Getting a Handle on the Role of Coenzyme M in Alkene Metabolism

Journal Article · Wed May 20 04:00:00 EDT 2009 · Microbiol. Mol. Biol. Rev. 72:445,2008

OSTI ID:953070

Krishnakumar, A M; Sliwa, D; Endrizzi, J A; Boyd, E S; Ensign, S A; Peters, J W

Coenzyme M (2-mercaptoethanesulfonate; CoM) is one of several atypical cofactors discovered in methanogenic archaea which participate in the biological reduction of CO{sub 2} to methane. Elegantly simple, CoM, so named for its role as a methyl carrier in all methanogenic archaea, is the smallest known organic cofactor. It was thought that this cofactor was used exclusively in methanogenesis until it was recently discovered that CoM is a key cofactor in the pathway of propylene metabolism in the gram-negative soil microorganism Xanthobacter autotrophicus Py2. A four-step pathway requiring CoM converts propylene and CO{sub 2} to acetoacetate, which feeds into central metabolism. In this process, CoM is used to activate and convert highly electrophilic epoxypropane, formed from propylene epoxidation, into a nucleophilic species that undergoes carboxylation. The unique properties of CoM provide a chemical handle for orienting compounds for site-specific redox chemistry and stereospecific catalysis. The three-dimensional structures of several of the enzymes in the pathway of propylene metabolism in defined states have been determined, providing significant insights into both the enzyme mechanisms and the role of CoM in this pathway. These studies provide the structural basis for understanding the efficacy of CoM as a handle to direct organic substrate transformations at the active sites of enzymes.

• Research Organization: Stanford Linear Accelerator Center (SLAC)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC02-76SF00515
• OSTI ID: 953070
• Report Number(s): SLAC-REPRINT-2009-214
• Journal Information: Microbiol. Mol. Biol. Rev. 72:445,2008, Journal Name: Microbiol. Mol. Biol. Rev. 72:445,2008 Journal Issue: 3 Vol. 72
• Country of Publication: United States
• Language: English

Related Subjects

03 NATURAL GAS
ALKENES
CARBOXYLATION
CATALYSIS
CHEMISTRY
COENZYMES
ENZYMES
METABOLISM
METHANE
MICROORGANISMS
Other
OTHER
BIO
PROPYLENE
SOILS
SUBSTRATES
TRANSFORMATIONS