1uzw

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==Overview==
==Overview==
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Isopenicillin N synthase (IPNS) is a non-haem iron oxidase that catalyses, the formation of bicyclic isopenicillin N from, delta-(L-alpha-aminoadipoyl)-L-cysteinyl-D-valine (ACV). In this study we, report a novel activity for the iron of the IPNS active site, which, behaves as a Lewis acid to catalyse the elimination of HF from the, fluorinated substrate analogue, delta-(L-alpha-aminoadipoyl)-L-cysteinyl-D-beta-fluorovaline (ACbetaFV)., X-Ray crystallographic studies of IPNS crystals grown anaerobically with, ACbetaFV reveal that the valinyl beta-fluorine is missing from the active, site region, and suggest the presence of the unsaturated tripeptide, delta-(L-alpha-aminoadipoyl)-L-cysteinyl-D-isodehydrovaline in place of, substrate ACbetaFV. (19)F NMR studies confirm the release of fluoride from, ACbetaFV in the presence of the active IPNS enzyme. These results suggest, a new mode of reactivity for the IPNS iron centre, a mechanism of action, that has not previously been reported for any of the iron oxidase enzymes.
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Isopenicillin N synthase (IPNS) is a non-haem iron oxidase that catalyses the formation of bicyclic isopenicillin N from delta-(L-alpha-aminoadipoyl)-L-cysteinyl-D-valine (ACV). In this study we report a novel activity for the iron of the IPNS active site, which behaves as a Lewis acid to catalyse the elimination of HF from the fluorinated substrate analogue, delta-(L-alpha-aminoadipoyl)-L-cysteinyl-D-beta-fluorovaline (ACbetaFV). X-Ray crystallographic studies of IPNS crystals grown anaerobically with ACbetaFV reveal that the valinyl beta-fluorine is missing from the active site region, and suggest the presence of the unsaturated tripeptide delta-(L-alpha-aminoadipoyl)-L-cysteinyl-D-isodehydrovaline in place of substrate ACbetaFV. (19)F NMR studies confirm the release of fluoride from ACbetaFV in the presence of the active IPNS enzyme. These results suggest a new mode of reactivity for the IPNS iron centre, a mechanism of action that has not previously been reported for any of the iron oxidase enzymes.
==About this Structure==
==About this Structure==
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[[Category: Isopenicillin-N synthase]]
[[Category: Isopenicillin-N synthase]]
[[Category: Single protein]]
[[Category: Single protein]]
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[[Category: Baldwin, J.E.]]
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[[Category: Baldwin, J E.]]
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[[Category: Clifton, I.J.]]
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[[Category: Clifton, I J.]]
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[[Category: Grummitt, A.R.]]
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[[Category: Grummitt, A R.]]
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[[Category: Rutledge, P.J.]]
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[[Category: Rutledge, P J.]]
[[Category: CDH]]
[[Category: CDH]]
[[Category: FE2]]
[[Category: FE2]]
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[[Category: penicillin biosynthesis]]
[[Category: penicillin biosynthesis]]
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''Page seeded by [http://oca.weizmann.ac.il/oca OCA ] on Sun Feb 3 10:13:10 2008''
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''Page seeded by [http://oca.weizmann.ac.il/oca OCA ] on Thu Feb 21 15:30:10 2008''

Revision as of 13:30, 21 February 2008


1uzw, resolution 1.30Å

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ISOPENICILLIN N SYNTHASE WITH L-D-(A-AMINOADIPOYL)-L-CYSTEINYL-D-ISODEHYDROVALINE

Overview

Isopenicillin N synthase (IPNS) is a non-haem iron oxidase that catalyses the formation of bicyclic isopenicillin N from delta-(L-alpha-aminoadipoyl)-L-cysteinyl-D-valine (ACV). In this study we report a novel activity for the iron of the IPNS active site, which behaves as a Lewis acid to catalyse the elimination of HF from the fluorinated substrate analogue, delta-(L-alpha-aminoadipoyl)-L-cysteinyl-D-beta-fluorovaline (ACbetaFV). X-Ray crystallographic studies of IPNS crystals grown anaerobically with ACbetaFV reveal that the valinyl beta-fluorine is missing from the active site region, and suggest the presence of the unsaturated tripeptide delta-(L-alpha-aminoadipoyl)-L-cysteinyl-D-isodehydrovaline in place of substrate ACbetaFV. (19)F NMR studies confirm the release of fluoride from ACbetaFV in the presence of the active IPNS enzyme. These results suggest a new mode of reactivity for the IPNS iron centre, a mechanism of action that has not previously been reported for any of the iron oxidase enzymes.

About this Structure

1UZW is a Single protein structure of sequence from Emericella nidulans with , and as ligands. Active as Isopenicillin-N synthase, with EC number 1.21.3.1 Known structural/functional Site: . Full crystallographic information is available from OCA.

Reference

Active-site-mediated elimination of hydrogen fluoride from a fluorinated substrate analogue by isopenicillin N synthase., Grummitt AR, Rutledge PJ, Clifton IJ, Baldwin JE, Biochem J. 2004 Sep 1;382(Pt 2):659-66. PMID:15175003

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