Redox-Active Biomolecular Architectures and Self-Assembled Monolayers Based on a Cyclodecapeptide Regioselectively Addressable Functional Template

Abstract

A nanometer scale redox active biomolecular architecture has been successfully synthesized through an efficient chemoselective oxime based coupling between ferrocenyl groups and a regioselectively addressable cyclodecapeptide. This molecular tool exhibits electronic, structural, and chemical properties driven by the biomimetic recognition activity of the polypeptide skeleton associated to the well-defined electrochemical activity of metallocenyl probes. Biomolecular materials obtained by confinement of the redox cyclopeptide in self-assembled monolayers on gold surfaces shows efficient through-bond electron transfer from the ferrocenes to the electrode surface via the peptidic backbone, as well as markedly improved sensing properties toward anionic species in organic electrolyte, as compared to those observed in homogeneous solution.

Synthesis of electrochemical probes for nucleic acid detection

“…4). The increase of the Fc number in the stem-loop structure is associated with a logarithmic decrease of the E which tends to the theoretical value of 58 mV corresponding to a reversible redox system [11]. This improvement of system reversibility could be correlated to the thermodynamic study described previously that revealed a better stability of the hairpin structure for ODNs modified with a higher number of Ferrocenes (Table 1).…”

Electrochemistry of redox-active self-assembled monolayers

“…Ferrocenyl groups were attached to a cyclodecapeptide (designed for anion sensing) and immobilized on a gold electrode [359]. Using CV, the Laviron method was applied only to the cathodic branch of the E p vs. υ plot (only for overpotentials higher than 0.1 V) as the anodic wave became indistinguishable at scan rates > 100V/s.…”

Multivalency: influence of the residence time and the retraction rate on rupture forces measured by AFM

“…37,38 Interestingly, they have also been used for the design of a nanometer scale redox active biomolecular architecture by using ferrocenyl units. 39 In this work we provide a comprehensive study of (i) the specic binding, (ii) the inuence of the residence time (i.e. contact time), and (iii) the inuence of the retraction rate on the hostguest rupture forces between a cyclodecapeptide scaffold bearing a monovalent or a tetravalent adamantyl (guest) group and two types of b-CD (host) covered substrates.…”