Electron transfer reaction of stellacyanin at a bare glassy carbon electrode

Direct (unmediated) electrochemistry of Rhus vernicifera stellacyanin at a glassy carbon electrode has been briefly investigated in phosphate buffer. The voltammetry was practically independent of the buffer concentration, suggesting that the interaction between stellacyanin and the glassy carbon electrode is mainly realized through the hydrophobic interaction. The quasi-reversible process was found to be diffusion controlled at a sweep rate < 80 mVs-1. From stellacyanin concentration dependence, a transformation from linear diffusion to radial diffusion was observed. Two-step voltammetry was affected by translocations of the active site (rotation of the protein molecule on the electrode surface and diffusion). Activation energies for reduction and oxidation processes were determined to be 24 kJmol-1 and 54 kJmol-1, respectively, by the stationary method, and 15 kJmol-1 and 66 kJmol-1, respectively, by cyclic voltammetry. The considerable difference in the activation energies is supposedly due to the reduction and oxidation which are performed utilizing different electron-transfer pathways or because only one electron-transfer pathway (probably through His92) is significantly changed during the reorganization between the oxidized and reduced forms. The fact that the diffusion constant estimated from one-step voltammetry (Dox = 4.2 x 10(-9) cm2 s-1 for 484 microM stellacyanin) is much smaller than that determined from cyclic voltammetry (7.5 x 10(-7) cm2 s-1) derives from the fact that motions of the stellacyanin molecule (rotation leading to translocation of the active site and diffusion) are not fast enough to allow data from potential step voltammetry to be treated as the reversible process, but are fast enough to allow data from cyclic voltammetry to be treated as a diffusion-controlled process.