| |
|
| |
|
|
Computational electrochemistry in extended systems.
|
Building up on the work of Prof. Sprik I extended the redox potential
and reorganisation free energy
calculations to molecules in complex environments. We elucidated the
role of the environment (solvent, protein scaffold) and its H-bond
network on the electrochemical
properties of several systems such as quinones and metalloproteins.
In the case of quinones we have been able to
rationalize the difference in redox potentials and reorganization
energies caused by chemical substituents and
changes in their environments. especitly including H-bond effects which couldn't be captured with a continuum approach[1].
In the case of rubredoxin, an iron-sulfur protein, we explained the role of the short and long range contributions to redox potential
and reorganisation free energies for two different variants.
Explicit inclusion of molecular and electronic aspect of the environment (e.g. electronic
polarisation) turned out to be crucial for a quantitative understanding of rubredoxin properties[2].
The relevance of this approach was recognised by two successful grants through the European grid computing infrastructure
(DEISA, http://www.deisa.eu), enabling effort for software development
in 2006-2007, project ETISP, and a generous computational grant in 2007-2008, project ETISP2).
We are currently investigating the effect of point mutation in ferredoxin and Rieske proteins.
The aim of this study is to gain insight in the interplay between short range chemical effects,
such as replacement of ligands or residues in the proximity of the redox center, and long range effects,
such as protein conformation and the regulation of solvent access to the redox center.
The role electron transfer through the protein/protein interface in the ferrodoxin/ferrodixin reductase is also
addressed. [1] J. VandeVondele, M. Sulpizi, M. Sprik, Angew. Chem. Int. Ed. 45 , 1936 (2006) |
To contact me:
sulpizi@uni-mainz.de
Tel: +49 6131 3923641
Fax: +49 6131 3920496
Dr Marialore Sulpizi
Johannes Gutenberg University Mainz,
Staudinger Weg 7
55099 Mainz
Germany.