title: Synthesis and scavenging role of furan fatty acids.
abstract: Fatty acids play important functional and protective roles in living systems. This paper reports on the synthesis of a previously unidentified 19 carbon furan-containing fatty acid, 10,13-epoxy-11-methyl-octadecadienoate (9-(3-methyl-5-pentylfuran-2-yl)nonanoic acid) (19Fu-FA), in phospholipids from Rhodobacter sphaeroides. We show that 19Fu-FA accumulation is increased in cells containing mutations that increase the transcriptional response of this bacterium to singlet oxygen ((1)O2), a reactive oxygen species generated by energy transfer from one or more light-excited donors to molecular oxygen. We identify a previously undescribed class of S-adenosylmethionine-dependent methylases that convert a phospholipid 18 carbon cis unsaturated fatty acyl chain to a 19 carbon methylated trans unsaturated fatty acyl chain (19M-UFA). We also identify genes required for the O2-dependent conversion of this 19M-UFA to 19Fu-FA. Finally, we show that the presence of (1)O2 leads to turnover of 19Fu-Fa in vivo. We propose that furan-containing fatty acids like 19Fu-FA can act as a membrane-bound scavenger of (1)O2, which is naturally produced by integral membrane enzymes of the R. sphaeroides photosynthetic apparatus.
authors.affiliation: Departments of Bacteriology.
authors.forename: Rachelle A S
authors.initials: RA
authors.lastname: Lemke
authors.affiliation: Chemistry, and.
authors.forename: Amelia C
authors.initials: AC
authors.lastname: Peterson
authors.affiliation: Departments of Bacteriology.
authors.forename: Eva C
authors.initials: EC
authors.lastname: Ziegelhoffer
authors.affiliation: Genome Center of Wisconsin, Madison, WI 53706; and.
authors.forename: Michael S
authors.initials: MS
authors.lastname: Westphall
authors.affiliation: Great Lakes Bioenergy Research Center, Madison, WI 53726;Department of Plant Biology, Michigan State University, East Lansing, MI 48824.
authors.forename: Henrik
authors.initials: H
authors.lastname: Tjellström
authors.affiliation: Chemistry, andGreat Lakes Bioenergy Research Center, Madison, WI 53726;Biomolecular Chemistry, University of Wisconsin-Madison, Madison, WI 53706;
authors.forename: Joshua J
authors.initials: JJ
authors.lastname: Coon
authors.affiliation: Departments of Bacteriology,Great Lakes Bioenergy Research Center, Madison, WI 53726; tdonohue@bact.wisc.edu.
authors.forename: Timothy J
authors.initials: TJ
authors.lastname: Donohue
mesh_terms: D002849:Chromatography, Gas; D005227:Fatty Acids / Q000096:biosynthesis* / Q000378:metabolism*; D005663:Furans / Q000378:metabolism*; D017382:Reactive Oxygen Species / Q000378:metabolism; D012242:Rhodobacter sphaeroides / Q000378:metabolism; D026082:Singlet Oxygen / Q000378:metabolism
chemical_list: D005227:Fatty Acids; D005663:Furans; D017382:Reactive Oxygen Species; D026082:Singlet Oxygen
keywords: fatty acyl methylase; oxygenated fatty acid; radical scavenger
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