Electroconductive and photocurrent generation properties of self‐assembled monolayers formed by functionalized, conformationally‐constrained peptides on gold electrodes

The electroconductive properties and photocurrent generation capabilities of self‐assembled monolayers formed by conformationally‐constrained hexapeptides were studied by cyclic voltammetry, chronoamperometry, and photocurrent generation experiments. Lipoic acid was covalently linked to the N‐terminus of the peptides investigated to exploit the high affinity of the disulfide group to the gold substrates. Smart functionalization of the peptide scaffold with a redox‐active (TOAC) or a photosensitizer (Trp) amino acid allowed us to study the efficiency of peptide‐based self‐assembled monolayers to mediate electron transfer and photoinduced electron transfer processes on gold substrates. Interdigitated microelectrodes have shown higher film stability under photoexcitation, lower dark currents, and higher sensitivity with respect to standard gold electrodes. Copyright © 2007 European Peptide Society and John Wiley & Sons, Ltd.

[1]  E. Gatto.  Conformationally constrained peptides as new nanomaterials for electrons and energy transfer , 2008 .

[2]  C. Toniolo,et al.  Peptide folding dynamics: a time-resolved study from the nanosecond to the microsecond time regime. , 2006, The journal of physical chemistry. B.

[3]  A. Misicka,et al.  Conductance of α-Helical Peptides Trapped within Molecular Junctions , 2006 .

[4]  C. Toniolo,et al.  Static and dynamic features of a helical hexapeptide chemisorbed on a gold surface , 2006 .

[5]  C. Toniolo,et al.  Densely-packed self-assembled monolayers on gold surfaces from a conformationally constrained helical hexapeptide , 2006 .

[6]  A. Misicka,et al.  Asymmetry of electron transmission through monolayers of helical polyalanine adsorbed on gold surfaces. , 2005, The journal of physical chemistry. B.

[7]  Y. Long,et al.  Peptide electron transfer: more questions than answers. , 2005, Chemistry.

[8]  T. Morita,et al.  Effects of dipole moment, linkers, and chromophores at side chains on long-range electron transfer through helical peptides. , 2005, The journal of physical chemistry. B.

[9]  Chad A. Mirkin,et al.  Nanobiotechnology :concepts, applications and perspectives , 2005 .

[10]  C. Padeste,et al.  Molecular assembly of redox-conductive ferrocene-streptavidin conjugates--towards bio-electrochemical devices. , 2004, Biosensors & bioelectronics.

[11]  S. Hotchandani,et al.  Single-Wall Carbon Nanotube Films for Photocurrent Generation. A Prompt Response to Visible-Light Irradiation , 2004 .

[12]  C. Toniolo,et al.  Self-Assembled Monolayers of Hexapeptides on Gold: Surface Characterization and Orientation Distribution Analysis † , 2004 .

[13]  Yukio Imanishi,et al.  A Molecular Photodiode System That Can Switch Photocurrent Direction , 2004, Science.

[14]  C. Toniolo,et al.  A combined spectroscopic and theoretical study of a series of conformationally restricted hexapeptides carrying a rigid binaphthyl-nitroxide donor-acceptor pair. , 2003, Chemistry.

[15]  T. Morita,et al.  Long-range electron transfer over 4 nm governed by an inelastic hopping mechanism in self-assembled monolayers of helical peptides. , 2003, Journal of the American Chemical Society.

[16]  R. P. Bajpai,et al.  DNA electronics , 2003, EMBO reports.

[17]  C. Nakamura,et al.  Quartz crystal microbalance sensor targeting low molecular weight compounds using oligopeptide binder and peptide-immobilized latex beads , 2002 .

[18]  R. Bilewicz,et al.  Contribution of Intermolecular Interactions to Electron Transfer through Monolayers of Alkanethiols Containing Amide Groups , 2002 .

[19]  K. Ghiggino,et al.  Distance Dependence of Photoinduced Electron Transfer along α-Helical Polypeptides , 2001 .

[20]  D. B. Hibbert,et al.  Electrochemical Metal Ion Sensors. Exploiting Amino Acids and Peptides as Recognition Elements , 2001 .

[21]  C. Toniolo,et al.  The secondary structure of a membrane-modifying peptide in a supramolecular assembly studied by PELDOR and CW-ESR spectroscopies. , 2001, Journal of the American Chemical Society.

[22]  Shiro Kobayashi,et al.  Photocurrent Generation under a Large Dipole Moment Formed by Self-Assembled Monolayers of Helical Peptides Having an N-Ethylcarbazolyl Group , 2000 .

[23]  W. Kutner,et al.  Microelectrodes. Definitions, characterization, and applications (Technical report) , 2000 .

[24]  Shiro Kobayashi,et al.  Negative surface potential produced by self-assembled monolayers of helix peptides oriented vertically to a surface , 1999 .

[25]  H. Sasabe,et al.  Macrodipole Interaction of Helical Peptides in a Self-Assembled Monolayer on Gold Substrate , 1998 .

[26]  C. Toniolo,et al.  A nitroxide derivative as a probe for conformational studies of short linear peptides in solution. Spectroscopic and Molecular Mechanics investigation. , 1998 .

[27]  H. Imahori,et al.  Chain Length Effect on Photocurrent from Polymethylene-Linked Porphyrins in Self-Assembled Monolayers , 1998 .

[28]  K. Uosaki,et al.  Very Efficient Visible-Light-Induced Uphill Electron Transfer at a Self-Assembled Monolayer with a Porphyrin−Ferrocene−Thiol Linked Molecule , 1997 .

[29]  E. Itoh,et al.  ELECTRONIC DENSITY OF STATE IN METAL/POLYIMIDE LANGMUIR-BLODGETT FILM INTERFACE AND ITS TEMPERATURE DEPENDENCE , 1997 .

[30]  C. Toniolo,et al.  Distinguishing helix conformations in alanine-rich peptides using the unnatural amino acid TOAC and electron spin resonance , 1996 .

[31]  L. A. Carpino.  1-Hydroxy-7-azabenzotriazole. An efficient peptide coupling additive , 1993 .

[32]  Harry O. Finklea,et al.  Electron-transfer kinetics in organized thiol monolayers with attached pentaammine(pyridine)ruthenium redox centers , 1992 .

[33]  H. Gerischer,et al.  Photoelectrochemical studies on gold electrodes with surface oxide layers , 1981 .

[34]  M. Goodman,et al.  Synthesis of peptide oxazolones and related compounds. , 1967, Tetrahedron.

[35]  Claudio Toniolo,et al.  Control of peptide conformation by the Thorpe-Ingold effect (C?-tetrasubstitution) , 2001 .

[36]  C. Toniolo,et al.  TOAC, a nitroxide spin‐labeled, achiral Cα‐tetrasubstituted α‐amino acid, is an excellent tool in material science and biochemistry , 1998 .