Effect of the Electrostatic Interaction on the Redox Reaction of Positively Charged Cytochrome c.pdfVIP

1470 Langmuir 2005, 21, Effect of the Electrostatic Interaction on the Redox Reaction of Positively Charged Cytochrome c Adsorbed on the Negatively Charged Surfaces of Acid-Terminated Alkanethiol Monolayers on a Au(111) Electrode Shin-ichiro Imabayashi,*,† Takahiro Mita,† and Takashi Kakiuchi*,‡ Department of Chemistry and Biotechnology, Faculty of Engineering, Yokohama National University, Yokohama 240-8501, Japan, and Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan Received August 10, 2004. In Final Form: November 18, 2004 The electrochemical properties of cytochrome c (cyt c) adsorbed on mixed self-assembled monolayers (SAMs) of 2-mercaptoethanesulfonate (MES)/2-mercaptoethanol (MEL) are compared with those on single- component SAMs of MES, MEL, and mercaptopropionic acid (MPA), using cyclic voltammetry and potential- modulated UVvis reflectance spectroscopy. The rate constant of electron transfer (ET), ket, of cyt c adsorbed on the SAM of MPA decreases from 1450 210 s1 at pH 7 to 890 100 s1 at pH 9. In contrast, the value of ket of cyt c on the SAM of MES is pH-independent at 100 15 s1. Those facts suggest that a large negative charge density on the SAM surface slows down the ET between cyt c and the electrode. The surface charge density of the SAM affects also the amount of electroactive cyt c, e, which decreases from 10.0 1.0 to 5.3 1.1 pmol cm2 with increasing pH from 7 to 9 on the SAM of MPA. Similarly, the ket of cyt c adsorbed on the mixed SAMs of MES/MEL sharply de