Cardiff University | Prifysgol Caerdydd ORCA
Online Research @ Cardiff 
WelshClear Cookie - decide language by browser settings

Probing eudesmane cation−π interactions in catalysis by aristolochene synthase with non-canonical amino acids

Faraldos, Juan A., Antonczak, Alicja K., Gonzalez, Veronica, Fullerton, Rebecca, Tippmann, Eric Michael and Allemann, Rudolf Konrad ORCID: https://orcid.org/0000-0002-1323-8830 2011. Probing eudesmane cation−π interactions in catalysis by aristolochene synthase with non-canonical amino acids. Journal of the American Chemical Society 133 (35) , pp. 13906-13909. 10.1021/ja205927u

Full text not available from this repository.

Abstract

Stabilization of the reaction intermediate eudesmane cation (3) through interaction with Trp 334 during catalysis by aristolochene synthase from Penicillium roqueforti was investigated by site-directed incorporation of proteinogenic and non-canonical aromatic amino acids. The amount of germacrene A (2) generated by the mutant enzymes served as a measure of the stabilization of 3. 2 is a neutral intermediate, from which 3 is formed during PR-AS catalysis by protonation of the C6,C7 double bond. The replacement of Trp 334 with para-substituted phenylalanines of increasing electron-withdrawing properties led to a progressive accumulation of 2 that showed a good correlation with the interaction energies of simple cations such as Na+ with substituted benzenes. These results provide compelling evidence for the stabilizing role played by Trp 334 in aristolochene synthase catalysis for the energetically demanding transformation of 2 to 3.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Cardiff Catalysis Institute (CCI)
Chemistry
Subjects: Q Science > QD Chemistry
Publisher: American Chemical Society
ISSN: 0002-7863
Funders: BBSRC
Last Modified: 18 Oct 2022 13:35
URI: https://orca.cardiff.ac.uk/id/eprint/14506

Citation Data

Cited 61 times in Scopus. View in Scopus. Powered By Scopus® Data

Actions (repository staff only)

Edit Item Edit Item