Hydrogenase-poly(viologen) complex monolayers and electrochemical properties in Langmuir-Blodgett films
Mixed monolayers of a hydrogenase (H2ase) purified from Thiocapsa roseopersicina and poly(viologen) or hexadecyltrimethylammonium bromide (HTAB) were formed at the air-subphase interface. A larger H2ase-occupied area was measured in the H2ase-poly(viologen) or in the H2ase-HTAB mixed monolayers than that in the pure H2ase monolayer. These monolayers were transferred onto solid supports by the Langmuir-Blodgett (LB) method. Spectroscopic measurement indicated that H2ase activity was retained in the LB films. Cyclic voltammograms (CVs) of the H2ase-HTAB LB film showed two waves at ~-560 and ~-530 mV corresponding to the reduction and oxidation potentials of the [4Fe-4S]2+/1+ clusters of H2ase. For the H2ase-poly(viologen) LB films, the CV curves showed two broad waves centered at ~-510 and ~-480 mV, which correspond to the reversible one-electron process of poly(viologen)2+/1+ with a small contribution of the [4Fe-4S]2+/1+ clusters of H2ase. Charge transfer properties of the modified electrodes are discussed by use of chronocoulometry.