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

Charge transfer in model peptides: obtaining Marcus parameters from molecular simulation

Heck, Alexander ; Woiczikowski, P. Benjamin ; Kubař, Tomáš ; Giese, Bernd ; Elstner, Marcus ; Steinbrecher, Thomas B.

In: The Journal of Physical Chemistry B, 2012, vol. 116, p. 2284–2293

Charge transfer within and between biomolecules remains a highly active field of biophysics. Due to the complexities of real systems, model compounds are a useful alternative to study the mechanistic fundamentals of charge transfer. In recent years, such model experiments have been underpinned by molecular simulation methods as well. In this work, we study electron hole transfer in helical model...

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

Elektronentransfer in Peptiden : Bildung von Silbernanopartikeln

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

In: Angewandte Chemie, 2015, vol. 127, no. 10, p. 2954-2958

Einige Mikroorganismen zeigen anaerobe mineralische Respiration, bei der sie Metallionen zu Metallnanopartikeln reduzieren. Hierbei werden Peptide als Medium für den Elektronentransfer (ET) verwendet. Diese Reaktionsklasse wird anhand eines Modellpeptids und Silber als Metall diskutiert. Erstaunlicherweise können Silberionen, die von Peptiden mit Histidin als silberbindender Aminosäure und...

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

The influence of dipole moments on the mechanism of electron transfer through helical peptides

Lauz, Miriam ; Eckhardt, Sonja ; Fromm, Katharina M. ; Giese, Bernd

In: Physical Chemistry Chemical Physics, 2012, vol. 14, no. 40, p. 13785-13788

The life time of aromatic radical cations is limited by reactions like β-elimination, dimerization, and addition to the solvent. Here we show that the attachment of such a radical cation to the C-terminal end of an α-/3₁₀-helical peptide further reduces its life time by two orders of magnitude. For PPII-helical peptides, such an effect is only observed if the peptide contains an adjacent...

Université de Fribourg

Kinetics and mechanism of mineral respiration: how iron hemes synchronize electron transfer rates

Chabert, Valentin ; Babel, Lucille ; Füeg, Michael P. ; Karamash, Maksym ; Madivoli, Edwin S. ; Herault, Nelly ; Dantas, Joana M. ; Salgueiro, Carlos A. ; Giese, Bernd ; Fromm, Katharina M.

In: Angewandte Chemie International Edition, 2020, vol. 59, no. 30, p. 12331-12336

Anaerobic microorganisms of the Geobacter genus are effective electron sources for the synthesis of nanoparticles, for bioremediation of polluted water, and for the production of electricity in fuel cells. In multistep reactions, electrons are transferred via iron/heme cofactors of c‐type cytochromes from the inner cell membrane to extracellular metal ions, which are bound to outer membrane...

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.

Université de Fribourg

Kinetik des Ionentransports durch supramolekulare Kanäle in Einkristallen

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

In: Angewandte Chemie, 2013, vol. 125, no. 17, p. 4780-4783

Einkristall-zu-Einkristall-Umwandlungen sind durch Ionenaustausch- und Transportreaktionen durch supramolekulare Kanäle möglich, die aus Kronenether- Molekülen bestehen und Trihalogenid-Ionen als Gerüst nutzen. In kinetischen Messungen des Ionentransports bei unterschiedlichen Temperaturen wurde die Aktivierungsenergie für solche Systeme bestimmt, und ein schneller Austausch zwischen K+-...