction(HER).Here,we report a PHCR system that couples Ru(bpy)32+photosensitizer with{001}faceted LiCoO₂ nanosheets photocatalyst to simultaneously yield 21.2 and 722μmol·g^-1·h^-1 of CO,and 4.42 and 108μmol·g^-1·h^-1 of CH4 under the visible light and the simulated sunlight irradiations,respectively,with completely suppressed HER.The experimental and theoretical studies reveal that the favored CO₂ adsorption on the exposed Li sites on{001}faceted LiCoO₂ surface is responsible for the completely suppressed HER.     

Detection of chemically induced DNA damage in layered films by catalytic square wave voltammetry using Ru(bpy)3(2+).

A sensor constructed by alternate layer-by-layer adsorption of PDDA cations and double-stranded (ds)-DNA on oxidized pyrolytic graphite electrodes was evaluated for detection of chemical damage to ds-DNA from known damage agent styrene oxide. Films made with PDDA ions of structure (PDDA/DNA)2 were approximately 6 nm thick and contained 0.23 microg of ds-DNA. Catalytic oxidation using 50 microM Ru(bpy)3(2+) (bpy = 2,2'-bipyridine) and square wave voltammetry (SWV) provided more sensitive detection of DNA damage than direct SWV oxidation. The catalytic peaks increased linearly with time during incubations with styrene oxide, but only minor changes were detected during incubation with nonreactive toluene. For best sensitivity, the outer layer of the film must be ds-DNA, and analysis should be done at low salt concentration. Studies of DNA and polynucleotides in solutions and films suggested that oxidation of guanine and chemically damaged adenine in partly unraveled, damaged DNA were the most likely contributors to the catalytic peak.     

Catalytic oxidation of anionic surfactants by electrochemical oxidation with CuO-Co2O3-PO4(3-) modified kaolin

A new catalytic oxidation of anionic surfactants by electrochemistry method was designed and used to investigate the removal of anionic surfactant from simulated wastewater. Synergetic effect on COD removal was studied when integrating the electrochemical reactor, using porous graphite as anode and cathode, with the effective CuO-Co2O3-PO4(3-) modified kaolin catalyst in a single undivided cell. The result showed that this combined process could effectively remove anionic surfactant. Its COD removal efficiency was much higher than those individual processes and could reach up to 90% in 60 min. The operating parameters such as initial pH, cell voltage, and current intensity were also investigated. Possible theory for COD removal was also proposed to predict the role of modified kaolin, electro-catalysis and oxidation in the combined process. The pollutants in wastewater could be decreased by the high reactive OH* that produced on the surface of catalyst by the decomposition of electrochemical generated H2O2. The result indicates that the catalytic oxidation by electrochemistry method is a promising wastewater treatment technique.     

Electrogenerated chemiluminescence sensor for formaldehyde based on Ru(bpy)32+-doped silica nanoparticles modified Au electrode

A novel and sensitive electrogenerated chemiluminescence (ECL) sensor for formaldehyde was developed with the amine-functionalized Ru(bpy)₃²⁺-doped silica nanoparticles (Ru-DSNPs) as ECL emitter. Ru(bpy)₃²⁺ doped on the silica nanoparticle can maintain its electrochemical activities, which made silica nano-beads a excellent carrier of Ru(bpy)₃²⁺ species. The uniform Ru-DSNPs (about 75 nm) were conjugated with Au electrode using mercaptoacetic acid as the intermediate to fabricate an ECL sensor for formaldehyde. The ECL analytical performances of this ECL sensor for formaldehyde based on its enhancement ECL emission of Ru(bpy)₃²⁺ were investigated in details. Under the optimum condition, the ECL intensity was linear with the formaldehyde concentration in the range of 1.0 × 10^? 8 mol/L to 1.0 × 10^? 6 mol/L. The detection limit was 6.0 × 10^? 9 mol/L (S/N = 3). This approach offered obvious advantages of being simpler, faster, and more stable compared with other sensors, and possessed great potential for formaldehyde detection which could be applied to determine directly the formaldehyde in real samples without pre-separation.