Hideo Notsu

Electrochemical selectivity for redox systems at oxygen-terminated diamond electrodes

Abstract Oxygen-terminated diamond electrodes were prepared by exposing as-grown hydrogen-terminated diamond thin films to oxygen plasma. The as-grown surfaces, which were highly hydrophobic, become hydrophilic after the oxygen plasma treatment. The apparent surface conductivity was not significantly changed after the oxygen plasma treatment. However, the electrochemical responses to several redox systems became remarkably different. For example, the cyclic voltammetric anodic–cathodic peak separations for the oxygen-terminated diamond electrodes became extremely large compared to those for the as-grown electrodes. This behavior was examined in comparison with as-grown diamond and glassy carbon electrodes.

Surface carbonyl groups on oxidized diamond electrodes

Abstract Oxygen-containing functional groups can be introduced onto the surface of polycrystalline boron-doped diamond electrodes by either anodic polarization or oxygen plasma treatment. Of these, the carbonyl groups are of particular interest and can be studied specifically by means of specific chemical modification with dinitrophenylhydrazine (DNPH). The modification of the surface carbonyl groups with DNPH retards the Fe2+/3+ redox reaction, which is known to be catalyzed by carbonyl groups. Anodic polarization generated a larger number of carbonyl groups per unit area that were reactive with DNPH than that generated by oxygen plasma treatment. The molar ratio of the DNPH-reactive carbonyl groups to the total of all types of oxygen atoms could be as high as 5% for electrochemically oxidized diamond surfaces. This value is reasonable in view of steric limitations. The total number of carbonyl groups per unit area introduced by oxygen plasma treatment was probably larger than that introduced by anodic polarization, but the number that can react with DNPH is lower due to disordering by energetic oxygen ions.

Super-hydrophobic/super-hydrophilic patterning of gold surfaces by photocatalytic lithography

Super-hydrophobic and super-hydrophilic gold surfaces were prepared by modifying microstructured gold surfaces with thiols. The perfluorodecanethiol (PFDT)-modified rough gold surface was converted from super-hydrophobic (water contact angle = 150–160°) to super-hydrophilic (0–10°) by photocatalytic remote oxidation using a TiO2 film. During the remote oxidation, oxygen-containing groups were introduced to the thiol, and finally, even sulfur atoms were removed. Super-hydrophobic/super-hydrophilic patterns were also obtained by photocatalytic lithography, by using a TiO2-coated photomask. On the basis of this technique, enzymes and algal cells were patterned on the gold surfaces to fabricate biochips.

Electrochemical glucose detection using nickel-implanted boron-doped diamond electrodes

Nickel-implanted boron-doped diamond electrodes (Ni-DlA) were fabricated in view of their application for carbohydrate detection. This electrode produced well-defined and reproducible voltammograms for 1 mM glucose in alkaline media. The electrode exhibited excellent electrochemical stability with low background current even after ultrasonic treatment, indicating the strong bonding of nickel with carbon. These results indicate the promising use of Ni-DIA for the detection of carbohydrates and amino acids, and thus, an application of ion implantation as the surface modification method is effective for controlling the electrochemical properties of polycrystalline diamond thin films.

Visible-light-induced patterning of Au– and Ag–TiO2 nanocomposite film surfaces on the basis of plasmon photoelectrochemistry

A novel technique for patterning based on visible light at Au-TiO2 and Ag-TiO2 nanocomposite film surfaces has been developed for the first time. TiO2 films loaded with Au and Ag nanoparticles were modified with hydrophobic thiols to obtain hydrophobic surfaces. The surfaces were converted to hydrophilic by visible light irradiation. Hydrophobic/hydrophilic patterning was also possible by visible light irradiation through a photomask. The patterning was due to removal of the thiol based on plasmon photoelectrochemistry. Visible-light-induced plasmon resonance at the Au and Ag nanoparticles gives rise to charge separation and redox reactions. The thiol is removed from the Au-TiO2 film probably by oxidative desorption, and from the Ag-TiO2 film owing chiefly to oxidation of Ag nanoparticles to Ag+.

Deprotonation of a dinuclear copper complex of 3,5-diamino-1,2,4-triazole for high oxygen reduction activity

A dinuclear copper(II) complex of 3,5-diamino-1,2,4-triazole is one of the highly active copper-based catalysts for the oxygen reduction reaction (ORR) in basic solutions. Our in situ X-ray absorption near edge structure measurements revealed that deprotonation of the triazole ligand might cause coordination geometrical changes, resulting in the enhancement of the ORR activity.

Simultaneous evaluation of toxicities using a mammalian cell array chip prepared by photocatalytic lithography

A prototype of a mammalian cell array chip was developed on a flat glass surface. A superhydrophilic (water contact angle=5 degrees)/highly hydrophobic (120 degrees) pattern was prepared on a fluorinated polymer-coated glass surface by means of photocatalytic lithography, and A549 (a human alveolar epithelial cell line), Hep G2 (a human hepatoma cell line) and mouse fibroblast 3T3 cells were inoculated onto the superhydrophilic regions. The cell populations were confined in the superhydrophilic regions for at least 24 h and separated from each other for at least one week. Organ-specific toxicity of aflatoxin B(1) and non-specific toxicity of adriamycin were successfully detected by using the cell array chip.

Biosensing of an indoor volatile organic compound on the basis of fungal growth

A fungal biosensor plate was applied to assessment of the harmfulness of air polluted by formaldehyde. Alternariaalternata, Eurotiumherbariorum and Aspergilluspenicillioides were used as fungal species. Fungal mycelium length and optical transparency of the biosensor plate were employed as indices of the fungal growth. Formaldehyde in air was detected on the basis of growth inhibition, reflected by suppression of the growth indices. Dynamic range of the measurement was 700-4000 microg m(-3) or broader. Eurotiumherbariorum and Aspergilluspenicillioides were the most suitable fungal species to formaldehyde sensing based on the mycelium length and that based on the transparency, respectively.