Université de Fribourg

Amide neighbouring-group effects in peptides: phenylalanine as relay amino acid in long-distance electron transfer

Nathanael, Joses G. ; Gamon, Luke F. ; Cordes, Meike ; Rablen, Paul R. ; Bally, Thomas ; Fromm, Katharina M. ; Giese, Bernd ; Wille, Uta

In: ChemBioChem, 2018, vol. 19, no. 9, p. 922–926

In nature, proteins serve as media for long‐distance electron transfer (ET) to carry out redox reactions in distant compartments. This ET occurs either by a single‐step superexchange or through a multi‐step charge hopping process, which uses side chains of amino acids as stepping stones. In this study we demonstrate that Phe can act as a relay amino acid for long‐distance electron...

Université de Fribourg

Formation of silver nanoparticles by electron transfer in peptides and c‐cytochromes

Vasylevskyi, Serhii I. ; Kracht, Sonja ; Corcosa, Paula ; Fromm, Katharina M. ; Giese, Bernd ; Füeg, Michael

In: Angewandte Chemie International Edition, 2017, p. -

The reduction of Ag⁺ ions to Ag⁰ atoms is a highly endergonic reaction step, only the aggregation to Agn clusters leads to an exergonic process. These elementary chemical reactions play a decisive role if Ag nanoparticles (AgNPs) are generated by electron transfer (ET) reactions to Ag⁺ ions. We studied the formation of AgNPs in peptides by photoinduced ET, and in...

Université de Fribourg

Electronic structure of hole-conducting states in polyprolines

Monney, Nicolas P.-A. ; Bally, Thomas ; Giese, Bernd

In: The Journal of Physical Chemistry B, 2015, vol. 119, no. 22, p. 6584–6590

Electron transfer over long distances in proteins by a hopping process requires transient relay stations that can harbor charge and spin for a short time span. Certain easily oxidizable or reducible side chains may assume that role, but it has been shown that charge transport in peptides can also take place in the absence of such groups which implies that the peptide backbone provides for hopping...

Université de Fribourg

Proline as a charge stabilizing amino acid in peptide radical cations

Monney, Nicolas P.-A. ; Bally, Thomas ; Giese, Bernd

In: Journal of Physical Organic Chemistry, 2015, vol. 28, no. 5, p. 347–353

Long distance electron transfer in proteins requires relay stations that can be transitorily oxidized or reduced. Although individual prolines cannot assume this function, because of their high ionization energy, it has been shown that polyprolines have the ability to transfer charges. In order to determine the role of the proline in the hole distribution and transport within a PheProPhe...

Université de Fribourg

Electron transfer in peptides: on the formation of silver nanoparticles

Kracht, Sonja ; Messerer, Matthias ; Lang, Matthieu ; Eckhardt, Sonja ; Lauz, Miriam ; Grobéty, Bernard ; Fromm, Katharina M. ; Giese, Bernd

In: Angewandte Chemie International Edition, 2015, vol. 54, no. 10, p. 2912–2916

Some microorganisms perform anaerobic mineral respiration by reducing metal ions to metal nanoparticles, using peptide aggregates as medium for electron transfer (ET). Such a reaction type is investigated here with model peptides and silver as the metal. Surprisingly, Ag⁺ ions bound by peptides with histidine as the Ag⁺-binding amino acid and tyrosine as photoinducible electron donor cannot...

Université de Fribourg

Fragment orbital based description of charge transfer in peptides including backbone orbitals

Heck, Alexander ; Woiczikowski, P. Benjamin ; Kubař, Tomáš ; Welke, Kai ; Niehaus, Thomas ; Giese, Bernd ; Skourtis, Spiros ; Elstner, Marcus ; Steinbrecher, Thomas B.

In: The Journal of Physical Chemistry B, 2014, vol. 118, no. 16, p. 4261–4272

Charge transfer in peptides and proteins can occur on different pathways, depending on the energetic landscape as well as the coupling between the involved orbitals. Since details of the mechanism and pathways are difficult to access experimentally, different modeling strategies have been successfully applied to study these processes in the past. These can be based on a simple empirical pathway...

Université de Fribourg

Kinetics of ion transport through supramolecular channels in single crystals

Assouma, Cyrille D. ; Crochet, Aurélien ; Chérémond, Yvens ; Giese, Bernd ; Fromm, Katharina M.

In: Angewandte Chemie International Edition, 2013, vol. 52, no. 17, p. 4682–4685

Single-crystal to single-crystal transformations are possible by ion-exchange and transport reactions through supramolecular channels that are composed of crown ether molecules and use trihalide ions as scaffolds. Kinetic measurements of ion transport at different temperatures provide activation energy data and show that a very fast.