Transition state of the sulfuryl transfer reaction of estrogen sulfotransferase

Richard H. Hoff, Przemyslaw G. Czyryca, Meihao Sun, Thomas S. Leyh, Alvan C. Hengge

Research output: Contribution to journalArticle

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Abstract

Kinetic isotope effects have been measured for the estrogen sulfotransferase-catalyzed sulfuryl (SO3) transfer from p-nitrophenyl sulfate to the 5′-phosphoryl group of 3′-phosphoadenosine 5′-phosphate. 18(V/K)nonbridge = 1.0016 ± 0.0005, 18(V/K)bridge = 1.0280 ± 0.0006, and 15(V/K) = 1.0014 ± 0.0004. (15(V/K) refers to the nitro group in p-nitrophenyl sulfate). The kinetic isotope effects indicate substantial S-O bond fission in the transition state, with partial charge neutralization of the leaving group. The small kinetic isotope effect in the nonbridging sulfuryl oxygen atoms suggests no significant change in bond orders of these atoms occurs, consistent with modest nucleophilic involvement. A comparison of the data for enzymatic and uncatalyzed sulfuryl transfer reactions suggests that both proceed through very similar transition states.

Original languageEnglish (US)
Pages (from-to)30645-30649
Number of pages5
JournalJournal of Biological Chemistry
Volume281
Issue number41
DOIs
StatePublished - Oct 13 2006

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Isotopes
Kinetics
Atoms
Oxygen
estrone sulfotransferase
4-nitrophenyl sulfate
adenosine 3'-phosphate-5'-phosphate

ASJC Scopus subject areas

  • Biochemistry

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Transition state of the sulfuryl transfer reaction of estrogen sulfotransferase. / Hoff, Richard H.; Czyryca, Przemyslaw G.; Sun, Meihao; Leyh, Thomas S.; Hengge, Alvan C.

In: Journal of Biological Chemistry, Vol. 281, No. 41, 13.10.2006, p. 30645-30649.

Research output: Contribution to journalArticle

Hoff, Richard H. ; Czyryca, Przemyslaw G. ; Sun, Meihao ; Leyh, Thomas S. ; Hengge, Alvan C. / Transition state of the sulfuryl transfer reaction of estrogen sulfotransferase. In: Journal of Biological Chemistry. 2006 ; Vol. 281, No. 41. pp. 30645-30649.
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