An SECM study on the influence of cationic, membrane-active peptides on a gold-supported self-assembled monolayer

The influence of the membrane active peptides, Tat44–57 (activator in HIV-1) and melittin (active content of bee venom), on self-assembled monolayers of 6-mercaptohexanoic acid (MHA) on gold electrodes has been studied with scanning electrochemical microscopy (SECM). It was found that MHA, when deprotonated at physiological pH, significantly affected the relative rates of electron transfer between the [Fe(CN)6]4− solution based mediator and the underlying gold electrode, predominantly by the electrostatic interaction between the mediator and MHA. Upon the introduction of Tat44–57 ormelittin to the electrolyte, the relative rate of electron transfer through the MHA layer could be increased or decreased depending on the mediator used. However, in all cases it was found that these peptides have the ability to be incorporated into synthetic SAMs, which has implications for future electrochemical studies carried out using cell mimicking membranes immobilised on such layers.

Renewable surface electrodes based on dopamine functionalized exfoliated graphite: NADH oxidation and ethanol biosensing

Exfoliated graphite (EG) was modified by covalently attaching dopamine (DA) (3,4-dihydroxyphenethylamine) through amide linkages, using -COOH groups introduced on the EG surface. The modified material was characterized by FT-IR spectroscopy, Xray photoelectron spectroscopy and electrochemical techniques. Composites of DA modified EG dispersed in organically modified silicates were prepared by a sol-get process. Electrodes were fabricated by casting the composites in glass tubes. The sol-gel based electrodes were found to be active for the electrocatalytic oxidation of NADH and biosensing of ethanol in presence of NAD(+) and alcohol dehydrogenase enzyme. The modified composite electrodes were found to be stable for several months. The surface of the electrode could be renewed just by mechanically polishing the electrode using emery sheets. The modified EG was also pressed and restacked in the form of a pellet and the use of this material as a binderless bulk-modified electrode was also demonstrated. The performance of sol-gel derived composite EG electrodes with binderless bulk-modified EG electrodes was compared. (C) 2002 Elsevier Science B.V. All rights reserved.

Multilayer assemblies of polyelectrolyte-gold nanoparticles for the electrocatalytic oxidation and detection of arsenic(III)

Multilayers of poly(diallyldimethylammonium chloride) (PDDA) and citrate capped Au nanoparticles (AuNPs) anchored on sodium 3-mercapto-1-propanesulfonate modified gold electrode by electrostatic layer-by-layer assembly (LbL) technique are shown to be an excellent architecture for the direct electrochemical oxidation of As(III) species. The growth of successive layers in the proposed LbL architecture is followed by atomic force microscopy, UV-vis spectroscopy, quartz crystal microbalance with energy dissipation, and electrochemistry. The first bilayer is found to show rather different physico-chemical characteristics as compared to the subsequent bilayers, and this is attributed to the difference in the adsorption environments. The analytical utility of the architecture with five bilayers is exploited for arsenic sensing via the direct electrocatalytic oxidation of As(III), and the detection limit is found to be well below the WHO guidelines of 10 ppb. When the non-redox active PDDA is replaced by the redoxactive Os(2,2'-bipyridine)(2)Cl-poly(4-vinylpyridine) polyelectrolyte (PVPOs) in the LbL assembly, the performance is found to be inferior, demonstrating that the redox activity of the polyelectrolyte is futile as far as the direct electro-oxidation of As(III) is concerned. (C) 2012 Elsevier Inc. All rights reserved.

Adsorption of human serum albumin onto gold: a combined electrochemical and ellipsometric study

Human serum albumin adsorption onto gold surfaces was investigated by electrochemical and ellipsometric methods. Albumin adsorption onto gold was confirmed by the change of the open circuit potential of gold and by the ellipsometric parameter variation during albumin immobilization. In both experiments the parameters reached stable values within 10-15 min. The albumin adsorption layer thickness measured with the ellipsometer was about 1.5 nm. The adsorption of albumin Under applied potential was also investigated and it was found that both positive and negative applied potential promote albumin adsorption. Changes in the optical parameters of bare gold and albumin adsorbed onto gold surface under applied potential were investigated with in Situ ellipsometry. The similarity and reversibility of the optical changes showed that adsorbed albumin was stable on the gold surface Under the applied potential range (-200-600 mV). The cyclic voltammograms of K3Fe(CN)(6) on the modified gold surface showed that albumin Could partly block the oxidation and reduction reaction. (C) 2004 Elsevier Inc. All rights reserved.

Interaction Between Tripeptide Gly-Gly-His and Cu2+ Probed by Microcantilevers

Gly-Gly-His tripeptide modified microcantilever was developed by carbodiimide attachment of the Gly-Gly-His tripeptide onto a 3-mercaptopropionic acid(MPA) modified gold surface. The interaction of peptide with Cu2+ ion was studied. At a relative high concentration of Cu2+, the cantilever bent toward the gold side initially as the N atom of imidazole ring and carboxyl group in different peptide coordinate with Cu2+, which results in a tensile surface stress. And then the reversed deflection of microcantilever was observed, which implies that the peptide-Cu2+ complex are formed with conformation transition. In another case, i.e., at a relative low concentration Of Cu2+, only the process of conformation transition was observed due to the coordination mode can not be formed initially. The influences of pH and salt concentration of the test solution on the performance of the sensor were studied. The results show that the maximum deflection was obtained at pH 7 and the bonding Of Cu2+ to the Gly-Gly-His tripeptide was inhibited due to the formation Of CuClx2-x.

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.

Electrochemical and bioelectrochemistry properties of room-temperature ionic liquids and carbon composite materials

Room-temperature ionic liquids (RTILs) are liquids at room temperature and represent a new class of nonaqueous but polar solvents with high ionic conductivity. The conductivity property of carbon nanotubes/RTILs and carbon microbeads/RTILs composite materials has been studied using ac impedance technology. Enzyme coated by RTILs-modified gold and glassy carbon electrodes allow efficient electron transfer between the electrode and the protein and also catalyze the reduction Of O-2 and H2O2,

Electrooxidative polymerization of phenothiazine derivatives on screen-printed carbon electrode and its application to determine NADH in flow injection analysis system

The electrooxidation polymerization of phenothiazine derivatives, including azure A and toluidine blue 0, has been studied at screen-printed carbon electrodes in neutral phosphate buffer. Both compounds yield strongly adsorbed electroactive polymer with reversible behavior and formal potentials closed to 0.04 V at pH 6.9. The modified electrodes exhibited good stability and electrocatalysis for NADH oxidation in phosphate buffer (pH 6.9), with an overpotential of more than 500 mV lower than that of the bare electrodes. Further, the modified screen-printed carbon electrodes were found to be promising as an amperometric detector for the flow injection analysis (FIA) of NADH, typically with a dynamic range of 0.5-100 muM.

Electropolymerization of azure B on a screen-printed carbon electrode and its application to the determination of NADH in a flow injection analysis system

The electrooxidation polymerization of azure B on screen-printed carbon electrodes in neutral phosphate buffer was studied. The poly(azure B) modified electrodes exhibited excellent electrocatalysis and stability for dihydronicotinamide adenine dinucleotide (NADH) oxidation in phosphate buffer (pH 6.9), with an overpotential of more than 400 mV lower than that at the bare electrodes. Different techniques, including cyclic voltammetry, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy have been employed to characterize the poly (azure B) film. Furthermore, the modified screen-printed carbon electrodes were found to be promising as an amperometric detector for the flow injection analysis (FIA) of NADH, typically with a dynamic range of 0.5 muM to 100 muM.

Assembly of multilayer films containing iron(III)- substituted Dawson-type heteropolyanions and its electrocatalytic properties: cyclic voltammetry, electrochemical impedance spectroscopy and UV-Vis spectrometry

Ultrathin multilayer films have been prepared by means of alternate adsorption of iron(Ill)-substituted heteropolytungstate anions and a cationic redox polymer on the 4-aminobenzoic acid modified glassy carbon electrode surface based on electrostatic layer-by-layer assembly. Cyclic voltammetry, electrochemical impedance spectroscopy and UV-Vis absorption spectrometry have been used to easily monitor the uniformity of thus-formed multilayer films. Especially, the electrochemical impedance spectroscopy is successfully used to monitor the multilayer deposition processes and is a very useful technique in the characterization of multilayer films because it provides valuable information about the interfacial impedance features. All these results reveal regular film growth with each layer adsorption. The resulting multilayer films can effectively catalyze the reduction of H2O2,NO2- and BrO3-.

The channel behavior of gramicidin in mercaptan self-assembled monolayer membrane

The present paper reports the channel behavior of gramicidin in mercaptan self-assembled monolayer on the surface of the gold electrode by using the electrochemical method. The current responses to K+ ions and the electrode potential for the gold electrodes modified with self-assembled mercaptan monolayer incorporating and not incorporating gramicidin D were compared. The results firstly indicated that gramicidin D molecules can be incorporated into the mercaptan monolayer assembled on the surface of the gold electrode and form monovalent ion channel. A mechanism of the phenomenon was proposed.

Study on surface acid-base property of carboxylic acid-terminated self-assembled monolayers by cyclic voltammetry and electrochemical impedance spectroscopy

Cyclic voltammetry and electrochemical impedance spectroscopy were used to study the surface acid-base property of carboxylic acid-terminated self-assembled monolayers (SAMs). A carboxylic acid-terminated thiol, such as thioctic acid (1,2-dithiolane-3-pentanoic add), was self-assembled on gold electrodes. Electron transfer between the bulk solution and the SAM modified electrode was studied at different pH using Fe(CN)(6)(3-) as a probe. The surface pK(a) of thioctic acid was determined by cyclic voltammetry and electrochemical impedance spectroscopy to be 5.6 +/- 0.1 and 5.8 +/- 0.1, respectively. The method is compared with other methods of monolayer pK(a) measurement.

EQCM characterization of self-assembled kinetics of 4-pyridyl hydroquinone at Pt surface and its ion transfer in electrochemical redox

The adsorbed kinetics, proton transportation in electrochemical redox process of 4-pyridyl hydroquinone (4PHQ) self-assembled monolayer (SAM) modified Pt electrode were studied by electrochemical quartz crystal microbalance (EQCM) in situ. It proved that the electrode was modified by a monolayer and underwent a rapid electron transfer. It was a slow adsorbed kinetic process. The ion transfer in the electrochemical redox at the SAM-modified electrode surface mainly involved into the hydrate hydrogen ion.

Synthesis of N-(n-octyl)-N'-(10-mercaptodecyl)-4,4'-bipyridinium dibromide and electrochemical behaviour of its monolayers on a gold electrode

A new viologen derivative of N-(n-octyl)-N'-(10-mercaptodecyl)-4,4'-bipyridinium dibromide has been prepared and characterized by elemental analysis, IR, H-1 NMR, MS and TG-DTA. X-Ray photoelectron spectroscopy, cyclic voltammetry and chronoamperometry have been used to characterize the monolayers formed by this compound on the bulk gold electrodes by self-assembly.

PROMOTER EFFECT OF POLY(4-VINYLPYRIDINE) ON THE DIRECT ELECTRON-TRANSFER BETWEEN CYTOCHROME-C AND GOLD ELECTRODE

The electrochemistry of cytochrome c was studied at the PVP-modified gold electrode. It was found that the promoter effect is related to the amount of PVP at the gold electrode. From our results, it can be seen that the nitrogen element in the polymer is important for accelerating the electron transfer of cytochrome c.