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 Hunt

doi:10.1021/jp107618n

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 Hunt

Research output: Contribution to journal › Article › peer-review

33 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 language	English
Pages (from-to)	15370-15379
Number of pages	10
Journal	The Journal of Physical Chemistry B
Volume	114
Issue number	46
DOIs	https://doi.org/10.1021/jp107618n
Publication status	Published - 22 Oct 2010

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10.1021/jp107618n

Cite this

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title = "Femtosecond to microsecond photochemistry of a [FeFe]hydrogenase enzyme model compound",

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.",

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T1 - Femtosecond to microsecond photochemistry of a [FeFe]hydrogenase enzyme model compound

AU - Kaziannis, Spyridon

AU - Santabarbara, Stefano

AU - Wright, Joseph A

AU - Greetham, Gregory M.

AU - Towrie, Michael

AU - Parker, Anthony W.

AU - Pickett, Christopher J

AU - Hunt, Neil

PY - 2010/10/22

Y1 - 2010/10/22

N2 - 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.

AB - 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.

U2 - 10.1021/jp107618n

DO - 10.1021/jp107618n

M3 - Article

VL - 114

SP - 15370

EP - 15379

JO - Journal of Physical Chemistry B

JF - Journal of Physical Chemistry B

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