دورية أكاديمية
Cofactor-independent C–C bond cleavage reactions catalyzed by the AlpJ family of oxygenases in atypical angucycline biosynthesis
| العنوان: | Cofactor-independent C–C bond cleavage reactions catalyzed by the AlpJ family of oxygenases in atypical angucycline biosynthesis |
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| المؤلفون: | Jinmin Gao, Liyuan Li, Shijie Shen, Guomin Ai, Bin Wang, Fang Guo, Tongjian Yang, Hui Han, Zhengren Xu, Guohui Pan, Keqiang Fan |
| المصدر: | Beilstein Journal of Organic Chemistry, Vol 20, Iss 1, Pp 1198-1206 (2024) |
| بيانات النشر: | Beilstein-Institut, 2024. |
| سنة النشر: | 2024 |
| المجموعة: | LCC:Science LCC:Organic chemistry |
| مصطلحات موضوعية: | angucyclines, aromatic polyketide, biosynthesis, cofactor-independent oxygenase, oxidative rearrangement reaction, Science, Organic chemistry, QD241-441 |
| الوصف: | Biosynthesis of atypical angucyclines involves unique oxidative B-ring cleavage and rearrangement reactions, which are catalyzed by AlpJ-family oxygenases, including AlpJ, JadG, and GilOII. Prior investigations established the essential requirement for FADH2/FMNH2 as cofactors when utilizing the quinone intermediate dehydrorabelomycin as a substrate. In this study, we unveil a previously unrecognized facet of these enzymes as cofactor-independent oxygenases when employing the hydroquinone intermediate CR1 as a substrate. The enzymes autonomously drive oxidative ring cleavage and rearrangement reactions of CR1, yielding products identical to those observed in cofactor-dependent reactions of AlpJ-family oxygenases. Furthermore, the AlpJ- and JadG-catalyzed reactions of CR1 could be quenched by superoxide dismutase, supporting a catalytic mechanism wherein the substrate CR1 reductively activates molecular oxygen, generating a substrate radical and the superoxide anion O2•−. Our findings illuminate a substrate-controlled catalytic mechanism of AlpJ-family oxygenases, expanding the realm of cofactor-independent oxygenases. Notably, AlpJ-family oxygenases stand as a pioneering example of enzymes capable of catalyzing oxidative reactions in either an FADH2/FMNH2-dependent or cofactor-independent manner. |
| نوع الوثيقة: | article |
| وصف الملف: | electronic resource |
| اللغة: | English |
| تدمد: | 1860-5397 |
| Relation: | https://doaj.org/toc/1860-5397 |
| DOI: | 10.3762/bjoc.20.102 |
| URL الوصول: | https://doaj.org/article/7ed50e33a9a54e1481349de7c06a9c12 |
| رقم الأكسشن: | edsdoj.7ed50e33a9a54e1481349de7c06a9c12 |
| قاعدة البيانات: | Directory of Open Access Journals |
Full Text Finder | تدمد: | 18605397 |
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| DOI: | 10.3762/bjoc.20.102 |