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a
Formation of compounds 6 and 8 might be two branching pathways
in OvoA catalysis. It may involve either a sulfenic acid intermediate
(11, Path A) or thiother intermediate (12, Path B). Formations of 6
and 8 may branch out from either the peroxy radical species (10, Path
C) or the sulfenic acid intermediate (11, Path D).
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2
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side product or have cysteine sulfenic acid as the oxidation
product (Supplementary Figure 23S), which then reacts with
Uden, P. C.; Maroney, M. J. J. Biol. Chem. 2005, 280, 9865.
(27) Simmons, C. R.; Hirschberger, L. L.; Machi, M. S.; Stipanuk, M.
H. Protein Expression Purif. 2006, 47, 74.
(28) Crawford, J. A.; Li, W.; Pierce, B. S. Biochemistry 2011, 50,
10241.
cysteine to form cystine. Due to the high reactivity of H O and
2
2
cysteine sulfenic acid under our assay conditions, initial
44−46
attempts on trapping them were unsuccessful.
Future
studies will be focused on trapping and characterization of
some of the proposed intermediates.
(29) Chai, S. C.; Bruyere, J. R.; Maroney, M. J. J. Biol. Chem. 2006,
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81, 15774.
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30) Joseph, C. A.; Maroney, M. J. Chem. Commun. 2007, 3338.
31) Krebs, C.; Fujimori, D. G.; Walsh, C. T.; Bollinger, J. M. Acc.
ASSOCIATED CONTENT
Supporting Information
■
*
S
Chem. Res. 2007, 40, 484.
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105, 2227.
(33) Kovaleva, E. G.; Lipscomb, J. D. Nat. Chem. Biol. 2008, 4, 186.
(
S. K.; Lehnert, N.; Neese, F.; Skulan, A. J.; Yang, Y. S.; Zhou, J. Chem.
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(
Experimental procedure, enzyme characterization data, copies
1
13
of the H and C NMR of compounds 8 and 9, and kinetic
34) Solomon, E. I.; Brunold, T. C.; Davis, M. I.; Kemsley, J. N.; Lee,
AUTHOR INFORMATION
■
35) Costas, M.; Mehn, M. P.; Jensen, M. P.; Que, L. Chem. Rev.
2
004, 104, 939.
*
(36) McCoy, J. G.; Bailey, L. J.; Bitto, E.; Bingman, C. A.; Aceti, D. J.;
Fox, B. G.; Phillips, G. N. Proc. Natl. Acad. Sci. U.S.A. 2006, 103, 3084.
Notes
(
37) Simmons, C. R.; Liu, Q.; Huang, Q. Q.; Hao, Q.; Begley, T. P.;
Karplus, P. A.; Stipanuk, M. H. J. Biol. Chem. 2006, 281, 18723.
38) Simmons, C. R.; Krishnamoorthy, K.; Granett, S. L.; Schuller, D.
The authors declare no competing financial interest.
(
ACKNOWLEDGMENTS
■
J.; Dominy, J. E., Jr.; Begley, T. P.; Stipanuk, M. H.; Karplus, P. A.
Biochemistry 2008, 47, 11390.
This work is partially supported by a NSF award (CHE-
(
39) Ye, S.; Wu, X.; Wei, L.; Tang, D. M.; Sun, P.; Bartlam, M.; Rao,
Z. H. J. Biol. Chem. 2007, 282, 3391.
40) Kumar, D.; Thiel, W.; de Visser, S. P. J. Am. Chem. Soc. 2011,
33, 3869.
1
309148) and NIH award (GM093903) to PL.
(
1
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