The mechanism of formic acid electro oxidation on iron tetrasulfophthalocyanine-modified platinum electrode

The mechanism of formic acid electrooxidation on iron tetrasulfophthalocyanine (FeTSPc) modified Pt electrode was investigated with electrochemical methods. It was found that a "third-body" effect of FeTSPc on Pt electrode predominates during the electrooxidation process based on unusual electrochemical results. The modification leads formic acid electrooxidation to take place through a desired direct pathway, in which the mechanism is proposed to be the gradual dehydrogenation of formic acid and the reaction of formate with hydroxyl species.

Charge Transport Processes of Immobilized Heteropolyanions at Self-assembled Monolayer Modified Gold Electrode by Electrochemical Quartz Crystal Microbalance Measurement

The in situ electrochemical quartz crystal microbalance(EQCM) technique was used to investigate the ion transport of immobilized heteropolyanions at a self-assembled monolayer(SAM) modified gold electrode during electrochemical redox process. A mixed transfer method was presented to analyse the abnormal change of resonant frequency based on the simultaneous insertion/extraction of different ions. The results indicate that the migration of HSO4- anions was indispensable in the redox process of the heteropolyan ions in a I mol/L H2SO4 solution and played a key role in the abnormal change of the resonant frequency. Such a change was attributed to different packing densities derived by means of differently immobilized methods.

Electrochemical catalysis and thermal stability characterization of laccase-carbon nanotubes-ionic liquid nanocomposite modified graphite electrode

The hydrophobic carbon nanotubes-ionic liquid (CNTs-IL) get forms a stable modified film on hydrophobic graphite electrode surface. Laccase immobilized on the CNTs-IL gel film modified electrode shows good thermal stability and enhanced electrochemical catalytic ability. The optimal bioactivity occurs with increasing temperature and this optimum is 20 degrees C higher in comparison to free laccase. The improvement of laccase thermal stability may be due to the microenvironment of hydrophobic CNTs-IL gel on graphite electrode surface. On the other hand, the sensitive detection of oxygen has been achieved due to the feasibility of oxygen reduction by both of laccase and nanocomposite of CNTs-IL gel. Furthermore, the laccase hybrid nanocomposite also shows the fast electrochemical response and high sensitivity to the inhibitors of halide ions with the approximate IC50 of 0.01, 4.2 and 87.5 mM for the fluoride, chloride and bromide ions, respectively. It implies the feasibility of laccase modified electrode as an inhibition biosensor to detect the modulators of laccase.

A novel hydrogen peroxide sensor based on horseradish peroxidase immobilized on colloidal Au modified ITO electrode

A novel method to fabricate a hydrogen peroxide sensor was developed by immobilizing horseradish peroxidase (HRP) on colloidal An modified ITO conductive glass support. The cleaned glass support was modified with (3-aminopropyl)trimethoxysilane (APTMS) first to yield an interface for the assembly of colloidal An. Then 15 nm colloidal Au particles were chemisorbed onto the amine groups of the APTMS. Finally, HRP was adsorbed onto the surface of the colloidal An. The immobilized HRP displayed excellent electrocatalytical response to the reduction of hydrogen peroxide. The performance and factors influencing the resulted biosensor were studied in detail. The resulted biosensor exhibited fast amperometric response (within 5 s) to H2O2. The detection limit of the biosensor was 8.0 mumol l(-1), and linear range was from 20.0 mumol l(-1) to 8.0 mmol l(-1). Furthermore, the resulted biosensor exhibited high sensitivity, good reproducibility, and long-term stability.

Surface-enhanced resonance Raman spectroscopy and spectroscopy study of redox-induced conformational equilibrium of cytochrome c adsorbed on DNA-modified metal electrode

The redox-induced conformational equilibrium of cytochrome c (cyt c) adsorbed on DNA-modified metal electrode and the interaction mechanism of DNA with cyt c have been studied by electrochemical, spectroscopic and spectroelectrochemical techniques. The results indicate that the external electric field induces potential-dependent coordination equilibrium of the adsorbed cyt c between its oxidized state (with native six-coordinate low-spin and non-native five-coordinate high-spin heme configuration) and its reduced state (with native six-coordinate low-spin heme configuration) on DNA-modified metal electrode. The strong interactions between DNA and cyt c induce the self-aggregation of cyt c adsorbed on DNA. The orientational distribution of cyt c adsorbed on DNA-modified metal electrode is potential-dependent, which results in the deviation from an ideal Nernstian behavior of the adsorbed cyt c at high electrode potentials. The electric-field-induced increase in the activation barrier of proton-transfer steps attributed to the rearrangement of the hydrogen bond network and the self-aggregation of cyt c upon adsorption on DNA-modified electrode strongly decrease the interfacial electron transfer rate.

Electrochemical and electrocatalytic properties of microperoxidase-11 adsorbed on the poly-L-lysine modified Ag electrode

It is found that Ply adsorbed roughed silver electrode, it is easy to immobilize MP-11 with the electrostatic interaction and to prepare the MP-11/Ply/Ag modified electrode. The preparation method of the modified electrode is simple. In addition, the modified electrode obtained shows the high and stable electrocatalytic activity for O-2 reduction. It is also found that when the sixth coordination of heme in MP-11 is replaced with other coordination species with stronger coordination ability, such as imidazole, its formal redox potential shifts to the negative direction and the electrocatalytic activity for O-2 reduction is reduced.

Self-gelatinizable copolymer immobilized glucose biosensor based on Prussian Blue modified graphite electrode

A novel poly(vinyl alcohol) grafting 4-vinylpyridine self-gelatinizable copolymer was adapted to immobilize glucose oxidase. The reduction of hydrogen peroxide (H2O2) was detected at a Prussian Blue (PB) modified graphite electrode. A stable and sensitive glucose amperometric biosensor is described. The copolymer is a good biocompatible polymer in which the glucose oxidase retains high activity. Moreover, the copolymer can adhere firmly to the inorganic PB membrane. The sensor showed an apparent Michaelis-Menten constant of 18 +/- 0.2 mM and a maximum current density of 1.14 mu A cm(-2) mM(-1). The linear range is from 5 mu M to 4.5 mM glucose and the detection limit is 0.5. mu M glucose. The catalytic efficiency of PB for the reduction of H2O2 is higher than that for the oxidation of H2O2. Glucose concentrations in serum samples from healthy persons and diabetic patients were determined using the sensor. The results compared well with those provided by the hospital using a spectroscopy method.

Permselectivity of 4-aminophenol, paracetanol and phenacetin on the self-assembled n-alkanethiol monolayer modified gold electrode

The gold electrodes coated by n-alkanethiol with various chain lengths were used to study the permeability of uric acid, ascorbic acid, 4-aminophenol, paracetanol and phenacetin by means of linear sweep voltammetry. The results show that the optimum chain length is n=10. The improvements in the selectivity and the stability of the amperometric detection of these compounds in a flow stream were obtained by n-alkanethiol self assembled monolayers modified electrodes based on their differences in the hydrophobicity and the permeability.

Improvements in the selectivity of electrochemical detectors for liquid chromatography and flow injection analysis using the self-assembled n-alkanethiol monolayer-modified au electrode

4-Aminophenol (4-AP), paracetamol (PRCT), norepinephrine (NE), and dopamine (DA) (all somewhat hydrophobic compounds) were HPLC electrochemically detected while the signals from uric acid (UA) and ascorbic acid (AA) (both hydrophilic compounds at the pH studied) were minimized, taking advantage of the permselectivity of the self-assembled n-alkanethiol monolayer (C-10-SAM)-modified Au electrodes based on solute polarity, The effects of various factors, such as the chain length of the n-alkanethiol modifier, modifying time, and pH value, on the permeability of C-10-SAM coatings were examined, The calibration curves, linear response ranges, detection limits, and reproducibilities of the EC detector for 4-AP, PRCT, NE, and DA were obtained, The result shows that the EC detector can be applied in the chromatographic detection of 4-AP, PRCT, NE, and DA in urine, effectively removing the influence of UA and AA in high concentrations existing in biological samples. As a result, a great improvement in the selectivity of EC detectors has been achieved by using Au electrodes coated with neutral n-alkanethiol monolayer.

ELECTROOXIDATION OF ASCORBIC-ACID AT THE BIS(4-PYRIDYL) DISULFIDE MODIFIED GOLD ELECTRODE

The electrooxidation of ascorbic acid (AA) at the bis(4-pyridyl)disulfide (PySSPy) modified gold electrode was studied. The results showed that the oxidation process was pH-dependent. It was mainly due to the static interaction between AA and the modified

ELECTROCATALYTIC OXIDATION OF ASCORBIC-ACID AT A PRUSSIAN BLUE FILM MODIFIED MICRODISK ELECTRODE

The preparation and the behaviour of a Prussian Blue (PB) film on a platinum microdisk electrode has been described. Electrocatalytic oxidation of ascorbic acid has occurred at the PB film modified microelectrode. This shows a typical example of a modified microelectrode in electrocatalysis following our previous theoretical studies (J. Electroanal. Chem., 309 (1991) 103) and the related catalytic reaction rate constant was determined.

EASTMAN-AQ/NIII MODIFIED ELECTRODE CHARACTERIZATION AND APPLICATION IN FLOW-INJECTION DETERMINATION OF CARBOHYDRATES AND AMINO-ACIDS

A novel Eastman-AQ/Ni(II) chemically modified electrode (CME) produced by "double coating step" deposition of a poly(ester sulphonic acid) polymer film and Ni2+-containing crystalline species onto glassy carbon instead of a metallic nickel electrode exhibited stable electrocatalytic oxidation of numerous alpha-hydrogen compounds including carbohydrates, amines and amino acids. In cyclic voltammetry, the electrocatalysis appeared with an irreversible anodic wave at +0.55 V (vs. Ag/AgCl). The CME was adapted for constant-potential amperometric detection of these compounds in flow injection analysis. Using the CME, the linear response concentration range was between 1.0 x 10(-5) and 5.0 x 10(-2) mol/l and the detection limit was 5.0 x 10(-6) mol/l for glucose. The stability of the CME was adequate for routine quantitative application.

Label free electrochemiluminescence protocol for sensitive DNA detection with a tris(2,2'-bipyridyl)ruthenium(II) modified electrode based on nucleic acid oxidation

Label free electrochemiluminescence (ECL) DNA detection based on catalytic guanine and adenine bases oxidation using tris(2,2'-bipyridyl)ruthenium(II) [Ru(bpy)(3)(2+)] modified glassy carbon (GC) electrode was demonstrated in this work. The modified GC electrode was prepared by casting carbon nanotubes (CNT)/Nafion/Ru(bpy)(3)(2+) composite film on the electrode surface. ECL signals of doublestranded DNA and their thermally denatured counterparts can be distinctly discriminated using cyclic voltammetry (CV) with a low concentration (3.04 x 10(-8) mol/L for Salmon Testes-DNA). Most importantly, sensitive single-base mismatch detection of p53 gene sequence segment was realized with 3.93 x 10(-10) mol/L employing CV stimulation (ECL signal of C/A mismatched DNA oligonucleotides was 1.5-fold higher than that of fully base-paired DNA oligonucleotides). Label free, high sensitivity and simplicity for single-base mismatch discrimination were the main advantages of the present ECL technique for DNA detection over the traditional DNA sensors.

Electrochemical detection of DNA immobilized on gold colloid particles modified self-assembled monolayer electrode with silver nanoparticle label

The target DNA was immobilized successfully on gold colloid particles associated with a cysteamine monolayer on gold electrode surface. Self-assembly of colloidal An onto a cysteamine modified gold electrode can enlarge the electrode surface area and enhance greatly the amount of immobilized single stranded DNA (ssDNA). The electrontransfer processes of [Fe(CN)(6)](4)-/[Fe(CN)(6)](3-) on the gold surface were blocked due to the procedures of the target DNA immobilization, which was investigated by impedance spectroscopy. Then single stranded target DNA immobilized on the gold electrode hybridized with the silver nanoparticle-oligonucleotide DNA probe, followed by the release of the silver metal atoms anchored on the hybrids by oxidative metal dissolution, and the indirect determination of the released solubilized Ag-1 ions by anodic stripping voltammetry (ASV) at a carbon fiber microelectrode. The results show that this method has good correlation for DNA detection in the range of 10-800 pmol/1 and allows the detection level as low as 5 pmol/1 of the target oligonucleotides.