Insight into bio-metal interface formation in vacuo: interplay of S-layer protein with copper and iron.
The mechanisms of interaction between inorganic matter and biomolecules, as well as properties of resulting hybrids, are receiving growing interest due to the rapidly developing field of bionanotechnology. The majority of potential applications for metal-biohybrid structures require stability of these systems under vacuum conditions, where their chemistry is elusive, and may differ dramatically from the interaction between biomolecules and metal ions in vivo. Here we report for the first time a photoemission and X-ray absorption study of the formation of a hybrid metal-protein system, tracing step-by-step the chemical interactions between the protein and metals (Cu and Fe) in vacuo. Our experiments reveal stabilization of the enol form of peptide bonds as the result of protein-metal interactions for both metals. The resulting complex with copper appears to be rather stable. In contrast, the system with iron decomposes to form inorganic species like oxide, carbide, nitride, and cyanide.
1] Institut für Festkörperphysik, Technische Universität Dresden, 01062 Dresden, Germany [2] Department of Physics, St. Petersburg State University, 198504 St. Petersburg, Russia.
Anna A
AA
Makarova
Department of Chemistry, St. Petersburg State University, 198504 St. Petersburg, Russia.
Elena V
EV
Grachova
Department of Chemistry, Moscow State University, 119991 Moscow, Russia.
Vera S
VS
Neudachina
Department of Chemistry, Moscow State University, 119991 Moscow, Russia.
Lada V
LV
Yashina
Professur für Physikalische Chemie, Mess- und Sensortechnik, Technische Universität Dresden, 01062 Dresden, Germany.
Anja
A
Blüher
1] Institut für Experimentelle Physik, Technische Universität Bergakademie Freiberg, 09599 Freiberg, Germany [2] European XFEL GmbH, 22761 Hamburg, Germany [3] ITMO University, 197101 St. Petersburg, Russia.
Serguei L
SL
Molodtsov
1] Professur für Physikalische Chemie, Mess- und Sensortechnik, Technische Universität Dresden, 01062 Dresden, Germany [2] Kurt-Schwabe-Institut für Messund Sensortechnik e.V. Meinsberg, 04736 Waldheim, Germany.
Michael
M
Mertig
Institut für Experimentelle Physik, Technische Universität Bergakademie Freiberg, 09599 Freiberg, Germany.
Hermann
H
Ehrlich
Department of Physics, St. Petersburg State University, 198504 St. Petersburg, Russia.
Vera K
VK
Adamchuk
Institut für Festkörperphysik, Technische Universität Dresden, 01062 Dresden, Germany.
Clemens
C
Laubschat
Institut für Festkörperphysik, Technische Universität Dresden, 01062 Dresden, Germany.
Denis V
DV
Vyalikh
D001426:Bacterial Proteins / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D008562:Membrane Glycoproteins / Q000737:chemistry*; D008956:Models, Chemical; D010084:Oxidation-Reduction; D056951:Photoelectron Spectroscopy; D011485:Protein Binding; D013499:Surface Properties; D014618:Vacuum; D056928:X-Ray Absorption Spectroscopy
D001426:Bacterial Proteins; D008562:Membrane Glycoproteins; C055764:S-layer proteins; D003300:Copper; D007501:Iron