Chemical Methods for Studying the Biosynthesis of Lantibiotics and Prostaglandins
type: CreativeWork
description: Prostaglandin H Synthase (PGHS) converts arachidonic acid (AA) into the first intermediate in the synthesis of prostaglandins via a radical mechanism. Prostaglandins play a number of roles in the body, including the regulation of blood flow to certain organs, controlling transport across membranes, and the stimulation of inflammation. A tyrosine radical is proposed to initiate the cyclooxygenase reaction by abstraction of the pro-S hydrogen atom at position 13 of AA to form a fatty acid radical, proposed to be a pentadienyl radical. Site-specifically deuterated AAs can contribute to corroboration of the proposed structure, as their reaction with the enzyme should lead to predictable changes in the hyperfine pattern observed in the EPR spectrum. We therefore designed syntheses for and prepared 15-[2H]-AA and four more deuterated compounds as structural probes. The EPR spectra obtained provide strong support for the assignment of the radical signal to a pentadienyl radical.
abstract: Prostaglandin H Synthase (PGHS) converts arachidonic acid (AA) into the first intermediate in the synthesis of prostaglandins via a radical mechanism. Prostaglandins play a number of roles in the body, including the regulation of blood flow to certain organs, controlling transport across membranes, and the stimulation of inflammation. A tyrosine radical is proposed to initiate the cyclooxygenase reaction by abstraction of the pro-S hydrogen atom at position 13 of AA to form a fatty acid radical, proposed to be a pentadienyl radical. Site-specifically deuterated AAs can contribute to corroboration of the proposed structure, as their reaction with the enzyme should lead to predictable changes in the hyperfine pattern observed in the EPR spectrum. We therefore designed syntheses for and prepared 15-[2H]-AA and four more deuterated compounds as structural probes. The EPR spectra obtained provide strong support for the assignment of the radical signal to a pentadienyl radical.
author: Okeley, Nicole Marie
language: eng
keywords: Chemistry, Organic
date published: 2015-09-25T22:12:41Z
date modified: 2026-07-22T22:26:22Z
provider: University of Illinois - Urbana-Champaign
publisher: Networked Digital Library of Theses and Dissertations
type: WebPage
source organization: University of Illinois at Urbana-Champaign

PropertyValue
property ID: Handle
value: http://hdl.handle.net/2142/84065