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在细菌叶绿素 a 生物合成中,氧化还原酶 BchC 对 C3 取代基进行立体选择性修饰和底物通道化。

Stereoselective C3-substituent modification and substrate channeling by oxidoreductase BchC in bacteriochlorophyll a biosynthesis.

机构信息

Graduate School of Life Sciences, Ritsumeikan University, Kusatsu, Japan.

Research and Development Center for Marine Biosciences, Japan Agency for Marine-Earth Science and Technology (JAMSTEC), Yokosuka, Japan.

出版信息

FEBS Lett. 2019 Apr;593(8):799-809. doi: 10.1002/1873-3468.13372. Epub 2019 Apr 4.

DOI:10.1002/1873-3468.13372
PMID:30908616
Abstract

We report the in vitro activity of recombinant BchC oxidoreductase involved in bacteriochlorophyll a biosynthesis. BchC of Rhodobacter capsulatus preferentially oxidizes 3 R-3-(1-hydroxyethyl)-chlorophyllide a and 3 R-3-(1-hydroxyethyl)-bacteriochlorophyllide a in the presence of NAD to 3-acetyl-chlorophyllide a and bacteriochlorophyllide a, respectively, leaving the unreacted 3 S-epimers. In the reverse reaction, BchC with NADH predominately produces 3 R-epimeric alcohols from the 3-acetyl-(bacterio)chlorins. BchC of Chlorobaculum tepidum demonstrates the same 3 R-selectivity, suggesting that utilization of 3 R-epimers in BchC-catalyzed reductions may be conserved across different phyla of photosynthetic bacteria. Additionally, the presence of BchC accelerates the 3-vinyl hydration by BchF hydratase of Chlorobaculum tepidum during conversion of chlorophyllide a to 3-acetyl-chlorophyllide a through 3-(1-hydroxyethyl)-chlorophyllide a, indicating that these enzymes work cooperatively to promote efficient bacteriochlorophyll a biosynthesis.

摘要

我们报告了参与细菌叶绿素 a 生物合成的重组 BchC 氧化还原酶的体外活性。荚膜红细菌的 BchC 在 NAD 的存在下优先氧化 3R-3-(1-羟乙基)叶绿素 a 和 3R-3-(1-羟乙基)细菌叶绿素 a,分别生成 3-乙酰叶绿素 a 和细菌叶绿素 a,而未反应的 3S-差向异构体则保留下来。在相反的反应中,BchC 与 NADH 主要从 3-乙酰-(细菌)胆绿素中产生 3R-差向异构体醇。来自嗜热盐杆菌的 BchC 表现出相同的 3R-选择性,表明在 BchC 催化的还原反应中,3R-差向异构体的利用可能在不同的光合细菌门中得到保守。此外,BchC 的存在加速了嗜热盐杆菌中 BchF 水合酶的 3-乙烯基水合作用,通过 3-(1-羟乙基)叶绿素 a 转化为 3-乙酰叶绿素 a,表明这些酶协同工作,以促进有效的细菌叶绿素 a 生物合成。

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