University of Siena
Doctoral School of Chemical Sciences
CYCLE XXIV – 2008/09
PhD student: Caterina Bernini - E-mail: caterinabernini@unisi.it
Area: molecular
Supervisor: Prof. Riccardo Basosi
Title of the research project: Experimental and computational investigation of transient
species and electron transfer pathways in proteins
A better understanding of the properties and functions of complex systems, like proteins and
enzymes, requires integrated strategies in which experimental and theoretical approaches are
combined in order to investigate their chemical reactivity and catalytic action.
Among other spectroscopic techniques, electron spin resonance (ESR) measurements are
highly informative on structural properties and dynamic behaviour of molecules in solution,
which is of fundamental importance to understand their stability, chemical functions and
activities. In addition, ESR spectroscopy allows to investigate free-radicals species occurring in
catalytic reactions.
The aim of this research project, that makes use of ESR spectroscopic techniques and state of
the art computational methods, is to achieve a detailed comprehension of reaction mechanisms
catalyzed by oxidative enzymes, like peroxidases and laccases, or by peroxidases like proteins,
such as cytochrome c.
It includes the investigation of radical intermediates and electron transfer pathways in proteinsubstrate interactions.
Integrated quantum mechanics/molecular mechanics (QM/MM) methods will be used for
accurate computations of structural, spectroscopic and magnetic properties of molecular
systems to interpret experimental observables and obtain atomic and electronic detailed
information on the enzymatic cycle.