Skip to main content
U.S. Department of Energy
Office of Scientific and Technical Information

Hybrid radical-polar pathway for excision of ethylene from 2-oxoglutarate by an iron oxygenase

Journal Article · · Science
 [1];  [2];  [2];  [2];  [3];  [3]
  1. Department of Chemistry, The Pennsylvania State University, University Park, PA 16802, USA.; OSTI
  2. Department of Chemistry, The Pennsylvania State University, University Park, PA 16802, USA.
  3. Department of Chemistry, The Pennsylvania State University, University Park, PA 16802, USA.; Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, PA 16802, USA.
Tracing a path to ethylene

Ethylene is produced industrially from fossil carbon sources, but plants and microbes produce small amounts through a handful of unusual enzymatic reactions. Copelandet al. studied a microbial ethylene-forming enzyme using oxygen isotope–tracing experiments and biochemical assays to test mechanistic proposals. This enzyme, which uses a non–heme iron center to activate oxygen, catalyzes two distinct oxidation reactions with different mechanisms. One reaction is entirely off-pathway and results in fragmentation of a co-substrate, arginine. The other reaction can completely fragment 2-oxoglutarate into ethylene, bicarbonate, and two molecules of carbon dioxide; however, it occasionally derails and yields an omega–hydroxy acid product. —MAF

Research Organization:
Pennsylvania State Univ., University Park, PA (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
DOE Contract Number:
SC0016255;
OSTI ID:
1852166
Journal Information:
Science, Journal Name: Science Journal Issue: 6562 Vol. 373; ISSN 0036-8075
Publisher:
AAAS
Country of Publication:
United States
Language:
English

References (29)

Conversion of (2S)-Arginine to (2S,3R)-Capreomycidine by VioC and VioD from the Viomycin Biosynthetic Pathway of Streptomyces sp. Strain ATCC11861 journal September 2004
Convenient synthesis of deuterated glutamic acid, proline and leucine via catalytic deuteration of unsaturated pyroglutamate derivatives journal January 2006
Dioxygen activation by nonheme iron enzymes with the 2-His-1-carboxylate facial triad that generate high-valent oxoiron oxidants journal January 2017
An enzymatic method for the determination of enantiomeric composition and absolute configuration of deuterated or tritiated succinic acid journal September 1984
Two reactions are simultaneously catalyzed by a single enzyme: The arginine-dependent simultaneous formation of two products, ethylene and succinate, from 2-oxoglutarate by an enzyme from Pseudomonas syringae journal October 1992
The HITRAN2016 molecular spectroscopic database journal December 2017
Quantitative infrared analysis of mixtures of isotopically labeled gases journal April 1968
Biochemical and Spectroscopic Characterization of the Non-Heme Fe(II)- and 2-Oxoglutarate-Dependent Ethylene-Forming Enzyme from Pseudomonas syringae pv. phaseolicola PK2 journal October 2016
Electrochemical Oxidation Induced Selective C–C Bond Cleavage journal October 2020
Atomic and Electronic Structure Determinants Distinguish between Ethylene Formation and l -Arginine Hydroxylation Reaction Mechanisms in the Ethylene-Forming Enzyme journal January 2021
Non-Heme Fe(IV)–Oxo Intermediates journal July 2007
Cysteine Is the General Base That Serves in Catalysis by Isocitrate Lyase and in Mechanism-Based Inhibition by 3-Nitropropionate journal December 2013
The Degradation Of Carboxylic Acid Salts By Means Of Halogen - The Hunsdiecker Reaction journal April 1956
THE STEREOCHEMISTRY OF THE SUCCINIC DEHYDROGENASE REACTION 1 journal August 1960
An Iron(IV)–Oxo Intermediate Initiating l -Arginine Oxidation but Not Ethylene Production by the 2-Oxoglutarate-Dependent Oxygenase, Ethylene-Forming Enzyme journal February 2021
Spectroscopic Evidence for the Two C–H-Cleaving Intermediates of Aspergillus nidulans Isopenicillin N Synthase journal July 2016
Structures and Mechanisms of the Non-Heme Fe(II)- and 2-Oxoglutarate-Dependent Ethylene-Forming Enzyme: Substrate Binding Creates a Twist journal August 2017
Visualizing the Reaction Cycle in an Iron(II)- and 2-(Oxo)-glutarate-Dependent Hydroxylase journal September 2017
Direct nitration and azidation of aliphatic carbons by an iron-dependent halogenase journal January 2014
Two interconverting Fe(IV) intermediates in aliphatic chlorination by the halogenase CytC3 journal January 2007
Hyperproduction of 3-hydroxypropionate by Halomonas bluephagenesis journal March 2021
Mechanisms of 2-Oxoglutarate-Dependent Oxygenases: The Hydroxylation Paradigm and Beyond book May 2015
Mechanistic insights into a non-heme 2-oxoglutarate-dependent ethylene-forming enzyme: selectivity of ethylene-formation versus l -Arg hydroxylation journal January 2019
A global view of isotopic effects on ro-vibrational spectra of six-atomic molecules: a case study of eleven ethylene species journal January 2020
New and improved methods for the radical decarboxylation of acids journal January 1983
Structural and stereoelectronic insights into oxygenase-catalyzed formation of ethylene from 2-oxoglutarate journal April 2017
Fe(II)/α-Ketoglutarate-Dependent Hydroxylases and Related Enzymes journal January 2004
Purification and properties of an ethylene-forming enzyme from Pseudomonas syringae pv. phaseolicola PK2 journal October 1991
Purification and some properties of a novel ethylene-forming enzyme produced by Penicillium digitatum journal May 1989

Similar Records

An Iron(IV)–Oxo Intermediate Initiating l-Arginine Oxidation but Not Ethylene Production by the 2-Oxoglutarate-Dependent Oxygenase, Ethylene-Forming Enzyme
Journal Article · 2021 · Journal of the American Chemical Society · OSTI ID:1774768

Ethylene-Forming Enzyme and Bioethylene Production
Journal Article · 2014 · Biotechnology for Biofuels · OSTI ID:1128615

A New Microbial Pathway for Organophosphonate Degradation Catalyzed by Two Previously Misannotated Non-Heme-Iron Oxygenases
Journal Article · 2019 · Biochemistry · OSTI ID:1513018