Density-functional calculations of the Cu, Zn superoxide dismutase redox potential: The influence of active site distortion

The effect of hydrogen bonds around the active site of Anabaena [2Fe-2S] ferredoxin (Fd) on a vertical ionization potential of the reduced state (IP(red)) is examined based on the density functional theory (DFT) calculations. The results indicate that a single hydrogen bond increases the relative stability of the reduced state, and shifts IP(red) to a reductive side by 0.31–0.33 eV, regardless of the attached sulfur atoms. In addition, the IP(red) value can be changed by the number of hydrogen bonds around the active site. The results also suggest that the redox potential of [2Fe-2S] Fd is controlled by the number of hydrogen bonds because IP(red) is considered to be a major factor in the redox potential. Furthermore, there is a possibility that the redox potentials of artificial iron-sulfur clusters can be finely controlled by the number of the hydrogen bonds attached to the sulfur atoms of the cluster.

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CuZn Superoxide Dismutase Geometry Optimization, Energetics, and Redox Potential Calculations by Density Functional and Electrostatic Methods

Inorganic Chemistry ◽

10.1021/ic980730w ◽

1999 ◽

Vol 38 (5) ◽

pp. 940-950 ◽

Cited By ~ 43

Author(s):

Robert Konecny ◽

Jian Li ◽

Cindy L. Fisher ◽

Valerie Dillet ◽

Donald Bashford ◽

...

Keyword(s):

Superoxide Dismutase ◽

Redox Potential ◽

Density Functional ◽

Geometry Optimization ◽

Cuzn Superoxide Dismutase

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Density Functional Calculations for Modeling the Active Site of Nickel−Iron Hydrogenases. 2. Predictions for the Unready and Ready States and the Corresponding Activation Processes

Inorganic Chemistry ◽

10.1021/ic020016l ◽

2002 ◽

Vol 41 (17) ◽

pp. 4424-4434 ◽

Cited By ~ 38

Author(s):

Christian Stadler ◽

Antonio L. de Lacey ◽

Yael Montet ◽

Anne Volbeda ◽

Juan C. Fontecilla-Camps ◽

...

Keyword(s):

Active Site ◽

Density Functional Calculations ◽

Density Functional ◽

Nickel Iron

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Density Functional and Electrostatic Calculations of Manganese Superoxide Dismutase Active Site Complexes in Protein Environments

Inorganic Chemistry ◽

10.1021/ic980731o ◽

1999 ◽

Vol 38 (5) ◽

pp. 929-939 ◽

Cited By ~ 38

Author(s):

Jian Li ◽

Cindy L. Fisher ◽

Robert Konecny ◽

Donald Bashford ◽

Louis Noodleman

Keyword(s):

Superoxide Dismutase ◽

Active Site ◽

Density Functional ◽

Manganese Superoxide Dismutase ◽

Manganese Superoxide ◽

Electrostatic Calculations

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Density-Functional and Electrostatic Calculations for a Model of a Manganese Superoxide Dismutase Active Site in Aqueous Solution

The Journal of Physical Chemistry ◽

10.1021/jp960713x ◽

1996 ◽

Vol 100 (32) ◽

pp. 13498-13505 ◽

Cited By ~ 26

Author(s):

Cindy L. Fisher ◽

Jun-Liang Chen ◽

Jian Li ◽

Donald Bashford ◽

Louis Noodleman

Keyword(s):

Aqueous Solution ◽

Superoxide Dismutase ◽

Active Site ◽

Density Functional ◽

Manganese Superoxide Dismutase ◽

Manganese Superoxide ◽

Electrostatic Calculations

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Intermediates in P450 catalysis

Philosophical Transactions of The Royal Society A Mathematical Physical and Engineering Sciences ◽

10.1098/rsta.2004.1537 ◽

2005 ◽

Vol 363 (1829) ◽

pp. 793-806 ◽

Cited By ~ 28

Author(s):

Thomas L Poulos

Keyword(s):

Oxygen Atom ◽

Active Site ◽

Density Functional Calculations ◽

Density Functional ◽

Cytochromes P450 ◽

Catalytic Cycle ◽

Nuclear Resonance ◽

Heme Group ◽

Electron Paramagnetic

Cytochromes P450 catalyse the insertion of one O 2 -derived oxygen atom in unactivated C–H bonds, and as such, are potent oxidants. A significant amount is known about the P450 catalytic cycle owing partly to the single heme group at the active site that provides spectroscopic handles in tracking various intermediates. A sophisticated array of electron paramagnetic, electron double nuclear resonance, and more traditional absorption spectroscopies have been able to identify key intermediates, while crystallography has defined the structure of the substrate-free, -bound, and oxy-complexes. What has remained elusive is the Fe(IV)=O intermediate, thought to be the active hydroxylating agent. Here, theory and especially density functional calculations have provided valuable insights.

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