Femtosecond to microsecond photochemistry of a [FeFe]hydrogenase enzyme model compound

Spyridon Kaziannis, Stefano Santabarbara, Joseph A. Wright, Gregory M. Greetham, Michael Towrie, Anthony W. Parker, Christopher J. Pickett, Neil T. Hunt

Research output: Contribution to journalArticle

27 Citations (Scopus)

Abstract

The photochemistry and dynamics of a model compound of the active site of the [FeFe]hydrogenase enzyme system have been studied on a wide range of time scales using a unique combination of femtosecond time-resolved infrared spectroscopy, nanosecond time-resolved infrared spectroscopy, and steady-state UV-FTIR methods. Using three different solvents, heptane, acetonitrile, and cyanoheptane, we have observed the rapid formation of solvent adduct species from the first solvation shell of the solute following photolysis of a carbonyl ligand and global fitting techniques have been employed to provide new insights into the ultrafast dynamics of this process. In addition, the use of solvent mixtures has enabled the observation of competitive ligand substitution processes at the newly created coordination site on time scales of a few nanoseconds, shedding new light on the chemical behavior of these enzyme models.

Original languageEnglish
Pages (from-to)15370-15379
Number of pages10
JournalJournal of Physical Chemistry B
Volume114
Issue number46
DOIs
Publication statusPublished - 25 Nov 2010

Keywords

  • effective core potentials
  • iron-only hydrogenase
  • molecular calculations
  • infrared-spectroscopy
  • active-site
  • subsitute
  • spectra
  • systems
  • bonds

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