title: Photoinduced electron transfer in thin layers composed of fullerene-cyclic peptide conjugate and pyrene derivative.
abstract: A bilayer structure was constructed on gold by Langmuir-Blodgett deposition of a fullerene (C 60)-cyclic peptide-poly(ethylene glycol) (PEG) conjugate and thereafter a pyrene derivative from the air/water interface. The cyclic peptide moiety acts as a scaffold to prevent the fullerenes from self-aggregation and accordingly makes the monolayer homogeneous and stable. In addition to this gold/C 60-cyclic peptide-PEG/pyrene bilayer, a pyrene monolayer, a gold/C 60-PEG conjugate/pyrene bilayer (lacking the peptide scaffold), and a gold/pyrene/C 60-cyclic peptide-PEG bilayer (with the opposite order of layers) were also prepared, and their anodic photocurrent generation were studied in an aqueous solution containing a sacrifice electron donor. The most efficient photocurrent generation was observed in the gold/C 60-cyclic peptide-PEG/pyrene bilayer. It is considered that the C 60 unit acts not only as sensitizer but also as an electron acceptor facilitating the electron transfer from the excited pyrene unit to gold, and that the fullerene layer suppresses quenching of the excited pyrene unit by energy transfer to gold. Furthermore, the cyclic peptide scaffold helps the fullerenes disperse without aggregation in the membrane and seems to protect their redox properties or inhibit self-quenching of their excited state. It is thus concluded that a bilayer structure with desired orientation of functional units is important for efficient photoinduced electron transfer and that a cyclic peptide scaffold is useful to locate hydrophobic functional groups properly in a thin layer.
authors.affiliation: Department of Material Chemsitry, Kyoto University, Kyoto, Japan.
authors.forename: Shigekatsu
authors.initials: S
authors.lastname: Fujii
authors.forename: Tomoyuki
authors.initials: T
authors.lastname: Morita
authors.forename: Shunsaku
authors.initials: S
authors.lastname: Kimura
mesh_terms: D001671:Biochemistry / Q000379:methods; D004563:Electrochemistry / Q000379:methods; D004583:Electrons; D037741:Fullerenes / Q000737:chemistry*; D006046:Gold / Q000737:chemistry; D008027:Light; D008051:Lipid Bilayers / Q000737:chemistry; D008956:Models, Chemical; D015394:Molecular Structure; D010455:Peptides / Q000737:chemistry*; D010777:Photochemistry; D013053:Spectrophotometry / Q000379:methods; D013499:Surface Properties; D013696:Temperature
chemical_list: D037741:Fullerenes; D008051:Lipid Bilayers; D010455:Peptides; D006046:Gold