Loizzi, Marianna, Miller, David J. and Allemann, Rudolf K.  ORCID: https://orcid.org/0000-0002-1323-8830
2019.
Silent catalytic promiscuity in the high-fidelity
terpene cyclase δ-cadinene synthase.
Organic & Biomolecular Chemistry
17
(5)
, pp. 1206-1214.
10.1039/C8OB02821D
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Abstract
δ-Cadinene synthase (DCS) is a high-fidelity sesquiterpene synthase that generates δ-cadinene as the sole detectable organic product from its natural substrate (E,E)-FDP. Previous work with this enzyme using substrate analogues revealed the ability of DCS to catalyse both 1,10- and 1,6-cyclisations of substrate analogues. To test whether this apparent promiscuity was an artefact of alternate substrate use or an inherent property of the enzyme, aza analogues of the proposed α-bisabolyl cation intermediate were prepared since this cation would be formed after an initial 1,6-cyclisation of FDP. In the presence of 250 μM inorganic disphosphate both (R)- and (S)-aza-bisaboyl cations were potent competitive inhibitors of DCS (Ki = 2.5 ± 0.5 mM and 3.44 ± 1.43 μM, respectively). These compounds were also shown to be potent inhibitors of the 1,6-cyclase amorpha-4,11-diene synthase but not of the 1,10-cyclase aristolochene synthase from Penicillium roquefortii, demonstrating that the 1,6-cyclase activity of DCS is most likely an inherent property of the enzyme even when the natural substrate is used and not an artefact of the use of substrate analogues.
| Item Type: | Article |
|---|---|
| Date Type: | Publication |
| Status: | Published |
| Schools: | Schools > Chemistry |
| Publisher: | Royal Society of Chemistry |
| ISSN: | 1477-0520 |
| Funders: | BBSRC |
| Date of First Compliant Deposit: | 22 January 2019 |
| Date of Acceptance: | 10 December 2018 |
| Last Modified: | 17 May 2023 16:27 |
| URI: | https://orca.cardiff.ac.uk/id/eprint/118614 |
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