Geometric and electronic structure/function correlations in non-heme iron enzymes.

@article{Solomon2000GeometricAE,
  title={Geometric and electronic structure/function correlations in non-heme iron enzymes.},
  author={Edward I. Solomon and Thomas C Brunold and M. I. Davis and Jyllian N. Kemsley and Sam Keun Lee and Nicolai Lehnert and Frank Neese and Andrew J. Skulan and Yinshan Yang and J Zhou},
  journal={Chemical reviews},
  year={2000},
  volume={100 1},
  pages={
          235-350
        }
}
ion step follows the decarboxylation, which is consistent with the deuterium isotopic effects observed for thymine 7-hydroxylase which indicate that an irreversible step (or steps) occurs prior to the C-H bond breaking.395 It has also been shown for prolyl 4-hydroxylase that a substrate-derived radical is generated in the reaction, which is consistent with a rebound mechanism.437 It is important to point out that no oxygen intermediate (i.e., bridged superoxo or oxo-ferryl) has been observed… Expand
Geometric and electronic structure contributions to function in non-heme iron enzymes.
TLDR
This methodology has developed a methodology that provides detailed geometric and electronic structure insights into these NHFe(II) active sites and defined a general mechanistic strategy that many of these enzymes use: they control O2 activation (and limit autoxidation and self-hydroxylation) by allowing Fe( II) coordination unsaturation only in the presence of cosubstrates. Expand
Spectroscopic and Electronic Structure Study of ETHE1: Elucidating the Factors Influencing Sulfur Oxidation and Oxygenation in Mononuclear Nonheme Iron Enzymes.
TLDR
It is demonstrated that GSS- binds directly to the iron active site, causing coordination unsaturation to prime the site for O2 activation, and correlation of these spectral features with those of monodentate cysteine binding in isopenicillin N synthase (IPNS) shows that the persulfide is a poorer donor but still results in an equivalent frontier molecular orbital for reactivity. Expand
Proton-Electron Transfer to the Active Site Is Essential for the Reaction Mechanism of Soluble Δ9-Desaturase.
TLDR
This study study in detail one intriguing representative of the NHFe2 family of enzymes: soluble Δ9 desaturase (Δ9D) which desaturates rather than performing the thermodynamically favorable hydroxylation of substrate. Expand
Nuclear Resonance Vibrational Spectroscopy Definition of O2 Intermediates in an Extradiol Dioxygenase: Correlation to Crystallography and Reactivity.
TLDR
Insight is provided into the relative reactivities of Fe III-superoxo and FeIII-hydroperoxo intermediates in nonheme Fe enzymes and into the role H200 plays in facilitating extradiol catalysis. Expand
A density functional investigation of the extradiol cleavage mechanism in non-heme iron catechol dioxygenases
  • R. Deeth, T. Bugg
  • Chemistry, Medicine
  • JBIC Journal of Biological Inorganic Chemistry
  • 2003
TLDR
The favoured proton-assisted pathway does not involve significant radical character and has features reminiscent of a Criegee rearrangement which involves the participation of the aromatic ring π-orbitals in the formation of the new carbon-oxygen bond. Expand
Density Functional Theory Study into the Reaction Mechanism of Isonitrile Biosynthesis by the Nonheme Iron Enzyme ScoE
The nonheme iron enzyme ScoE catalyzes the biosynthesis of an isonitrile substituent in a peptide chain. To understand details of the reaction mechanism we created a large active site cluster modelExpand
Structure-function correlations in oxygen activating non-heme iron enzymes.
TLDR
A spectroscopic methodology has been developed which allows the elucidation of the geometric and electronic structures of these active sites and provides molecular level insight into the mechanisms of catalysis and its application to the determination of important active site structure-function correlations in mononuclear non-heme iron enzymes. Expand
Quantum chemical studies of dioxygen activation by mononuclear non-heme iron enzymes with the 2-His-1-carboxylate facial triad.
TLDR
Density functional theory with the B3LYP hybrid functional has been used to study the mechanisms for dioxygen activation by four families of mononuclear non-heme iron enzymes, finding that the substrate oxidation and the O-O bond cleavage are found to be coupled. Expand
Spectroscopic and electronic structure studies of the role of active site interactions in the decarboxylation reaction of alpha-keto acid-dependent dioxygenases.
The alpha-ketoglutate (alpha-KG)-dependent dioxygenases are a large class of mononuclear non-heme iron enzymes that require Fe(II), alpha-KG and dioxygen for catalysis, with the alpha-KG cosubstrateExpand
Non-heme Fe(IV)-oxo intermediates.
TLDR
The observation of non-heme Fe(IV)-oxo intermediates and Fe(II)-containing product(s) complexes with almost identical spectroscopic parameters in the reactions of two distantly related alphaKG-dependent hydroxylases suggests that members of this subfamily follow a conserved mechanism for substrate hydroxyation. Expand
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References

SHOWING 1-10 OF 57 REFERENCES
Structure of Ribonucleotide Reductase from Escherichia coli
The last few years have experienced a giant leap in our understanding of the structure and function of ribonucleotide reductases. This fascinating group of enzymes makes use of a free radicalExpand
Diiron–Oxygen Proteins
Publisher Summary This chapter reviews an emerging class of proteins called the “diiron–oxygen proteins,” which are part of a general class of iron–oxygen proteins. The chapter focuses on proteinsExpand
Cytochrome P450
TLDR
It is shown that in allylic hydroxyl ations (catalyzed by either model metalloporphyrins or cytochrome P450) rehydridization could occur to yield multiple products. Expand
Inorganic electronic structure and spectroscopy
Preface. Contributors, Volume I. Contents, Volume II. Contributors, Volume II. 1. Ligand Field Theory and the Properties of Transition Metal Complexes (A. Lever & E. Solomon). 2. ElectronExpand
Hemoglobin. Cooperativity and electronic properties.
  • M. Weissbluth
  • Chemistry, Medicine
  • Molecular biology, biochemistry, and biophysics
  • 1974
TLDR
The Huckel Method with Self-Consistent Charge and the Jahn-Teller Effect and Cooperativity in Hemoglobin are studied, which provide insights into the determinants of Cooperativity and Amino Acids, Peptides and Proteins. Expand
Probing of nucleic acids by metal ion complexes of small molecules
Molecular modelling of transition metal adducts with nucleic acids and their constituents zinc complexes as targeting agents for nucleic acids metallocene interactions with DNA and DNA processingExpand
Degradation of environmental pollutants by microorganisms and their metalloenzymes
General strategies in the biodegradation of pollutants, Thomas W. Egli oxidation of aromatic pollutants by lignin-degrading fungi and their extracellular peroxidases, Kenneth E. Hammel biodegradationExpand
Molecular magnetism : from molecular assemblies to the devices
William E. Hatfield, 1937-1995 R.D. Willett. Part I: Basic Concepts, Models and Physical Techniques. Magnetic Phenomena in Molecular Materials F. Palacio. Exchange Interactions I. Mechanisms E.Expand
Mössbauer Spectroscopy and Transition Metal Chemistry
1. Introduction.- 2. Basic Physical Concepts.- 3. Hyperfine Interactions.- 4. Experimental.- 5. Mathematical Evaluation of Mo ssbauer Spectra.- 6. Interpretation of Mo ssbauer Parameters of IronExpand
The Theory of Transition-Metal Ions
Preface 1. Introduction 2. Angular momentum and related matters 3. Electromagnetic radiation 4. The structure of free atoms and ions 5. Magnetic effects in atomic structure 6. Groups and their matrixExpand
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