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1.
A controllable assembly technique of [Ru(bpy)2IP]3+/2+ (where bpy = 2,2′-bipyridine and IP = imidazo[4,5,f][1,10]phenanthroline) promoted by calf thymus DNA at an ITO electrode is proposed. The stable assembled layer containing [Ru(bpy)2IP]3+/2+ and double stranded DNA is obtained on the ITO electrode using repetitive voltammetric sweeping, confirmed by ex situ voltammetry, X-ray photoelectron spectroscopy (XPS) and the inverted fluorescence microscopy. There exist two pairs of diffusion-controlled waves and two pairs of prewaves for [Ru(bpy)2IP]2+ in the voltammetric sweeping process. The half-wave potentials of the prewaves are far more negative than those of the diffusion-controlled waves. These experimental results suggest that double stranded DNA is enable to accelerate and increase the controllable assembly of Ru(bpy)2IP]3+/2+ by using the ITO surface. The fluorescence microscopy imaging reveals that [Ru(bpy)2IP]3+/2+ has the ability to bind with double strand DNA. The fluorescence intensity of [Ru(bpy)2IP]3+/2+ with DNA is stronger than that without DNA.  相似文献   

2.
A [Ru(bpy)3]2+ (bpy = 2,2′-bipyridine)/WO3 hybrid (denoted as Ru-WO3) film was prepared as a base layer on an indium tin oxide electrode by electrodeposition from a colloidal solution containing peroxotungstic acid, [Ru(bpy)3]2+ and poly(sodium 4-styrenesulfonate). A ruthenium purple (RP, FeIII4[RuII(CN)6]3, denoted as FeIII-RuII) layer was electrodeposited on a neat WO3 film or a Ru-WO3 film from an aqueous RP colloid solution to yield a WO3/RP bilayer film or a Ru-WO3/RP bilayer film, respectively. The spectrocyclic voltammetry measurement reveals that FeII-RuII is oxidized to FeIII-RuII by a geared reaction of [Ru(bpy)3]2+/3+ and FeIII-RuII is reduced by a geared reaction of HxWO3/WO3 in the Ru-WO3/RP film. These geared reactions produced electrochromic hysteresis of the RP layer. However, the absorbance change in the hysteresis was smaller than that for the Ru-WO3/Prussian blue bilayer film reported previously, resulting from the lower electroactivities of any redox component for the Ru-WO3/RP film. The lower electroactivities could be explained by the specific interface between the Ru-WO3 and RP layers. It might contribute to either an increase of the interfacial resistance between the Ru-WO3 and RP layers, or formation of the physically precise interface between the layers to make it difficult for counter ions to be transported in the interfacial liquid phase involved in the redox reactions in the film. The specific interface at the Ru-WO3 and RP layers could be formed possibly by the electrostatic interaction between [Ru(bpy)3]2+ and terminal [Ru(CN)6]4− moieties of RP. It could be suggested by the decreased redox potential of [Ru(bpy)3]2+ in the Ru-WO3 layer from 1.03 to 0.61 V by formation of the RP layer.  相似文献   

3.
A simple method was developed for the preparation of [Ru(bpy)2tatp]2+-based aggregates (where bpy = 2,2′-bipyridine, tatp = 1,4,8,9-tetra-aza-triphenylene) on an indium tin oxide (ITO) electrode in the presence of DNA-stabilized single-walled carbon nanotubes (DNA–SWCNTs). The presence of SWCNTs in the concentration range from 0.02 to 0.125 g L−1 dispersed with 0.25 mmol L−1 DNA was found to promote the immobilization of [Ru(bpy)2tatp]2+ on the ITO electrode by the method of repetitive voltammetric sweeping. The photoluminescence of [Ru(bpy)2tatp]2+ incorporating DNA–SWCNTs both in solution and on the ITO electrode was systematically investigated by emission spectra and fluorescence microscopic imaging. An excess amount of SWCNTs can quench the photoluminescence of [Ru(bpy)2tatp]2+ enhanced by DNA. The anodic potentials combined with CW green laser via an optical microscope was found to significantly increase the emission intensity of [Ru(bpy)2tatp]2+–DNA–SWCNTs aggregates on the ITO electrode. In addition, the electrochemical fabrication and photoluminescence principles of [Ru(bpy)2tatp]2+–DNA–SWCNTs aggregates on the ITO electrode tuned by the external electric fields were discussed in detail.  相似文献   

4.
A novel technique for controllable assembly of [Ru(bpy)2ITATP]3+/2+ (where bpy = 2,2′-bipyridine, ITATP = isatino[1,2-b]-1,4,8,9-tetraazatriphenylene) on an ITO electrode in the absence and presence of calf thymus DNA is proposed. The [Ru(bpy)2ITATP]3+/2+ and double stranded DNA is assembled onto the ITO electrode using repetitive voltammetric sweeping. The assembly is confirmed by ex situ cyclic voltammetry and the fluorescence microscopy. A pair of diffusion-controlled waves and prewaves for [Ru(bpy)2ITATP]3+/2+ is observed in the voltammetric sweeping process. The formal potential of the prewaves is found to be much negative than that of the diffusion-controlled waves. The controllable assembly of [Ru(bpy)2ITATP]3+/2+ on the ITO surface is accelerated by DNA and affected by ionic strength. With this DNA-prompted electrochemical technique, a multifunctional biomolecular film containing surface-confined redox center of controllable thickness is fabricated.  相似文献   

5.
Electrochemical oxidation of guanine mediated by [Ru(bpy)2dpp]2+ (where bpy = 2,2′-bipyridine, dpp = 2,3-bis (2-pyridyl) pyrazine) and their electrochemical assembly at an ITO electrode prompted by guanine have been investigated with cyclic voltammetry and differential pulse voltammetry. It is found that [Ru(bpy)2dpp]2+ can serve as an excellent mediator to induce the oxidation of guanine, and the mediated peak currents increase linearly with the rise of guanine concentration in the range from 0.01 to 0.20 mmol L−1. Interestingly, with the increase of repetitive voltammetric sweeping numbers, [Ru(bpy)2dpp]3+/2+ can be assembled onto the ITO electrode and guanine has the ability to enhance the peak currents of prewaves. Also, with the rise of guanine concentration from 0.01 to 0.15 mmol L−1, the peak currents of prewaves increase gradually. Meanwhile, the mediated mechanism of guanine oxidation by [Ru(bpy)2dpp]2+ and the assembled process of [Ru(bpy)2dpp]3+/2+ on the ITO surface in the presence of guanine are discussed in detail.  相似文献   

6.
The electrochemical assembly of [Ru(bpy)2tatp]2+ (where bpy = 2,2′-bipyridine, tatp = 1,4,8,9-tetra-aza-triphenylene) on the multi-walled carbon nanotubes-modified glassy carbon electrode (MWNTs/GC) in the presence of anionic and cationic surfactants has been investigated. A diffusion-controlled wave and three prewaves are exhibited on the differential pulse voltammogram of [Ru(bpy)2tatp]2+. The formal potential of the prewaves is found to be much negative than that of the diffusion-controlled wave. An appropriate amount of anionic surfactants including dihexadecyl phosphate (DHP) and deoxyribonucleic acid (DNA) can prompt the assembly of [Ru(bpy)2tatp]2+ on the MWNTs/GC electrode by using the method of repetitive voltammetric sweeping. In contrast, cationic surfactant such as hexadecyl trismethyl ammonium chrolide (HTAC) dispersed on the MWNTs surface is found to inhibit the assembly of [Ru(bpy)2tatp]2+. Meanwhile, the assembled principle of [Ru(bpy)2tatp]2+ on the MWNTs/GC electrode with the participation of surfactants is discussed in detail.  相似文献   

7.
Glyphosate, a phosphorus-containing amino acid type herbicide was used as a coreactant for studying of electrochemiluminescence (ECL) reaction of tris(2,2′-bipyridyl)ruthenium(II) [Ru(bpy)32+] in an aqueous solution. In a phosphate buffer solution of pH 8, glyphosate itself was known to be electrochemically inactive at glassy carbon electrode, however, it participated in a homogeneous chemical reaction with the electrogenerated Ru(bpy)33+, and resulted in producing Ru(bpy)32+ species at the electrode surface. Kinetic and mechanistic information for the catalysis of glyphosate oxidation were evaluated by the steady-state voltammetric measurement with an ultramicroelectrode. The simulated cyclic voltammogram based on this mechanism was in good agreement with that obtained experimentally. ECL reaction of Ru(bpy)32+/glyphosate system was found to be strongly dependent on the media pH. In a pH region of 5-9, an ECL wave appeared at ca. +1.1 V vs. Ag/AgCl, which was caused by the generation of *Ru(bpy)32+ via a Ru(bpy)33+-mediated oxidation of glyphosate. When pH >10, a second ECL wave was observed at ca. +1.35 V vs. Ag/AgCl, which was believed to be associated with a reaction between Ru(bpy)33+ and the species from direct oxidation of GLYP at a GC electrode surface.  相似文献   

8.
We developed a new electrochromic device by using compact Prussian blue (PB)/antimony tin oxide (ATO) nano-composites as anodic electrode and viologen anchoring on titanium dioxide (TiO2) nano-particles as cathodic electrode. The anodic electrode was based on a transparent nanostructured ATO nano-particle film and was electro-deposited by Prussian blue to form compact Prussian blue/ATO nano-composites by means of galvanostatic electrodeposition process. Nanocrystalline TiO2 thin films on conducting glass were modified with a mono-layer of viologen with two anchoring groups, which were much strongly adsorbed onto the surface of TiO2 nano-particles. A polymer gel electrolyte sandwiched between the anodic and cathodic layers is used as the ionic transport layer. The 2.5 cm × 2.5 cm electrochromic device shows high contrast (64.8%, at 600 nm) very low transmittance at colored stage (0.1%, at 600 nm), fast switching time (600 and 720 ms for coloration and bleaching, respectively), high coloration efficiency of 912 cm2 C−1 at 600 nm and good stability. The enhanced performance of the electrochromic device can be attributed to the ATO nano-particles as inter-conductive materials.  相似文献   

9.
A sensitive electrogenerated chemiluminescence (ECL) detection of DNA hybridization, based on tris(2,2′-bipyridyl)ruthenium(II)-doped silica nanoparticles (Ru(bpy)32+-doped SNPs) as DNA tags, is described. In this protocol, Ru(bpy)32+-doped SNPs was used for DNA labeling with trimethoxysilylpropydiethylenetriamine(DETA) and glutaraldehyde as linking agents. The Ru(bpy)32+-doped SNPs labeled DNA probe was hybridized with target DNA immobilized on the surface of polypyrrole (PPy) modified Pt electrode. The hybridization events were evaluated by ECL measurements and only the complementary sequence could form a double-stranded DNA (dsDNA) with DNA probe and give strong ECL signals. A three-base mismatch sequence and a non-complementary sequence had almost negligible responses. Due to the large number of Ru(bpy)32+ molecules inside SNPs, the assay allows detection at levels as low as 1.0 × 10−13 mol l−1 of the target DNA. The intensity of ECL was linearly related to the concentration of the complementary sequence in the range of 2.0 × 10−13 to 2.0 × 10−9 mol l−1.  相似文献   

10.
TiO2–Ni(OH)2 bilayer electrodes were prepared by the cathodic electrodeposition of Ni(OH)2 layer on a TiO2/ITO substrate. The porous Ni(OH)2 layers were obtained at relatively high current densities (≥1.0 mA cm−2), and the particle size increased with increasing the deposition current density. A porous nanostructured TiO2–Ni(OH)2 bilayer was obtained at a current density of 1.0 mA cm−2. The effects of OH concentration in the electrolyte and surface structure in the Ni(OH)2 layer on storage of the oxidative energy of TiO2 were investigated. In our experimental conditions the oxidative energy storage of an UV-irradiated TiO2 photocatalyst in Ni(OH)2 was obviously enhanced in the electrolyte with 1.0 M OH. The porous nanostructured TiO2–Ni(OH)2 bilayer electrode showed the notably improved oxidative energy storage performance, resulting from its porous structure and nanostructured Ni(OH)2 particles. The TiO2–Ni(OH)2 bilayer electrode during UV irradiation exhibited much higher potentials and larger photocurrent than the TiO2/ITO electrode. The transition from Ni(OH)2 to NiOOH under UV irradiation proceeded in the potential range of −0.5 to −0.2 V, much more negative than the Ni(OH)2/NiOOH redox potential. A possible mechanism on the oxidative energy storage of an UV-irradiated TiO2 photocatalyst in Ni(OH)2 was proposed, and the related experimental results were discussed in terms of the suggested model.  相似文献   

11.
The homogeneous and mediated oxidation of guanine by [Ru(bpy)3]2+ (2,2′-bipypyridine) in the presence of surfactants and single-walled carbon nanotubes (SWCNTs) has been investigated using cyclic voltammetry, repetitive differential pulse voltammetry and rotating electrode method. In acidic medium, the oxidation of guanine was controlled by mass transport process of [Ru(bpy)3]2+ in solution, leading to a homogeneous electrocatalysis. In neutral medium, the result from emission spectroscopy suggested the formation of the aggregates containing [Ru(bpy)3]2+, dihexadecyl phosphate (DHP) and guanine. The electrocatalysis of [Ru(bpy)3]2+ toward guanine oxidation was promoted by anionic surfactant DHP and, however, hindered by an excess amount of hexadecyl trismethyl ammonium chloride (HTAC) or SWCNTs added to solutions. The electrocatalytic mechanism of [Ru(bpy)3]2+ for guanine oxidation becomes evident, strongly depending on the presence of anionic or cationic surfactants and SWCNTs.  相似文献   

12.
The surface of a platinum electrode was anodically polarized at 3 V vs standard hydrogen electrode in 1 N H2SO4at 300 K for 16 h so that a thick uniform oxidation layer was formed. Analysis by X-ray photoelectron spectroscopy (XPS) showed that the stoichiometry O-to-Pt of this layer was equal to four, with O1s and Pt4f72 binding energies at 53.1 and 74.4 eV respectively. The oxidation layer is therefore proposed to consist of Pt(OH)4. Cyclic voltammograms showed a single cathodic oxygen peak in support of a single uniform oxidation compound.The comparison with spectra of thinner layers, grown at potentials between 1.2 and V vs she for only 15min, led to the conclusion that those are also made up predominantly of platinum hydroxide. Surface Pt(OH)4 thermally decomposes at 405 ± 5 K into a mixture of Pt4/Pt2+ hydroxides and oxides and Pt-metal with a measured ratio Pt:O = 1. At about 700 ± 50 K only a monolayer of adsorbed oxygen is left and at 1070 K all oxygen is desorbed.  相似文献   

13.
Charge transport (CT) in a Nafion membrane containing μ-oxobis[aquabis(2,2′-bipyridine)ruthenium(III)] complex, [(bpy)2(H2O)RuORu(H2O)(bpy)2]4+ (bpy=2,2′-bipyridine, abbreviated to RuIIIORuIII) was investigated by potential-step chronocoulospectrometry (PSCCS). Electrochemical reduction of RuIIIORuIII in the membrane occurred irreversibly to form [Ru(bpy)2(OH2)2]2+ monomer. The CT by reduction of RuIIIORuIII in the membrane was suggested to take place by physical displacement of the complex, which is quite different from the mechanism in the CT by oxidation of RuIIIORuIII in the same membrane in which charge is transported by charge hopping based on reversible redox reaction between RuIIIORuIII and RuIIIORuIV. The fractions of the electrochemically reacted complex in the membrane for the oxidative CT was dependent on the complex concentration, and the yield was low (maximum fraction=0.42 at 0.87 M) relative to the reductive CT. By contrast, the fraction for the reductive CT was independent of the concentration over 0.12 M and close to unity. The different concentration dependence of the fraction was discussed related to the difference in the CT mechanism.  相似文献   

14.
An electrogenerated chemiluminescence (ECL) reaction of the Ru(bpy)32+ (2,2′-bipyridyl, bpy)/co-reactant system in the extremely high-potential region (over 2.6 V versus Ag/AgCl) was probed using a boron-doped diamond (BDD) electrode. At the BDD electrode, three ECL waves (1.25, 2.30 and 3.72 V) were observed in cyclic voltammograms for 20 mM ascorbic acid (AA). For the ECL peaks observed at 1.25 V corresponding to the oxidation potential for Ru(bpy)32+ (1.15 V), the light intensities and current densities were found to depend on the square root of the AA concentration. This suggests that AA oxidation, followed by the formation of the reducing radical that is necessary for generating the excited state of Ru(bpy)32+* occurred through homogeneous electron-transfer between Ru(bpy)33+ and the AA species. However, for the ECL peaks at 2.30 V, the current densities and light intensities linearly increased with increasing AA concentration, suggesting that the reducing radical was formed through the direct oxidation at the electrode surface. The ECL reaction at 3.72 V was observed only at the BDD electrode and not at other electrodes. The onset potentials for the light intensity were approximately 2.6 V, independently of the type of the co-reactants (e.g. 2-propanol and AA). The peak potentials exhibited linear relation with the co-reactant concentration. In the analysis of the ECL intensity for various co-reactants (alcohols) that show different reactivity for the hydrogen abstraction reaction, the order of the light intensities at the peaks for alcohols was found to be consistent with that for the rate constants of the hydrogen abstraction reaction. These results indicate that the co-reactant radical was formed through the hydrogen abstraction reaction with the hydroxyl radical (HO) generated during the oxygen evolution reaction.  相似文献   

15.
The detection of proteins is very important in the study of biochemistry procedure, and electrochemiluminescence method is a very practical tool for the study of protein folding, structure and quantification. In this work, bovine serum albumin (BSA) and casein were found to be able to significantly quench the electrochemiluminescence (ECL) of Ru(bpy)32+/TPrA system, based on which a highly sensitive approach for the detection of protein was proposed. Under the optimized conditions, the logarithmic plot of the inhibited ECL versus the concentration of BSA and casein were linear over the ranges of 1–30 μg/L and 0.1–1.6 μg/L, respectively. The corresponding limit of detection (LOD) was 0.45 μg/L for BSA and 0.026 μg/L for casein (S/N = 3). UV, ECL and fluorescence methods were used to investigate the mechanism of the inhibited ECL of Ru(bpy)32+/TPrA/BSA system. A mechanism based on the formation of protein-Ru(bpy)32+ super molecule was proposed, which would prevent Ru(bpy)32+ from reaching the working electrode surface so that induced ECL quenching.  相似文献   

16.
The electrochemical assembly of [Ru(bpy)2dpp]3+/2+ (where bpy = 2,2′-bipyridine, dpp = 2,3-bis (2-pyridyl) pyrazine) promoted by calf thymus DNA on an ITO electrode based on the introduction of copper(II) ion has been investigated. There exists a diffusion-controlled wave and two prewaves for the complex in the differential pulse voltammetric sweeping process. The formal potential of the high prewave shift ca. 0.530 V negatively compared with that of the diffusion-controlled wave. Dpp ligand with two vacant chelating N sites in the complex can bite Cu2+ and the resultant heterometallic complex shows a weakened assembly in contrast to that of [Ru(bpy)2dpp]3+/2+ alone. Furthermore, double stranded DNA is able to accelerate the assembly of the ruthenium complex and heterometallic complex generated by chelating with Cu2+ by using the ITO surface, the prompted strength of the latter is far stronger than the former. Their assembled mechanism enhanced by DNA is proposed.  相似文献   

17.
The photoelectrochemical properties of polycrystalline TiO2 prepared at high temperature and doped polycrystalline TiO2 with noble metals have been investigated. The polycrystalline TiO2 prepared at high temperature give a cathodic photocurrent as well as a visible light response. These phenomena can be explained by a model based on the d-band formed by the interstitial Ti ion in TiO2 lattice. The doped polycrystalline TiO2 with noble metals (Rh, Ru, Pt, Au) prepared at low temperature also show a cathodic photocurrent and a visible light response. These are based on the impurity band formed by the doping metals. It is judged that the impurity band is near the π* conduction band for the doped TiO2 with Rh, Ru and Pt, but is near the π valence band for the Au doped TiO2 in energy position. It is found that there exist overlap potentials of the anodic and cathodic photocurrents at the doped TiO2 with noble metals. This will provide evidence on the mechanism of the enhancement of the photocatalysis on TiO2 owing to the doping of noble metals.  相似文献   

18.
The modification of a gold electrode surface by electropolymerization of trans-[Ru(NH3)4(Ist)SO4]+ to produce an electrochemical sensor for nitric oxide was investigated. The influence of dopamine, serotonin and nitrite as interferents for NO detection was also examined using square-wave voltammetry (SWV). The characterization of the modified electrode was carried out by cyclic voltammetry, electrochemical quartz crystal microbalance (EQCM) and SERS techniques. The gold electrode was successfully modified by the trans-[Ru(NH3)4(Ist)SO4]+ complex ion using cyclic voltammetry. The experiments show that a monolayer of the film is achieved after ten voltammetric cycles, that NO in solution can coordinate to the metal present in the layer, that dopamine, serotonin and nitrite are interferents for the detection of NO, and that the response for the nitrite is much less significant than the responses for dopamine and serotonin. The proposed modified electrode has the potential to be applied as a sensor for NO.  相似文献   

19.
Hydrogen evolution from 0.5 M H2SO4 on Ti electrodes coated with a RuxTi1−xO2 (x=0.04-0.5) layer has been studied by potentiostatic polarisation, cyclic voltammetry and ac-impedance spectroscopy. The results indicate that after a certain activation period the performance of such an electrode coating is comparable to platinum. The addition of small amounts of sodium molybdate increased the capacitance of the electrode and a reduction of the performance was observed. Increasing the temperature of the pure electrolyte from 20 to 75 °C caused an increase in the rate of the hydrogen evolution and in addition an increase of the electrode capacitance. The electrodes have been found to be rather tolerant to chloride and Fe2+ ions, and could hence be promising candidates as catalyst materials for solid polymer water electrolysis systems. From steady state measurements the Tafel slopes were found to change from −105 mV/decade for pure titanium to about −40 mV/decade for the (RuTi)O2 coated electrodes. The exchange current densities were calculated from the steady state curves, as well as from impedance data, to be about 10−4 A cm−2 after activation.  相似文献   

20.
A novel ruthenium(II) complex, [Ru(bpy)2pzip]2+ has been synthesized and characterized. The DNA-binding properties of this complex have been studied by spectroscopic and viscosity measurements. The results indicated that the complex [Ru(bpy)2pzip]2+ bound to double-stranded DNA in an intercalation mode. In the presence of Co2+, the emission of DNA–[Ru(bpy)2pzip]2+ can be quenched. And when EDTA was added, the emission was recovered. The experiment results show that [Ru(bpy)2pzip]2+ exhibited the “on–off–on” properties of molecular “light switch”.  相似文献   

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