kinetic isotope effect of prostaglandin h synthase exhibits inverted temperature dependence

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ID: 135423
2014
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Abstract
Conversion of arachidonic acid to prostaglandin G2/H2 catalyzed by prostaglandin H synthase (PGHS) is proposed to involve initial transfer of the C13 pro-(S) hydrogen atom from arachidonate to the Tyr385 radical in PGHS, followed by insertion of two oxygen molecules and several chemical bond rearrangements. The initial hydrogen-transfer was recently concluded to be a rate-limiting step in cyclooxygenase catalysis based on the observed intrinsic deuterium kinetic isotope effect values (Dkcat). In the present study, we have found that Dkcat values of both PGHS-1 and -2 show an unusual increase with temperatures in the range of 288–310 K, exhibiting an inverted temperature dependence. The value of lnDkcat, however, decreased linearly with 1/T, consistent with a typical Arrhenius relationship.
Reference Key
wu2014catalystskinetic Use this key to autocite in the manuscript while using SciMatic Manuscript Manager or Thesis Manager
Authors ;Gang Wu;Richard J. Kulmacz;Ah-Lim Tsai
Journal journal of essential oil research
Year 2014
DOI
10.3390/catal4020174
URL
http://www.mdpi.com/2073-4344/4/2/174
Keywords
temperature dependence of kiechemical technologychemistry

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