We report on the observation of chirality induced spin selectivity for electrons transmitted through monolayers of oligopeptides, both for energies above the vacuum level as well as for bound electrons and for electrons conducted through a single molecule. The dependence of the spin selectivity on the molecular length is measured in an electrochemical cell for bound electrons and in a photoemission spectrometer for photoelectrons. The length dependence and the absolute spin polarization are similar for both energy regimes. Single molecule conductance studies provide an effective charge transport barrier between the two spin channels and it is found to be on the order of 0.5 eV

Self-assembled monolayers of alpha-helical peptides on a gold surface were employed as model systems for the investigation of mediated electron transfer. The peptides contained 14, 15, 16, and 17 amino acid residues. The measurements of electron transmission through single molecules of helical peptides were performed using scanning tunneling spectroscopy (STS). The molecules were trapped between the gold tip and the substrate. Electrical contact between the molecule and the gold probe was achieved by the use of peptides containing thiol groups present at each end of the helix. The conductance behavior of the peptides was examined as a function of tip-substrate distance at fixed bias voltage. Measurements performed with peptides containing different numbers of amino acid residues indicate that the distance dependence of electron transmission through an alpha-helix is weaker than that through simple n-alkyl bridges.

We synthesized an alpha-helical peptide containing two terminal thiol groups and demonstrated the method of preparation of a self-assembled monolayer (SAM) on gold with uniform orientation of the molecules on the surface. The monolayers were employed as model systems for the investigations of mediated electron transfer. The measurements of electron transfer efficiency through the peptide were performed using scanning tunneling spectroscopy (STS). The molecules were trapped between the gold tip and the substrate using a Au-S linkage. The electron transfer behavior of the peptide was examined as a function of the tip-substrate distance at fixed bias voltage and as a function of bias voltage at a fixed distance between the tip and the substrate. The data obtained from these experiments indicated that the electron transfer through alpha-helical peptide is very efficient, and its conductivity is comparable to those observed for dodecanedithiol. There is also a directional dependence of electron transmission through the peptide, which is connected with the electric field generated by the molecular dipole of the helix.

Polyalanine derivatives containing cysteamine linker R-(Ala)14NH-(CH2)2-SH, where R is ferrocenecarbonyl or hydrogen, were synthesized and then used to form self-assembled monolayers on gold. The tilt angles and the packing density of the molecules within monolayer assemblies were determined by FTIR spectroscopy and scanning tunneling microscopy, respectively. Electrochemical properties of monolayer-modified electrodes were studied using cyclic voltammetry and impedance spectroscopy. Measurements of electron-transfer rates using electrochemical techniques and scanning tunneling spectroscopy revealed asymmetry dependent on the applied voltage. It is suggested that the observed electron-transfer behavior is connected with the electric field generated by the molecular dipole of the polyalanine helix.

Organothiol molecules with one or two amide moieties replacing the methylene groups in the alkyl chain were synthesized and self-assembled in mixed monolayers on the gold electrode. Structures of the monolayer films were studied by STM and electrochemical methods. Reflectance infrared spectroscopy confirmed the formation of intermolecular hydrogen bonds between the amide groups. In the case of diamides, the extent of hydrogen bonding in the external and internal planes of the monolayer were compared and both the odd and the even-membered molecules were considered. Impedance spectroscopy and chronoamperometry were employed to measure the electron transfer rate across mixed monolayers containing less than 10% of electroactive ferrocene organothiol with one or two amide groups in the chain. In the present paper, we focus on the amide location effects on kinetics of mediated electron transfer. Our results indicate that the distance between the planes where amide moieties are located and the electrode surface is of crucial importance. Deeply “buried” (i.e., located close to the electrode surface) amide groups were found to be responsible for the significant increase of electronic coupling comparing to simple n-alkanethiol monolayers. The effect of external amides was much less pronounced. This observation was explained as due to the different extent of hydrogen bonding in the internal and external plane of amide groups.