The first enzyme-based catalyst that is superior to platinum in the four-electron electroreduction of oxygen to water is reported. The smooth Pt cathode reached half and 90% of the mass transport-limited current density at respective overpotentials of -0.4 and -0.58 V in 0.5 M sulfuric acid, and only at even higher overpotentials in pH 7.2 phosphate buffer. In contrast, the smooth "wired" bilirubin oxidase cathode reached half and 90% of the mass transport-limited current density at respective overpotentials as low as -0.2 and -0.25 V. The mass transport-limited current density for the smooth "wired" enzyme cathode in PBS was twice that with smooth Pt in 0.5 M sulfuric acid. Under 1 atm O2 pressure, O2 was electroreduced to water on a polished carbon cathode, coated with the "wired" BOD film, in pH 7.2 saline buffer (PBS) at an overpotential of -0.31 V at a current density of 9.5 mA cm-2. At the same overpotential, the current density of the polished platinum cathode in 0.5 M H2SO4 was 16-fold lower, only 0.6 mA cm-2.

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We found that CODH is a fascinating enzyme for the electrochemical conversion of CO2 to CO. It could reduce CO2 to CO at -0.57 V vs NHE with approximately 100% current efficiency in 0.1 M phosphate buffer (pH 6.3). Nature's unique structure of C-cluster in CODH would be responsible for the low overpotential and the selective and fast conversion of CO2. The turnover number per C-cluster is 700 h-1, and the pH optimum is 6.3.

The electrochemical sandwich-type, enzyme-amplified assay of Zhang, Kim, and Heller (Anal. Chem. 2003, 75, 3267-3269) was simplified by replacing the amplifying horseradish peroxidase with bilirubin oxidase (BOD). BOD catalyzes the reduction of ambient O(2) to water and obviates the need for adding H(2)O(2). Femtomolar (10(-)(15) M) concentrations of DNA were detected at a 10-microm-diameter tip of a carbon fiber electrode. Correspondingly, a few thousand copies of DNA were detected in approximately 5-microL samples. The sandwich is formed in an electron-conducting redox hydrogel, to the polymer of which a DNA capture sequence is bound. Capture of the analyte DNA and its hybridization with a BOD-labeled complementary DNA sequence, electrically connects the BOD label to the electron-conducting redox polymer, which is in electrical contact with the electrode. Placing the BOD in contact with the redox polymer thus converts the noncatalytic base layer into a catalyst for the electroreduction of O(2) to water at +0.12 V (vs Ag/AgCl) (Figure 1). In an exemplary assay, approximately 3000 copies of the iron transporting sequence of the sit gene of Shigella flexneri were detected without PCR amplification.

Adsorption of carboxylic acids from liquid solutions on gold was investigated by electrochemical experiments including voltammetric measurements and quartz crystal microgravimetry. The adsorption was found to occur at gold surfaces held at relatively high electrical potentials, and the adsorption step was associated with anodic currents. From the experimental evidences, we propose that the carboxylic acid molecules adsorb on a gold surface through an anodic reaction that is analogous to the previously studied adsorption reaction of organic sulfur compounds forming self-assembled monolayers. The potentials at which the carboxylic acids adsorb to appreciable extents were much higher than the potentials at which thiols start to adsorb. In all of the adsorption reactions of thiols, disulfides, and carboxylic acids, oxidation of the metal surface, assisted by the adsorbate−metal interaction, appears to be a common requirement for the adsorption.