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1.
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   

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 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   

4.
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   

5.
We have prepared thin films of arc discharge single walled nanotubes by vacuum filtration. For film thicknesses greater than 40 nm, the films are of high optical quality; the optical transmission varies by <2% over the film area when measured with a spatial resolution of 4 μm. However, the films become spatially non-uniform for film thickness below 40 nm. The in-plane DC conductivity correlates with the uniformity, increasing from ∼3800 S/m for a 10 nm thick film to ∼2-2.5 × 105 S/m for films of thickness >40 nm. Conductive atomic force microscopy maps show reasonably uniform current flow out of the plane of the film. For all thicknesses, the optical transmittance scales with film thickness as expected for a thin conducting film with optical conductivity of 1.7 × 104 S/m (λ = 550 nm). For films with t > 40 nm the ratio of DC to optical conductivity was σDC/σOp = 13.0, leading to values of transmittance and sheet resistance such as T = 80% and Rs = 110 Ω/□ for the t = 40 nm film. Electromechanically, these films were very stable showing conductivity changes of <5% and <2% when cycled over 2000 times in compression and tension respectively.  相似文献   

6.
An electrochemical impedance analysis of the doping kinetics of polydicarbazole films is reported. Polymer films of varying thickness were analyzed using an impedance model that considers spatially-restricted diffusion of ionic species. The main bulk parameters for diffusion and charge accumulation during doping were determined from fits. These parameters resulted independent of film thickness after considering the experimental error. The equilibrium (bulk) capacitance C0 varies in the range of 100-800 F cm−3. The chemical diffusion coefficient D varies within the range of 10−10 to 10−8 cm2 s−1 and increases as the steady-state potential reaches the oxidation peak potential.  相似文献   

7.
The surface of an aluminum (Al) electrode was modified with a thin film of nickel hexacyanoruthenate (NiHCR) as a novel electrode material. The modification procedure of Al surface, includes two consecutive procedures: (i) the electroless deposition of metallic nickel on the Al electrode surface from NiCl2 solution, and (ii) the chemical transformation of deposited nickel to nickel hexacyanoruthenate films in solution of 20 mM K3[Ru(CN)6] + 0.5 M KNO3. Cyclic voltammogram of the modified Al electrode showed a well-defined redox reaction due to [NiIIRuIII/II(CN)6]1−/2− system. The effects of different supporting electrolytes and solution pH were studied on the electrochemical characteristics of the modified electrode. The diffusion coefficients of K+ and Na+ cations in the film (D), the transfer coefficient (α), and the charge transfer rate constant at the modifying film/electrode interface (ks), were calculated in the presence of both K+ and Na+ cations. The stability of the modified electrode was investigated under various experimental conditions.  相似文献   

8.
Self-organized macroporous tungsten trioxide (WO3) films are obtained by anodic oxidation of DC-sputtered tungsten (W) layers on 10 mm × 25 mm indium tin oxide (ITO)-coated glass. Under optimized experimental conditions, uniformly macroporous WO3 films with a thickness of ca. 350 nm are formed. The film shows a connected network with average pore size of 100 nm and a pore wall thickness of approximately 30 nm. The anodized film becomes transparent after annealing without significant change in macroporous structure. In 0.1 M H2SO4, the macroporous WO3 films show enhanced electrochromic properties with a coloration efficiency of 58 cm2 C−1. Large modulation of transmittance (∼50% at 632.8 nm) and a switching speed of about 8 s are also achieved with this macroporous film.  相似文献   

9.
Thin films of amine functionalised mesoporous silica were deposited on tin-doped indium oxide (ITO) slides by dip-coating mixtures of TEOS (tetraethyl orthosilicate), APTES ((3-aminopropyl)triethoxysilane), and the non-ionic surfactant Brij56. The pore structure of the films was found to depend on the temperature use during calcination to remove the templates. Films calcined at 350 °C had highly ordered mesostructures with face-centred cubic pore arrangements, while films calcined at 275 °C had primitive cubic pore structures. The as-prepared films, or films extracted with acidic ethanol solutions had very poorly ordered mesopores. Calcination at 275 °C was sufficient to remove the Brij56 templates, without damaging the organic amine chains. Calcination at 350 °C however, also resulted in the lost of the organic groups. The use of ITO substrates allowed the dip-coated films to be used directly as working electrodes. At pH 4.7, the voltammetric response of [Ru(bpy)3]2+ was completely suppressed by the amine functionalised films. This was attributed to protonation of the amine groups that gave the films positive charges. At higher pH, the amine groups were no longer protonated and the voltammetric response of [Ru(bpy)3]2+ was restored. Conversely, [Ru(bpy)3]2+ was adsorbed by the unmodified films that carried negative charges at pH 4.7, resulting in a 4-fold increase in the peak currents compared to uncoated ITO. For [Fe(CN)6]3? at low pH the unmodified films blocked the response of the ions, while the functionalised films gave small but distinct voltammetric peaks.  相似文献   

10.
π-Conjugated polymers consisting of 1,10-phenanthroline units and crown ether subunits (Poly-1, Poly-2, and Poly-3) were prepared by dehalogenation polycondensation of the corresponding dibromo monomers using a zero-valent nickel complex as a condensing agent. They were characterized by elemental analysis, 1H NMR and UV–Vis spectroscopies, and cyclic voltammetry (CV). They were partly soluble in CHCl3, and the number average molecular weight of the soluble part of Poly-2, which had 15-crown-5 subunits, was estimated to be 5300. The polymers exhibited UV–Vis peaks at approximately λmax = 360 nm, which was reasonable. Complexation with [Ru(bpy)2]2+ and alkaline metal ions made the polymer soluble in organic solvents. The complexation of [Ru(bpy)2]2+ to the 1,10-phenanthroline unit proceeded quantitatively, and the [Ru(bpy)2]2+ complexes exhibited CV curves characteristic of [Ru(N-N)3]2+ complexes.  相似文献   

11.
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   

12.
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   

13.
Investigation of thin sputtered Mn films for electrochemical capacitors   总被引:2,自引:0,他引:2  
Pseudocapacitive manganese oxide films have been synthesized by anodic oxidation of metallic films deposited by sputtering. Results are presented from an electrochemical investigation into properties of these thin sputtered manganese films. Mn films with thickness ranging from 20 to 200 nm have been sputtered onto Pt coated Si wafers in an Argon atmosphere. Electrochemical oxidation converts the metal film into a porous, dendritic structure which displays significant pseudocapacitance. We have observed a specific capacitance (Cs) of 700 F/g when cycled very slowly at a constant current density of 160 μA/cm2. The same films probed by cyclic voltammetry (CV) at a rate of 5 mV/s yielded a lower specific capacitance of 400-450 F/g. Post-oxidation material loading was measured to be in the range of 25-75 μg/cm2.  相似文献   

14.
Electrochemical deposition of materials with hard magnetic properties in the as-deposited state is essential for the efficient integration of micro-magnetic components into MEMS devices. Here we discuss the growth process and the microstructure-magnetic properties correlation for two Co-rich alloys, Co-Ni-P and Co-Pt. Under suitable synthesis conditions, these materials exhibit perpendicular anisotropy and hard magnetic properties in the as-deposited state; in addition, such properties are maintained up to several micrometer film thickness through close control of the film microstructure. In the case of Co-Ni-P films we achieved a saturation magnetization of 1.21 T (963 emu/cm3), perpendicular coercivity up to 188 kA/m (2.36 kOe) at a thickness of 10 μm, and energy products up to 4.2 kJ/m3. Co-rich Co-Pt films were grown on several substrates - Cr, Cu(0 0 1), Cu(1 1 1), and Ru(0 0 0 1) - in order to control magnetic anisotropy and achieve optimum hard magnetic properties. Cu(1 1 1) contributes to stabilize the hexagonal hcp phase at high current density yielding excellent hard magnetic properties, although only in films thicker than 100 nm; saturation magnetization in these films was about 1.04 T (828 emu/cm3). Perpendicular coercivities up to 485.6 kA/m (6.1 kOe) were obtained in 1 μm thick film deposited at 50 mA/cm2. Ru(0 0 0 1) seed layers provide an appropriate interface structure to further facilitate the epitaxial growth of hcp films, yielding hard magnetic properties and perpendicular coercivity with a squareness ∼1 in films as thin as 10 nm. The hard magnetic properties were only marginally compromised at large film thickness. Deposition at higher current density (50 mA/cm2) favored markedly improved hard magnetic properties. The Co-Pt films on Ru exhibited perpendicular anisotropy with anisotropy constant up to 1.2 MJ/m3. The electrodeposition process was further extended to fill lithographically patterned hole arrays (850 nm diameter, center-to-center distance 2550 nm and about 700 nm thick resist), yielding arrays of micron-sized hard magnetic cylinders with perpendicular coercivity of 361 kA/m (4.54 kOe) and high squareness.  相似文献   

15.
A relatively new promising method for surface temperature measurement is the use of thermographic phosphors. For this application, the temperature-dependent luminescence properties of europium (III)-doped anatase (TiO2:Eu3+) thin films were studied. The films were prepared by the sol–gel method using dip coating. The structures and the morphology of the films were determined by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. Electron dispersive X-ray spectroscopy (EDX) was used to verify the europium concentration within the films. For using the films as temperature sensors the optical properties are the main concern. Therefore, the emission spectra of the films were measured after ultraviolet laser excitation (355 nm). They indicate that the red characteristic emission (617 nm) of TiO2:Eu3+ due to the 5D0 → 7F2 electric dipole transition is the strongest. The decay time constant of the exponential emission decay under UV excitation with a Nd:YAG laser (355 nm, f = 10 Hz) is strongly temperature dependent in the range from 200 °C up to 400 °C; making it useful for temperature evaluation. The temperature dependence was measured for the emission line at 617 nm; the results demonstrate that anatase doped europium (III) can be used as a thermographic phosphor.  相似文献   

16.
Transparent and adherent CeO2-ZrO2 thin films having film thicknesses ∼543-598 nm were spray deposited onto the conducting (fluorine doped tin oxide coated glass) substrates from a blend of equimolar concentrations of cerium nitrate hexahydrate and zirconium nitrate having different volumetric proportions (0-6 vol.% of Zr) in methanol. CeO2-ZrO2 films were polycrystalline with cubic fluorite crystal structure and the crystallinity was improved with increasing ZrO2 content. Films were highly transparent (T ∼ 92%), showing decrease in band gap energy from 3.45 eV for pristine CeO2 to 3.08-3.14 eV for CeO2-ZrO2 films. The different morphological features of the film obtained at various CeO2-ZrO2 compositions had pronounced effect on the ion storage capacity and electrochemical stability. CeO2-ZrO2 film prepared at 5 vol.% Zr concentration exhibited higher ion storage capacity of 24 mC cm−2 and electrochemical stability of 10,000 cycles in 0.5 M LiClO4 + PC electrolyte due to its film thickness (584 nm) coupled with relatively larger porosity (8%). The optically passive behavior of such CeO2-ZrO2 film (with 5 vol.% Zr) is affirmed by its negligible transmission modulation irrespective of repeated Li+ and electron insertion/extraction. The coloration efficiency of spray deposited WO3 thin film is found to enhance from 47 to 107 cm2 C−1 when CeO2-ZrO2 is coupled as a counter electrode with WO3 in an electrochromic device (ECD). These films can be used as stable ‘passive’ counter electrodes in electrochromic smart windows as they retain full transparency in both the oxidized and reduced states and ever-reported longevity.  相似文献   

17.
Electroformed iron and FeCo alloy   总被引:1,自引:0,他引:1  
Iron and FeCo alloys were electroformed from additive-free acidic chloride baths. Film stress and magnetic properties were strongly influenced by deposition current density and operating temperature. In general, low film stress and low coercivity (HC) was achieved with low current density and high operating temperature baths. SEM micrographs indicated that these conditions promote large grain growth. Coercivity of electroformed iron films linearly increased with increasing film stress, indicating that magnetoelastic energy is a dominant anisotropy. The addition of 0.25 M CaCl2 improves current efficiency while maintaining low film stress. The lowest iron film stress of 5 MPa was achieved from 1.5 M FeCl2 in the absence of CaCl2 at 20 mA cm−2 with a current efficiency of 91%. A “normal” codeposition of FeCo was observed in acidic chloride baths, where the deposition rate of Co2+ was faster than Fe2+. Film compositions also played an important role in magnetic properties of FeCo films in addition to film stress. Magnetic saturation (MS) of FeCo films increased linearly with an increase in deposited Fe content. High magnetic saturation with low-stress (MS of 2.3 T and σ=70 MPa) were achieved from 71Fe29Co films.  相似文献   

18.
The present work focuses on the investigation of the effect of the different crystallographic orientation of titanium grains on the formation of anodic oxide films and consequently their dielectric and semiconductive properties. By using a microcapillary cell the formation process and the electrochemical impedance spectroscopy (EIS) can be performed at high lateral resolution on variously orientated single grains of polycrystalline titanium. The oxide films were potentiodynamically formed by cyclovoltammetry. EIS measurements immediately followed by the oxide formation were used for a detailed investigation of the film properties, in particular, the relative permittivity ?r and the donor concentration ND. In contrast to the most publications it was found that under the chosen conditions the crystallographic orientation of titanium substrate has no significant influence on the oxide thickness d, the relative permittivity ?r or on the donor concentration ND of the oxide films. The relative permittivity ?r is approximately 50. The donor concentration depends on the film thickness and amounts to approximately 3 × 1018 cm−3 in minimum.  相似文献   

19.
This paper describes the electrogenerated chemiluminescence (ECL) processes of Ru(bpy)32+/nicotine system at ITO working electrode. An ECL-based method for rapid and sensitive detection of nicotine in phosphate buffer solution at pH 8.0 is established. Strong ECL emission was observed at a positive potential of 1.4 V vs. Ag/AgCl. A possible ECL mechanism is proposed for the Ru(bpy)32+/nicotine system, the oxidation product of nicotine at the electrode surface reacts with the 3+ state of ruthenium bipyridyl (2+) complex and form ruthenium complex exited state ions and thus releases photons. Effect of pH (medium/electrolyte), working potential, buffer composition, buffer concentration, reactant and co-reactant (nicotine) concentration, flow rate and loop size on the ECL spectrum of the Ru(bpy)32+/nicotine were studied. At the optimized experimental conditions, lower detection limit for nicotine was observed as 1.2 nmol L−1 (S/N = 3). Linear relationship between ECL current and concentration of nicotine was observed (up to 100 μmol L−1) with R-value of 0.997. The relative standard deviation with 5 μmol L−1 concentration of nicotine for 20 analyses was only 1.4%. A 94% recovery rate was observed in a real sample analysis without any complications/disturbance in measurement. Interferences of humid acid, camphor and SDS were not observed in their presence in the sample solution. The established procedure for nicotine quantification manifests fascinating results and can be suggested for further applications.  相似文献   

20.
A sensitive and rapid electrochemiluminescence (ECL) method for the detection of N6-Methyladenosine (m6A) in urine samples on a heated indium-tin-oxide (ITO) electrode is presented. The ECL intensity of Tris(2,2′-bipyridyl) dichlororuthenium(II)hexahydrate (Ru(bpy)32+) can be enhanced by the presence of m6A. Experimental results showed that the change of ECL intensities (ΔI) of the Ru(bpy)32+ between before and after addition of m6A was affected by the working electrode surface temperature (Te); the highest ΔI occurred at 31 °C. Under optimum conditions, the ΔI had a linear relationship with the m6A concentration in the range of 1.9 × 10−9-3.9 × 10−6 mol/L and a detection limit of 7.7 × 10−10 mol/L (S/N = 3) at Te = 31 °C. The recovery of m6A standards added to urine samples verified the accuracy of the proposed method.  相似文献   

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