title: Discovery of multiple modified F(430) coenzymes in methanogens and anaerobic methanotrophic archaea suggests possible new roles for F(430) in nature.
abstract: Methane is a potent greenhouse gas that is generated and consumed in anaerobic environments through the energy metabolism of methanogens and anaerobic methanotrophic archaea (ANME), respectively. Coenzyme F430 is essential for methanogenesis, and a structural variant of F430, 17(2)-methylthio-F430 (F430-2), is found in ANME and is presumably essential for the anaerobic oxidation of methane. Here we use liquid chromatography-high-resolution mass spectrometry to identify several new structural variants of F430 in the cell extracts of selected methanogens and ANME. Methanocaldococcus jannaschii and Methanococcus maripaludis contain an F430 variant (denoted F430-3) that has an M(+) of 1,009.2781. This mass increase of 103.9913 over that of F430 corresponds to C3H4O2S and is consistent with the addition of a 3-mercaptopropionate moiety bound as a thioether followed by a cyclization. The UV absorbance spectrum of F430-3 was different from that of F430 and instead matched that of an F430 derivative where the 17(3) keto moiety had been reduced. This is the first report of a modified F430 in methanogens. In a search for F430-2 and F430-3 in other methanogens and ANME, we have identified a total of nine modified F430 structures. One of these compounds may be an abiotic oxidative product of F430, but the others represent naturally modified versions of F430. This work indicates that F430-related molecules have additional functions in nature and will inspire further research to determine the biochemical role(s) of these variants and the pathways involved in their biosynthesis.
authors.affiliation: Department of Biochemistry, Virginia Polytechnic Institute and State University, Blacksburg, Virginia, USA.
authors.forename: Kylie D
authors.initials: KD
authors.lastname: Allen
authors.affiliation: Max Planck Institute for Marine Microbiology, Bremen, Germany.
authors.forename: Gunter
authors.initials: G
authors.lastname: Wegener
authors.affiliation: Department of Biochemistry, Virginia Polytechnic Institute and State University, Blacksburg, Virginia, USA rhwhite@vt.edu.
authors.forename: Robert H
authors.initials: RH
authors.lastname: White
mesh_terms: D000693:Anaerobiosis; D019605:Euryarchaeota / Q000302:isolation & purification / Q000378:metabolism; D013058:Mass Spectrometry / Q000379:methods; D008665:Metalloporphyrins / Q000737:chemistry* / Q000302:isolation & purification / Q000378:metabolism*; D063747:Methanocaldococcus / Q000737:chemistry / Q000378:metabolism*; D017017:Methanococcus / Q000378:metabolism*; D015394:Molecular Structure; D013056:Spectrophotometry, Ultraviolet
chemical_list: D008665:Metalloporphyrins; C023540:factor F430
references.citation: Nature. 2003 Dec 18;426(6968):878-81
references.pmid: 14685246
references.citation: ISME J. 2011 Dec;5(12):1946-56
references.pmid: 21697963
references.citation: Cell Mol Life Sci. 2014 Aug;71(15):2837-63
references.pmid: 24515122
references.citation: Annu Rev Microbiol. 2009;63:311-34
references.pmid: 19575572
references.citation: Trends Biochem Sci. 2004 May;29(5):243-9
references.pmid: 15130560
references.citation: Arch Microbiol. 2004 Jan;181(1):68-73
references.pmid: 14655002
references.citation: Biochemistry. 2006 Oct 3;45(39):11915-33
references.pmid: 17002292
references.citation: Curr Opin Biotechnol. 2014 Oct;29:70-5
references.pmid: 24662145
references.citation: Crit Rev Biochem Mol Biol. 2008 Jan-Feb;43(1):63-88
references.pmid: 18307109
references.citation: Science. 1997 Nov 21;278(5342):1457-62
references.pmid: 9367957
references.citation: Biochemistry. 2010 Dec 28;49(51):10902-11
references.pmid: 21090696
references.citation: J Bacteriol. 1977 Jun;130(3):1404-6
references.pmid: 324989
references.citation: J Bacteriol. 1981 Nov;148(2):459-64
references.pmid: 7298577
references.citation: Biochim Biophys Acta. 2012 Nov;1824(11):1213-22
references.pmid: 22326745
references.citation: Nat Chem Biol. 2013 May;9(5):333-8
references.pmid: 23542644
references.citation: Nature. 2010 Jun 3;465(7298):606-8
references.pmid: 20520712
references.citation: Environ Microbiol. 2005 Dec;7(12):1937-51
references.pmid: 16309392
references.citation: Microbiol Mol Biol Rev. 2009 Sep;73(3):510-28, Table of Contents
references.pmid: 19721088
references.citation: J Bacteriol. 1989 Dec;171(12):6610-6
references.pmid: 2512282
references.citation: Appl Environ Microbiol. 2007 May;73(10):3348-62
references.pmid: 17369343
references.citation: J Biomol Struct Dyn. 1993 Aug;11(1):203-14
references.pmid: 8216945
references.citation: Appl Environ Microbiol. 1999 Nov;65(11):5059-65
references.pmid: 10543823
references.citation: Chemistry. 2012 May 14;18(20):6309-15
references.pmid: 22488738
references.citation: Proc Natl Acad Sci U S A. 2011 Dec 27;108(52):E1484-90
references.pmid: 22160711
references.citation: J Am Chem Soc. 2013 Oct 9;135(40):14985-95
references.pmid: 24003767
references.citation: Curr Opin Chem Biol. 2009 Feb;13(1):58-73
references.pmid: 19297239
references.citation: Curr Opin Struct Biol. 2010 Dec;20(6):684-92
references.pmid: 20951571
references.citation: Biol Chem. 2005 Oct;386(10):971-80
references.pmid: 16218869
references.citation: Met Ions Life Sci. 2010;7:71-110
references.pmid: 20877805
references.citation: Environ Microbiol. 2008 Sep;10(9):2287-98
references.pmid: 18498367
references.citation: Anal Chem. 2014 Apr 1;86(7):3633-8
references.pmid: 24605937
references.citation: Appl Environ Microbiol. 2005 Jan;71(1):467-79
references.pmid: 15640223
references.citation: J Am Chem Soc. 2013 Oct 16;135(41):15404-15416
references.pmid: 23991893
references.citation: Proc Natl Acad Sci U S A. 2012 Nov 20;109(47):19321-6
references.pmid: 23129626
references.citation: Antonie Van Leeuwenhoek. 1988;54(3):207-20
references.pmid: 3421667
references.citation: J Am Chem Soc. 2008 Aug 13;130(32):10758-67
references.pmid: 18642902
references.citation: Arch Biochem Biophys. 2014 Feb 15;544:142-52
references.pmid: 24036122
references.citation: J Inorg Biochem. 2007 Nov;101(11-12):1657-66
references.pmid: 17716738
references.citation: Science. 2004 Sep 3;305(5689):1457-62
references.pmid: 15353801