10.1021/jp511104m.s001
Manuel Gensler
Manuel
Gensler
Christian Eidamshaus
Christian
Eidamshaus
Arthur Galstyan
Arthur
Galstyan
Ernst-Walter Knapp
Ernst-Walter
Knapp
Hans-Ulrich Reissig
Hans-Ulrich
Reissig
Jürgen P. Rabe
Jürgen P.
Rabe
Mechanical
Rupture of Mono- and Bivalent Transition
Metal Complexes in Experiment and Theory
American Chemical Society
2015
Å.
dissociation mechanism
ab initio DFT calculations
bivalent model systems
monovalent interactions show
pyridine coordination complexes
scanning force microscopy
rupture
Bivalent Transition Metal Complexes
length
2015-02-26 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Mechanical_Rupture_of_Mono_and_Bivalent_Transition_Metal_Complexes_in_Experiment_and_Theory/2192209
Biomolecular
systems are commonly exposed to a manifold of forces,
often acting between multivalent ligands. To understand these forces,
we studied mono- and bivalent model systems of pyridine coordination
complexes with Cu<sup>2+</sup> and Zn<sup>2+</sup> in aqueous environment
by means of scanning force microscopy based single-molecule force
spectroscopy in combination with <i>ab initio</i> DFT calculations.
The monovalent interactions show remarkably long rupture lengths of
approximately 3 Å that we attribute to a dissociation mechanism
involving a hydrogen-bound intermediate state. The bivalent interaction
with copper dissociates also via hydrogen-bound intermediates, leading
to an even longer rupture length between 5 and 6 Å. Although
the bivalent system is thermally more stable, the most probable rupture
forces of both systems are similar over the range of measured loading
rates. Our results prove that already in small model systems the dissociation
mechanism strongly affects the mechanical stability. The presented
approach offers the opportunity to study the force-reducing effects
also as a function of different backbone properties.