Application of 2-(3,4-dihydroxyphenyl)-1,3-dithialone self-assembled monolayer on gold electrode as a nanosensor for electrocatalytic determination of dopamine and uric acid.

The electrooxidation of dopamine (DA), uric acid (UA) and their mixture on a gold electrode modified by a self-assembled monolayer of 2-(3,4-dihydroxyphenyl)-1,3-dithialone has been studied by cyclic voltammetry (CV), chronoamperometry and differential pulse voltammetry (DPV). CV was used to investigate the redox properties of the modified electrode at various scan rates and the apparent charge transfer rate constant (k(s)), and transfer coefficient (α) were calculated. The mediated oxidation of DA at the modified electrode under the optimum condition (pH = 7.0) in CV occurs at a potential about 220 mV less positive than that of the unmodified gold electrode. The values of electron transfer coefficients (α), catalytic rate constant (k) and diffusion coefficient (D) were calculated for DA, using electrochemical methods. DPV exhibited a linear dynamic range over the concentration range of 0.2-250.0 µM and a detection limit (3σ) of 0.07 µM for DA. The modified electrode was used for simultaneous determination of DA and UA by DPV. The results showed that the electrode is highly efficient for the catalytic electrooxidation of DA and UA, leading to a remarkable peak resolution (~350 mV) for two compounds. The electrode was used for the determination of DA in an injection sample.

Frequency effects on the surface coverage of nitrophenyl films ultrasonically grafted onto indium tin oxide.

The covalent attachment of various organic molecules on conductive supports including indium tin oxide (ITO) using diazonium chemistry has been known for many years. A commonly used method to achieve this is the electrochemical reduction of diazonium compounds leading to radicals, followed by binding of the radicals to the support. In the present report, an alternative method using ultrasound at different frequencies (20, 582, 863, and 1142 kHz) to induce the surface grafting of nitrobenzene diazonium onto an ITO surface is described. It is shown that the grafting on ITO is more efficient in the lower ultrasonic frequency range that is ascribed to changes in the balance between the physical and chemical effects of cavitation with frequency. Both the physical and chemical effects of cavitation play important roles at all frequencies, but at high ultrasound frequencies, the physical effects are relatively small. At 20 kHz, the physical component, including mass transport, is larger than at higher frequencies, and mechanisms based on these observations have been proposed. Ultrasonic grafting has an advantage over electrografting in that it may provide more control over surface coverage, thus it is suggested that the ultrasonic method is used where the surface concentration of the organic layer must be controlled.

A highly sensitive nanostructure-based electrochemical sensor for electrocatalytic determination of norepinephrine in the presence of acetaminophen and tryptophan.

A new electrochemical sensor for the determination of norepinephrine (NE), acetaminophen (AC) and tryptophan (Trp) is described. The sensor is based on carbon paste electrode (CPE) modified with 3,4-dihydroxybenzaldehyde-2,4-dinitrophenylhydrazone (DDP) and takes the advantages of carbon nanotubes (CNTs), which makes the modified electrode highly sensitive for the electrochemical detection of these compounds. Cyclic voltammetry (CV) at various scan rates was used to investigate the redox properties of the modified electrode. The apparent charge transfer rate constant, k(s), and transfer coefficient, α, for electron transfer between DDP and CNT paste electrode were calculated. The mediated oxidation of NE at the modified electrode was investigated by CV and the values of k, α and diffusion coefficient (D) were calculated. Under the optimum pH of 7.0, the oxidation of NE occurs at a potential about 215 mV less positive than that of the unmodified CPE. Differential pulse voltammetry (DPV) of NE at the modified electrode exhibited two linear dynamic ranges with a detection limit (3σ) of 77±2 nM. DPV was used for simultaneous determination of NE, AC and Trp at the modified electrode, and quantitation of NE in some real samples by the standard addition method.

Simultaneous and selective voltammetric determination of , and at a nanoparticles modified paste electrode.

A new carbon paste electrode modified with ZrO2 nanoparticles (ZONMCPE) was prepared, and used to study the electrooxidation of epinephrine (EP), acetaminophen (AC), folic acid (FA) and their mixtures by electrochemical methods. The modified electrode displayed strong resolving function for the overlapping voltammetric responses of EP, AC and FA into three well-defined peaks. The potential differences between EP - AC, AC - FA and EP - FA were 210, 290 and 500 mV respectively. Differential pulse voltammetry (DPV) peak currents of EP, AC and FA increased linearly with their concentration at the ranges of 2.0 × 10-7-2.2 × 10-3 M, 1.0 × 10-6-2.5 × 10-3 M and 2.0 × 10-5-2.5 × 10-3 M, respectively. The detection limits for EP, AC and FA were found to be 9.5 × 10-8, 9.1 × 10-7and 9.8 × 10-6 M, respectively.

Electrocatalytic oxygen reduction on functionalized gold nanoparticles incorporated in a hydrophobic environment.

The electrocatalytic properties of gold nanoparticles covalently capped with a monolayer film of 1,4-decylphenyl groups for oxygen reduction in an alkaline solution have been studied. Functionalized nanoparticles were adsorbed on a film of the same capping ligand previously grafted to a glassy carbon electrode. The molecular film-nanoparticle assembly was characterized by cyclic voltammetry and XPS. It is shown that although the attachment of the capping ligand to the electrode surface blocks direct electron transfer, the metal centers of the incorporated nanoparticles provide sites for electron tunneling from the electrode surface thus leading to sites where oxygen reduction can take place. Rotating disk voltammetry shows that the oxygen reduction reaction follows mainly a peroxide formation channel on these nanostructured surfaces. The capping ligand greatly influences the reduction mechanism by establishing a local hydrophobic environment at the reaction centers within the film.

Electrochemical reduction of oxygen on nanoparticulate gold electrodeposited on a molecular template.

The reduction of oxygen on gold electrodeposited on an organic template has been investigated. The template consisted of reduced 4-nitrophenyl groups attached to glassy carbon (GC) by the electrochemical reduction of the corresponding diazonium compound. The electrode modified by this Au nanostructured film shows electrocatalytic properties for the oxygen reduction reaction (ORR) different from those of bulk Au, GC or GC grafted with 4-nitrophenyl groups. The reduced nitrophenyl film inhibits the O2 reduction reaction. A two-step reduction mechanism with production of hydrogen peroxide in the first step and water in the second was observed in alkaline solutions. The standard heterogeneous rate constants for this two-electron transfer sequential reaction (EE reduction mechanism) have been calculated using non-linear regression analysis (NLR).

Synthesis of metal nanoparticles stabilized by metal-carbon bonds.

A new method for the preparation of metal nanoparticles in organic media is proposed. This is based on the formation of metal-carbon bonds after reduction of the corresponding diazonium derivative of the capping ligand. The particles are very stable due to the strong metal-ligand covalent bond, and the proposed method appears to be an alternative for the preparation of monolayer-protected metal nanoparticles when the formation of metal-sulfur or metal-nitrogen bonds needs to be avoided.