Ferrocene-modified Electrode Research Articles

Interfacial Electron Transfer of Ferrocene Immobilized onto Indium Tin Oxide through Covalent and Noncovalent Interactions.

The immobilization of molecular species onto electrodes presents a direct route to modifying surface properties with molecular fidelity. Conventional methods include direct covalent attachment and physisorption of pyrene-appended molecular compounds to electrodes with aromatic character through π-π interactions. A recently reported hybrid approach extends the synthetic flexibility of the latter to a broader range of electrode materials. We report an application of this approach to immobilization of pyrene-appended ferrocene onto pyrene-functionalized indium tin oxide (ITO). The modified ITO surfaces were characterized using X-ray photoelectron spectroscopy, fluorescence spectroscopy, and electrochemical techniques. An electron-transfer rate constant ( kapp) of 100 ± 8 s-1 was measured between the electrode and immobilized ferrocene using electrochemical methods. For comparison, a ferrocene-modified electrode using conventional covalent attachment of vinylferrocene was also prepared, and kapp was measured to be 9 ± 2 s-1.

Molecular Architecture Studied by the Surface Forces Measurement.

This feature article reviews the surface forces measurement as a tool for studying molecular architecture chemistry. The history of the measurement is briefly described in the Introduction. The general overview covers specific features of the surface forces measurement as a tool for studying and using molecular architecture. This measurement is powerful for understanding interaction forces and for characterizing and discovering the phenomena at solid-liquid interfaces and soft complex matter. An apparatus for opaque samples was developed, which can be used to study not only opaque samples in various media but also electrochemical processes under various electrochemical potentials. Our studies of molecular architecture are reviewed; they include biological molecular recognition especially involved in the enzyme-substrate interaction; polyelectrolyte brushes exhibiting steric repulsion, which can be reproduced by the osmotic pressure of the counterions, and a density-dependent transition; the hydrogen-bonded molecular macrocluster formation of alcohol and carboxylic acids adsorbed on silica in nonpolar solvents such as cyclohexane; and surface forces between ferrocene-modified electrodes under various applied potentials. These studies demonstrate how the forces measurement is used to identify interacting species such as in biological systems to reveal unknown phenomena and to characterize soft complex matter and the effective potential of the electrodes. Readers will be introduced to the broad applications of the force measurement.

Selective in situ potential-assisted SAM formation on multi electrode arrays

The selective modification of individual components in a biosensor array is challenging. To address this challenge, we present a generalizable approach to selectively modify and characterize individual gold surfaces in an array, in an in situ manner. This is achieved by taking advantage of the potential dependent adsorption/desorption of surface-modified organic molecules. Control of the applied potential of the individual sensors in an array where each acts as a working electrode provides differential derivatization of the sensor surfaces. To demonstrate this concept, two different self-assembled monolayer (SAM)-forming electrochemically addressable ω-ferrocenyl alkanethiols (C11) are chemisorbed onto independent but spatially adjacent gold electrodes. The ferrocene alkanethiol does not chemisorb onto the surface when the applied potential is cathodic relative to the adsorption potential and the electrode remains underivatized. However, applying potentials that are modestly positive relative to the adsorption potential leads to extensive coverage within 10 min. The resulting SAM remains in a stable state while held at potentials <200 mV above the adsorption potential. In this state, the chemisorbed SAM does not significantly desorb nor do new ferrocenylalkythiols adsorb. Using three set applied potentials provides for controlled submonolayer alkylthiol marker coverage of each independent gold electrode. These three applied potentials are dependent upon the specifics of the respective adsorbate. Characterization of the ferrocene-modified electrodes via cyclic voltammetry demonstrates that each specific ferrocene marker is exclusively adsorbed to the desired target electrode.

Direct detection of enzyme-catalyzed products by FET sensor with ferrocene-modified electrode

An FET-based biosensor with a ferrocene-modified gold electrode detects the enzyme-produced electrons by using mediators that transfer the electrons from the enzyme to the sensor. Since an extended-gate FET sensor with a light-shielding mask can be operated without a light-shielding box, a small portable instrument will soon be realised. However, when the FET sensor detected enzyme-catalyzed products with the mediators under light conditions, measurements fluctuated due to photo-reduction of the mediators, resulting in decreased sensitivity. To improve sensitivity by reducing the fluctuation, we developed a procedure for directly detecting enzyme-catalyzed products without using the mediators. The key technique used in this procedure was a measurement technique using our developed potential-keeping method, in which the modified electrode of the FET sensor was oxidised by ferricyanide solution to make its surface the same high potential every time, and this high potential was kept until measurement because of the high input impedance of the FET structure. After this method was applied, the interfacial potential of the gold electrode decreased depending on the amount of enzyme-catalyzed products due to the ferrocene molecules immobilised on the gold electrode directly reacting with the products. The results obtained in light conditions indicated that model compounds of the products were detected from 10 μM to 10 mM with the Nernstian response of 59.2 mV/decade. Also, this method was applied to pesticide detection by using the enzyme inhibition by pesticide, and 5 ppb of diazinon was successfully detected by using only a sensor chip.

Electron-transfer characteristics of ferrocene attached to single-walled carbon nanotubes (SWCNT) arrays directly anchored to silicon(1 0 0)

High-density, surface-mounted ferrocene has been prepared using covalent immobilisation of an alcohol substituted ferrocene derivative to a pre-assembled single-walled carbon nanotubes directly anchored to silicon(1 0 0) surface (SWCNTs-Si). The formation of these ferrocene-modified electrodes (Fc-SWCNTs-Si) has been followed using X-ray photoelectron spectroscopy and atomic force microscopy. Electrochemical results show the surface concentration of ferrocenemethanol molecules is 9.26 × 10 −8 mol cm −2, which is about 500–1000 times greater than the experimentally measured coverage of ferrocene directly attached to flat Si(1 0 0) surfaces. The reversible one-electron wave of the ferrocene/ferrocenium couple was observed at 490 mV versus Ag +/Ag and the apparent rate constant of electron transfer, k app, was 21 s −1. These results suggest these ferrocene-modified electrodes are excellent candidates for molecular memory devices.

Electrochemical killing of Vibrio alginolyticus using ferrocene-modified electrode

Electrochemical killing of the marine gram-negative bacterium, Vibrio alginolyticus, attached to a basal-plane pyrolytic graphite electrode modified with ferrocene was carried out. The survival ratio decreased to 43% when a low potential of 0.2 V versus a saturated calomel electrode was applied for 30 min and was 3% after applying 0.4 V. After the potentials were applied, the cells were stained with the fluorescent dye, propidium iodide (PI), and the change in cell membrane permeability was observed. PI-stained cell ratio almost correlated with the dead cell ratio obtained by the colony formation method when using the bare graphite electrode. In contrast, when using the ferrocene-modified electrode, PI-stained cell ratio did not correlate with the dead cell ratio and increased when potentials of above 0.8 V were applied. When using the ferrocene-modified electrode, the killing effect was not due to the change in cell membrane permeability and might be due to the electrocatalytic oxidation of intracellular substances.

Electrocatalytic oxidation of ascorbic acid and voltammetric determination with a ferrocene-modified platinum electrode

Ferrocene attached to the surface of a platinum electrode catalyses the electrochemical oxidation of ascorbic acid in acidic buffer solutions. The overpotential for ascorbic acid oxidation is decreased by 150 mV at pH 2.2 compared with reaction at bare platinum; and an increase in anodic current and decrease in cathodic current for the redox reaction of ferrocene occurs on addition of ascorbic acid to the solution. The ferrocene-modified electrode is useful for the voltammetric determination of ascorbic acid in natural fruit juices. The advantages result from the electrocatalytic effect and from the prevention of adsorption of inhibitory substances from solution.