Syuhei Yoshino

Self-Regulating Enzyme−Nanotube Ensemble Films and Their Application as Flexible Electrodes for Biofuel Cells

Nanostructured carbons have been widely used for fabricating enzyme-modified electrodes due to their large specific surface area. However, because they are random aggregates of particular or tubular nanocarbons, the postmodification of enzymes to their intrananospace is generally hard to control. Here, we describe a free-standing film of carbon nanotube forest (CNTF) that can form a hybrid ensemble with enzymes through liquid-induced shrinkage. This provides in situ regulation of its intrananospace (inter-CNT pitch) to the size of enzymes and eventually serves as a highly active electrode. The CNTF ensemble with fructose dehydrogenase (FDH) showed the oxidation current density of 16 mA cm(-2) in stirred 200 mM fructose solution. The power density of a biofuel cell using the FDH-CNTF anode and the Laccase-CNTF cathode reached 1.8 mW cm(-2) (at 0.45 V) in the stirred oxygenic fructose solution, more than 80% of which could be maintained after continuous operation for 24 h. Application of the free-standing, flexible character of the enzyme-CNTF ensemble electrodes is demonstrated via their use in the patch or wound form.

Flexible, layered biofuel cells.

Similar to conventional electrolyte batteries, biofuel cells often need to be stacked in order to boost their single cell voltage (<1 V) up to a practical level. Here, we report a laminated stack of biofuel cells that is composed of bioanode fabrics for fructose oxidation, hydrogel sheets containing electrolyte and fuel (fructose), and O(2)-diffusion biocathode fabrics. The anode and cathode fabrics were prepared by modifying fructose dehydrogenase and bilirubin oxidase, respectively, on carbon nanotubes-decorated carbon fiber fabrics. The total thickness of the single set of anode/gel/cathode sheets is just 1.1mm. The laminated triple-layer stack produces an open-circuit voltage of 2.09 V, which is a 2.8-fold increase over that of a single set cell (0.74 V). The present layered cell (5 mm × 5 mm) produces a maximum power of 0.64 mW at 1.21 V, a level that is sufficient to drive light-emitting diodes.

Organic transdermal iontophoresis patch with built-in biofuel cell.

A completely organic iontophoresis patch is reported. A built-in biofuel cell is mounted on the patch that generates transdermal iontophoretic administration of compounds into the skin. The amplitude of transdermal current is tuned by integrating a conducting polymer-based stretchable resistor of predetermined resistance.

Surfactant-assisted direct electron transfer between multi-copper oxidases and carbon nanotube-based porous electrodes.

The effects of pre-treatment with surfactants on the electrocatalytic reaction of multi-copper oxidases were quantitatively evaluated using a well-structured carbon nanotube forest electrode. It was found that both the charge polarity of the head group and the aromatics in the tail part of the surfactants affect the efficiency of enzymatic electrocatalysis.

Automatic, sequential power generation for prolonging the net lifetime of a miniature biofuel cell stack.

A sequential power generation system for prolonging the net lifetime of a miniature biofuel cell stack has been developed. The system consists of layered chambers of enzyme fuel cells designed to be exposed sequentially to fuel solution by automatically switched fuel flow. The cell chambers were initially separated by magnetized plastic covers sealed with a degradable glue, poly(lactic-co-glycolic acid) (PLGA). The time that the cover was opened by attraction with an external magnet, thereby activating the following cell, was adjustable from a few hours to a few weeks by controlling the weight ratio of Fe(3)O(4) in the covers and the molecular weight of PLGA. By using sequential power generation in this way, the power output of the system was stable for longer periods, and therefore the net lifetime of the stack has been extended as compared with that of a single biofuel cell.

Self-powered sugar indicator using CNT-enzyme ensemble film

We report the stepwise modification of Os-complex mediator (polyvinylimidazole-[Os(bipyridine)2Cl] (PVI-[Os(bpy)2Cl]) and glucose oxidase (GOD) within the inner nano-space of a carbon nanotube forest (CNTF) film. Owing to the controlled alignment of enzyme/mediator/electrode in the ensemble, the prepared film electrode has both a high-efficiency (turnover rate of ca. 650 s−1) and a large net oxidation current (ca. 15 mA cm−2). The previous GOD electrodes developed by monolayer-based and polymer-based approaches have either of the performances (efficiency or net activity). In addition, the present GOD electrode is a flexible film that could be used by winding on needle devices.

Microfluidic Biological Fuel Cells: Automatic Series-Connection and Relay Systems

Enzymatic biofuel cells have attracted attention. However, there are drawbacks to be overcome for practical applications: the lower output voltage and shorter life time. In this paper, I will present our recent progress in MEMS techniques-based challenge to these problems. The possible output voltage of a single biofuel cell is generally lower than 1 V. The series connection of biofuel cells requires a system for ionic isolation between each cell. We will report an automatic air-valve to connect biofuel cells in series based on the air-trapping at a lotus leaf-like superhydrophobic structure that is manufactured between fuel cells arrayed in a microfluidic channel. The lifetime of an operating enzymatic fuel cell is limited typically within one week. We have been developing the parallel-connected biological micro fuel cells, each of which is shielded from fuel solutions by using degradable materials such as PLGA.