A non-enzymatic pathway with superoxide in intracellular terpenoid synthesis

A non-enzymatic pathway with superoxide in intracellular terpenoid synthesis
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细胞内萜类化合物合成中超氧化物的非酶促途径

DOI:
10.1002/anie.201805383
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发表时间:
2018
期刊:
Angew. Chem. Int. Ed.
影响因子:
--
通讯作者:
T.
T.
中科院分区:
--
文献类型:
--
作者:
Ueda;D.;Matsugane;S.;Okamoto;W.;Hashimoto;M.;Sato;T.

文献摘要

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具有乙酰基的非C5 -单位萜类化合物(降异戊二烯类)广泛分布于自然界。然而,生物合成类异戊二烯的研究很少。目前,从芽孢杆菌中鉴定出c33norisopopoid (all‐E)‐farnesylfarnesylacetone),并首次阐明了在皂化处理过程中,超氧化物介导甲基萘醌(维生素K)裂解生成norisopopoid。利用基因破坏的枯草芽孢杆菌菌株对甲基萘醌生物合成酶和超氧化物歧化酶进行了体内实验,结果表明,甲基萘醌与超氧化物的非酶裂解(自氧化)导致芽孢杆菌细胞合成了类去甲异戊二烯。此外,该合成体系还在芽孢杆菌细胞中生成了具有生物活性的类去甲异戊二烯、法尼基丙酮和植酮。
Non‐C5‐units terpenoids (norisoprenoids) with an acetonyl group are widely distributed in nature. However, studies on the biosynthesis of norisoprenoids are scarce. Now, the C33norisoprenoid, (all‐E)‐farnesylfarnesylacetone, was identified from Bacillus spp. and it was elucidated for the first time that superoxide mediates the cleavage of menaquinones (vitamin K) to form norisoprenoids in saponification treatment. From in vivo experiments using gene‐disrupted Bacillus subtilis strains targeted for enzymes responsible for menaquinone biosynthesis and for superoxide dismutase, it was suggested that the non‐enzymatic cleavage (autoxidation) of menaquinone with superoxide resulted in norisoprenoid synthesis in Bacillus cells. Furthermore, the bioactive norisoprenoids, farnesylacetone and phytone, were produced in Bacillus cells by this novel synthesis system.