Getting a handle on the role of coenzyme M in alkene metabolism.
Coenzyme M (2-mercaptoethanesulfonate; CoM) is one of several atypical cofactors discovered in methanogenic archaea which participate in the biological reduction of CO(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(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.
Krishnakumar
Arathi M
AM
Chemistry and Biochemistry Building, Montana State University, Bozeman, MT 59717, USA.
Sliwa
Darius
D
Endrizzi
James A
JA
Boyd
Eric S
ES
Ensign
Scott A
SA
Peters
John W
JW
D000475:Alkenes / Q000378:metabolism*; D000595:Amino Acid Sequence; D015080:Mesna / Q000737:chemistry* / Q000378:metabolism*; D008958:Models, Molecular; D008969:Molecular Sequence Data; D013329:Structure-Activity Relationship; D020584:Xanthobacter / Q000201:enzymology* / Q000235:genetics / Q000254:growth & development
D000475:Alkenes; C013658:propylene; D015080:Mesna
Science. 1997 Nov 21;278(5342):1457-62
9367957
Biochemistry. 2005 Oct 4;44(39):13151-62
16185083
J Biol Chem. 1974 Aug 10;249(15):4879-85
4367810
Nucleic Acids Res. 1994 Nov 11;22(22):4673-80
7984417
Appl Environ Microbiol. 1976 Dec;32(6):781-91
827241
J Biol Chem. 1994 Apr 22;269(16):11695-8
8163465
Annu Rev Microbiol. 1991;45:1-35
1741611
Appl Environ Microbiol. 1998 Aug;64(8):2800-5
9687433
J Biol Chem. 2001 Feb 9;276(6):4485-93
11073950
Eur J Biochem. 1998 Apr 1;253(1):292-9
9578488
Biochemistry. 1995 May 9;34(18):6003-13
7742302
PLoS Biol. 2005 Feb;3(2):e31
15630480
J Biol Chem. 2004 Oct 22;279(43):44235-8
15326182
J Bacteriol. 2001 Apr;183(7):2172-7
11244054
Biochemistry. 2002 Apr 16;41(15):5005-14
11939797
Eur J Biochem. 1991 Dec 18;202(3):1217-22
1662605
Proc Natl Acad Sci U S A. 1999 Jul 20;96(15):8432-7
10411892
Electrophoresis. 1997 Dec;18(15):2714-23
9504803
Biochemistry. 2004 Jun 1;43(21):6763-71
15157110
Eur J Biochem. 2002 Sep;269(18):4409-17
12230552
J Biol Chem. 1974 Aug 10;249(15):4886-90
4152560
Microbiology (Reading). 1998 Sep;144 ( Pt 9):2377-2406
9782487
Arch Microbiol. 2005 Feb;183(2):95-106
15599705
Biochemistry. 2002 Oct 29;41(43):12907-13
12390015
Science. 1993 Aug 27;261(5125):1164-7
8395079
Biochemistry. 1996 Sep 24;35(38):12228-34
8823155
J Biol Chem. 1989 Nov 5;264(31):18714-8
2509466
J Biol Chem. 1997 Dec 19;272(51):32121-8
9405410
J Biol Chem. 2003 Nov 14;278(46):45858-63
12952952
J Bacteriol. 1998 Apr;180(8):2072-8
9555888
Eur J Biochem. 1990 Oct 5;193(1):255-61
2121478
Mol Biol Evol. 1987 Jul;4(4):406-25
3447015
Eur J Biochem. 2000 May;267(9):2498-504
10785368
J Bacteriol. 2003 Sep;185(18):5536-45
12949106
Appl Environ Microbiol. 2006 May;72(5):3756-8
16672529
Biochemistry. 1971 Jun 8;10(12):2317-24
4398893
Annu Rev Biochem. 2003;72:55-76
12524213
Dalton Trans. 2005 Nov 7;(21):3451-8
16234924
Biochemistry. 1999 Oct 19;38(42):13991-8
10529246
Mutat Res. 1978 Nov;58(2-3):217-23
370573
Biochemistry. 1997 Dec 16;36(50):15749-57
9398304
J Bacteriol. 1979 Jan;137(1):256-63
104960
J Bacteriol. 1979 Jan;137(1):264-73
33148
J Bacteriol. 1997 May;179(10):3110-5
9150202
Eur J Biochem. 2001 Oct;268(19):5176-88
11589710
Acta Crystallogr A. 1991 Mar 1;47 ( Pt 2):110-9
2025413
J Bacteriol. 2000 May;182(9):2629-34
10762269
Biochemistry. 1999 Nov 30;38(48):15915-26
10625458
Nat Prod Rep. 2002 Apr;19(2):133-47
12013276
Biochemistry. 2001 Oct 30;40(43):13068-78
11669645
J Bacteriol. 2000 Jul;182(13):3688-92
10850983
Appl Environ Microbiol. 2003 Oct;69(10):6041-6
14532060
Biochemistry. 2006 Jul 25;45(29):8831-40
16846226
Proc Natl Acad Sci U S A. 1998 Apr 28;95(9):4876-81
9560196
J Bacteriol. 1999 Apr;181(7):2094-101
10094686
Mol Biol Evol. 2007 Aug;24(8):1596-9
17488738
Biochemistry. 1993 Dec 28;32(51):14089-94
8260490
Biochemistry. 2001 May 22;40(20):5845-53
11352719
Biochemistry. 2001 Jan 30;40(4):987-93
11170420
Vitam Horm. 2001;61:299-337
11153270
Biochemistry. 2000 Feb 15;39(6):1294-304
10684609
Evolution. 1985 Jul;39(4):783-791
28561359
Biochemistry. 2006 Jan 10;45(1):113-20
16388586
Curr Opin Chem Biol. 1997 Oct;1(3):332-9
9667865
J Bacteriol. 1974 Nov;120(2):974-5
4376145