Analytical applications of the electrochemiluminescence of tris (2.2 '-bipyridyl) ruthenium and its derivatives

This article presents the state of the art of analytical applications of the electrochemiluminescence (ECL) of tris (2,2'-bipyridyl) ruthenium (Ru(bpy)(3)(2+)) and its derivatives. in the last seven years, Ru(bpy)(3)(2+) ECL has attracted much interest from analysts and been successfully exploited as a detector of flow injection analysis (FIA), high-performance liquid chromatography (HPLC), capillary electrophoresis (CE), and micro total analysis systems (TAS). Immobilization of Ru(bPY)(3)(2+) on a solid surface provides several advantages over the solution-phase ECL procedure, such as the simplicity of experimental design and cost-effectiveness. After a brief discussion of the mechanism of Ru(bpy)(3)(2+) ECL, we discuss its applications in FIA, HPLC, CE and TAS and give special attention to the design of Ru(bpy)(3)(2+) ECL cells and some immobilization techniques of Ru(bpy)(3)(2+); we focus on papers published after 1997.

Electrochemical design of ultrathin platinum-coated gold nanoparticle monolayer films as a novel nanostructured electrocatalyst for oxygen reduction

The deliberate tailoring of nanostructured metallic catalysts at the monolayer-level is an ongoing challenge and could lead to new electronic and catalytic properties, since surface-catalyzed reactions are extremely sensitive to the atomic-level details of the catalytic surface. In this article, we present a novel electrochemical strategy to nanoparticle-based catalyst design using the recently developed underpotential deposition (UPD) redox replacement technique. A single UPD Cu replacement with Pt2+ yielded a uniform Pt layer on colloid gold surfaces. The ultrathin (nominally monolayer-level) Pt coating of the novel nanostructured particles was confirmed by cyclic voltammetry and X-ray photoelectron spectra (XPS). The present results demonstrate that ultrathin Pt coating effects efficiently and behaves as the nanostructured monometallic Pt for electrocatalytic oxygen reduction, and also shows size-dependent, tunable electrocatalytic ability. The as-prepared ultrathin Pt-coated Au nanoparticle monolayer electrodes reduce O-2 predominantly by four electrons to H2O, as confirmed by the rotating ring-disk electrode (RRDE) technique.

Simultaneous determination of dopamine and ascorbic acid at an in-site functionalized self-assembled monolayer on gold electrode

The in-site functionalization of 4-aminothiophenol (4-ATP) self-assembled monolayer on gold electrode at physiological pH yields a redox active monolayer of 4'-mercapto-N-phenylquinone diimine (MNPD). The functionalized electrode exhibits excellent electrocatalytic responses towards dopamine (DA) and ascorbic acid (AA), reducing the overpotentials by about 0.22 V and 0.34 V, respectively, with greatly enhanced current responses. Due to its different catalytic activities toward DA and AA, the modified electrode resolves the overlapping voltammetric responses of DA and AA into two well-defined voltammetric peaks by differential pulse voltammetry (DPV), which can be used for the simultaneous determination of these species in a mixture. The catalytic peak current obtained from DPV was linearly related to DA and AA concentration in the ranges of 5.0 x 10-6 - 1.25 x 10-4 M and 8.0 x 10-6 - 1.3 x 10-4 M with correlation coefficient of 0.999 and 0.998, respectively. The detective limits (3sigma) for DA and AA were found to be 1.2 x 10-6 M and 2.4 x 10-6 M, respectively.

Direct electrochemistry and bioelectrocatalysis of horseradish peroxidase immobilized on active carbon

For the first time horseradish peroxidase (HRP) immobilized on the surface of active carbon powder modified at the surface of a glassy carbon electrode has been shown to undergo a direct quasi-reversible electrochemical reaction. Its formal potential, E-o/, is -0.363 V in phosphate buffer solution (pH 6.8) at a scan rate of 100 mV/s and is almost independent of the scan rate in the range of 50-700 mV/s. The dependence of E-o/ on the pH of the buffer solution indicated that the conversion of HRP-Fe(III)/HRP-Fe(II) is a one-electron-transfer reaction process coupled with one-proton-transfer. The experimental results also demonstrated that the immobilized HRP retained its bioelectrocatalytic activity to the reduction of H2O2. Furthermore, the HRP adsorbed oil the surface of the active carbon powder can be stored at 4 degreesC for several months without any loss of the enzyme activity. The method presented for immobilizing HRP can be easily extended to immobilize and obtain the direct electrochemistry of other enzymes.

Immobilization and direct electrochemistry of copper-containing enzymes on active carbon

Two typical and important copper-containing enzymes, laccase (Lac) and tyrosinase (Tyr), have been immobilized on the surface of active carbon with simple adsorption method. The cyclic voltammetric results indicated that the active carbon could promote the direct electron transfer of both Lac and Tyr and a pair of well-defined and nearly symmetric redox peaks appeared on the cyclic voltammograms of Lac or Tyr with the formal potential, E-0', independent on the scan rate. The further experimental results showed that the immobilized copper-containing oxidase displayed an excellent electrocatalytic activity to the electrochemical reduction of O-2. The immobilization method presented here has several advantages, such as simplicity, easy to operation and keeping good activity of enzyme etc., and could be further used to study the direct electrochemistry of other redox proteins and enzymes and fabricate the catalysts for biofuel cell.

Novel hole-transporting materials based on 1,4-bis(carbazolyl)benzene for organic light-emitting devices

Novel hole-transporting molecules containing 1,4-bis(carbazolyl)benzene as a central unit and different numbers of diphenylamine moieties as the peripheral groups have been synthesized and characterized. These compounds are thermally stable with high glass transition temperatures of 141-157 degreesC and exhibit chemically reversible redox processes. Their amorphous state stability and hole transport properties can be significantly improved by increasing the number of diphenylamine moieties in the outer part and by controlling the symmetry of the carbazole-based molecules. These compounds can be used as good hole-tran sporting materials for organic electroluminescent (EL) devices. The device performance based on tri- and tetra-substituted carbazole derivatives is comparable to that of a typical 4,4'-bis[N-(1-naphthyl)-N-phenylamino] biphenyl (NPB)-based device.

Electrochemical deposition of silver in room-temperature ionic liquids and its surface-enhanced Raman scattering effect

The use of room-temperature ionic liquids (RTILs) as media for electrochemical application is very attractive. In this work, the electrochemical deposition of silver was investigated at a glassy carbon electrode in hydrophobic 1-n-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF6) and hydrophilic 1-n-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF4) RTILs and in KNO3 aqueous solution by cyclic voltammetric and potentiostatic transient techniques. The voltammograms showed the presence of reduction and oxidation peaks associated with the deposition and dissolution of silver from AgBF4 in both BMIMPF6 and BMIMBF4, resembling the redox behavior of AgNO3 in KNO3 aqueous solution. A crossover loop was observed in all the cyclic voltammograms of these electrochemical systems, indicating a nucleation process. From the analysis of the experimental current transients, it was shown that the electrochemical deposition process of silver in these media was characteristic of 3D nucleation with diffusion-controlled hemispherical growth, and the silver nucleation closely followed the response predicted for progressive nucleation in BMIMPF6 and instantaneous nucleation in KNO3 aqueous solution, respectively.

IrO2/SnO2 electrodes: prepared by sol-gel process and their electrocatalytic for pyrocatechol

IrO2/SnO2 (10%:90%, molar ratio) electrodes (ITEs) were prepared by the sol-gel method as an alternative to the electrode-position and thermal decomposition process. The electrodes were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), atomic force microscope (AFM), cyclic voltammetry (CV) and electrochemical impedance spectra (EIS). From the results of XRD, oxide films prepared at low temperature were in amorphous state, while hydrous IrO2 crystal and cassiterite phase SnO2 were formed at 300 degreesC or even to 500 degreesC. The highly porous structure was confirmed by AFM. The electrochemical experiments demonstrated that the sol-gel method made the ITEs having a fast electron transfer process with good stability and the optimal preparation temperature was 400 degreesC for the highest electroactivity. Furthermore, the electrocatalysis of pyrocatechol on the electrodes was investigated. A quasi-reversible process occurred and a linear range over three orders magnitude (1 x 10(-2) - 10 mM) was obtained by differential pulse voltammetry (DPV). Meanwhile the detection limit of pyrocatechol was 5 x 10(-3) mM. This study indicated that the sol-gel method was an appropriate route to prepare the IrO2/SnO2 electrodes for the electrocatalytic of pyrocatechol.

Application of impedance spectroscopy for monitoring colloid Au-enhanced antibody immobilization and antibody-antigen reactions

We used colloidal An to enhance the amount of antibody immobilized on a gold electrode and ultimately monitored the interaction of antigen-antibody by impedance measurement. Self-assembly of 6 nm (diameter) colloidal An onto the self-assembled monolayers (SAMs) of 4-aminothiophenol modified gold electrode resulted in an easier attachment of antibody. The redox reactions of [Fe(CN)(6)](4-)/[Fe(CN)(6)](3-) on the gold surface were blocked due to the procedures of self-assembly of 4-aminothiophenol and antibody immobilization, which were investigated by cyclic voltammetry and impedance spectroscopy. The interaction of antigen with grafted antibody recognition layers was carried out by soaking the modified electrode into a phosphate buffer at pH 7.4 with various concentrations of antigen at 37 degreesC for 30 min. The antibody recognition layers and their interactions with various concentrations of antigen could be detected by measurements of the impedance change. The results show that this method has good correlation for detection of Hepatitis B virus surface antigen in the range of 0.5-200 mug/l and a detection limit of about 50 ng/l.

Immunosensors based on layer-by-layer self-assembled Au colloidal electrode for the electrochemical detection of antigen

Colloidal Au particles have been deposited on the gold electrode through layer-by-layer self-assembly using cysteamine as cross-linkers. Self-assembly of colloidal Au on the gold electrode resulted in ail easier attachment of antibody, larger electrode surface and ideal electrode behavior. The redox reactions of [Fe(CN)(6)]-/[Fe(CN)(6)](3-) on the gold surface were blocked due to antibody immobilization, which were investigated by cyclic voltammetry and impedance spectroscopy. The interaction of antigen with grafted antibody recognition layers was carried out by soaking the modified electrode into a phosphate buffer at pH 7.0 with various concentrations of antigen at 37degreesC for 30 min. Further, an amplification strategy to use biotin conjugated antibody was introduced for improving the sensitivity of impedance measurements. Thus, the sensor based oil this immobilization method exhibits a large linear dynamic range, from 5 - 400 mug/L for detection of Human IgG. The detection limit is about 0.5 mug/L.

Effect of DNA flanking sequence on charge transport in short DNA duplexes

Several factors can influence charge transport (CT)-mediated DNA, such as sequence, distance, base stacking, base pair mismatch, conformation, tether length, etc. However, the DNA context effect or how flanking sequences influence redox active drugs in the DNA CT reaction and later in DNA enzymatic repair and synthesis is still not well understood. The set of seven DNA molecules in this study have been characterized well for the study of flanking sequence effects. These DNA duplexes are formed from self-complementary strands and contain the common central four-base sequence 5'-A-G-C-T-3', flanked on both sides by either (AT)(n) or (AA)(n) (n = 2, 3, or 4) or AA(AT)(2). UV-vis, fluorescence, UV melting, circular dichroism, and cyclic voltammetry experiments were used to study the flanking sequence effect on CT-mediated DNA by using daunomycin or adriamycin cross-linked with these seven DNA molecules. Our results showed that charge transport was related to the flanking sequence, DNA melting free energy, and ionic strength. For (AA)(n) or (AT)(n) species of the same length, (AA)(n) series were more stable and more efficient CT was observed through the (AA)(n) series. The same trend was observed for (AA)(n) and (AT)(n) series at different ionic strengths, further supporting the idea that flanking sequence can result in different base stacking and modulate charge transport through these seven DNA molecules.

Syntheses of fully sulfonated polyaniline nano-networks and its application to the direct electrochemistry of cytochrome c

Fully sulfonated polyaniline nano-particles, nano-fibrils and nano-networks have been achieved for the first time by electrochemical homopolymerization of orthanilic acid using a three-step electrochemical deposition procedure in a mixed solvent of acetonitrile (ACN) and water. The diameter of the uniform nano-particles is about 60nm, and the nano-fibrils can be organized in two-dimensional (21)) or three-dimensional (313) non-periodic networks with good electrical contact. Average distance between contacts is about 850 and 600 nm for a 2D and 3D system, respectively. The details of the poly(orthanilic acid) (POA) nano-structure were examined with a field emission scanning electron microscope (SEM). The structure and properties of POA were characterized with FTIR, UV-vis and electrochemical methods. The 3D POA nano-networks coated platinum electrode gave a direct electrochemical behavior of horse heart cytochrome c (Cyt c) immobilized on this electrode surface, a pair of well-defined redox waves with formal potential (E-ol) of -0.032 V (versus Ag/AgCl) was achieved. The interaction between Cyt c and POA makes the formal potential shift negatively compared to that of Cyt c in solution. Spectrophotometric and electrochemical methods were used to investigate the interaction of Cyt c with POA.

Assemble of poly(aniline-co-o-aminobenzenesulfonic acid) three-dimensional tubal net-works onto ITO electrode and its application for the direct electrochemistry and electrocatalytic behavior of cytochrome c

Stable electroactive film of poly(aniline-co-o-aminobenzenesulfonic acid) three-dimensional tubal net-works was assembled on indium oxide glass (ITO) successfully, and the cytochrome c was immobilized on the matrix by the electrostatic interactions. The adsorbed cytochrome c showed a good electrochemical activity with a pair of well-defined redox waves in pH 6.2 phosphate buffer solution, and the adsorbed protein showed more faster electron transfer rate (12.9 s(-1)) on the net-works matrix than those of on inorganic porous or even nano-materials reported recently. The immobilized cytochrome c exhibited a good electrocatalytic activity and amperometric response (2 s) for the reduction of hydrogen peroxide (H2O2). The detection limit for H2O2 was 1.5 mu M, and the linear range was from 3 mu M to 1 mM. Poly(aniline-co-o-aminobenzenesulfonic acid) three-dimensional tubal net-works was proved to be a good matrix for protein immobilization and biosensor preparation.

Modification of electrode surface through electrospinning followed by self-assembly multilayer film of polyoxometalate and its photochromic

Electrospun poly (vinyl alcohol) (PVA) nanofibers mat was collected on indium tin oxide (ITO) substrate. Heat crosslinked nanofibers mat became water-insoluble and firmly fixed on ITO substrate even in water. Oppositely charged poly (allylamine hydrochloride) (PAH) and Dawson-type polyoxometalate (POM), Na6P2Mo18O62 (P2Mo18), were alternately assembled on PVA nanofibers-coated ITO substrate to construct multilayer film through an electrostatic layer-by-layer (LBL) technique. The scanning electron microscope (SEM) images showed that P2Mo18 multilayer film was selectively deposited on PVA nanofibers while the unoccupied space by nanofibers on bare ITO was acted as substrate at the same time because the electrospun nanofibers have larger surface area and surface energy than the flat substrate. The cyclic voltammograms current responses of the P2Mo18 multilayer film on PVA/ITO electrode showed three well-defined redox couples of P2Mo18, but very small because P2Mo18 multilayer film was selectively deposited on PVA nanofibers with poor conductivity. In addition, the photochromic behavior of P2Mo18 multilayer film on PVA/ITO was investigated through UV-vis spectra and electron spin resonance (ESR). Fourier-transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS) proved that the charge-transfer complex was formed between PAH and P2Mo18 after UV irradiation.

Carboxyl-cored dendrimer and toluene-assisted fabrication of uniform platinum nanodendrites at a water/oil interface and their potential application as a catalyst

Uniform platinum nanodendrites have been prepared at a water/oil interface by a facile catalyst-free method at room temperature. This is carried out by introducing NaBH4 into the platinum precursor solution in the presence of the second generation of carboxyl-cored dendrimer ([G-2]-CO2H dendrimer) and toluene to act as a protective agent and a linker, respectively. The average fractal dimension of 1.61 of the obtained platinum nanodendrites is calculated by analysing the transmission electron micrographs using the programs Fractal Dimension Version 1.1 and Fractal Dimension Calculator. Control experiments show that the fabrication of platinum nanodendrites can be operated with a wide parameter window, which undoubtedly raises the degree of control of the synthesis process. The potential application of such a nanostructure as a catalyst is investigated, and the results reveal that they show highly efficient catalytic properties for the typical redox reaction between hexacyanoferrate (III) and thiosulfate ions at 301 K.