在[Fe]-基酶辅因子中,在光解过程中,和CO干在[Fe]-基酶辅因子中发生混乱
Sebastian Schaupp1, Francisco J Arriaza-Gallardo1, Nicole Paczia1
1Max Planck Institute for Terrestrial Microbiology, Karl-von-Frisch-Straße 10, 35043, Marburg, Germany.
Angewandte Chemie (International ed. in English)
|December 15, 2023
概括
在[Fe]-酶的铁-烯烯醇 (FeGP) 辅因子中发生的联体混杂发生在光解过程中,而不是生物合成过程中. 这说明了这种H2激活酶的光敏性质.
科学领域:
- 生物化学 生物化学
- 酶学 是一种酶学.
- 生物有机化学 生物有机化学
背景情况:
- [Fe]-酶酶含有独特的铁-烯 (FeGP) 辅因子,对H2激活至关重要.
- 紫外线A/蓝光暴露会分解FeGP辅因子,但与生物合成或光解相比,连接体杂乱 (乙与CO) 的时间是未知的.
研究的目的:
- 为了阐明FeGP辅因子中的联体混杂是否在体外生物合成或光解过程中发生.
- 研究FeGP辅因子在暴露于光线时的连接物交换的机制和影响.
主要方法:
- 在体外生物合成使用18O标记的前体来追踪乙烯基组的结合.
- 质谱/质谱 (MS/MS) 分析以确定FeGP辅因子中的18O标签的位置.
- 时间分辨率红外光谱学用于监测光解过程中的中间物种.
主要成果:
- 在体外生物合成过程中,成功地将18O标记的基组纳入FeGP辅因子.
- MS/MS分析证实,18O标记的乙基组在生物合成过程中没有与CO合体交换,这表明生物合成后发生了杂乱.
- 时间分辨率红外光谱检测显示,在光解过程中有一种acyl-Fe(CO) 3中间体,在光诱导分解过程中支持了acyl和CO干的混杂.
结论:
- 在[Fe]-酶的FeGP辅因子中的干混杂 (乙和CO) 仅在光解过程中发生,而不是在生物合成过程中.
- 这些发现排除了涉及乙/CO干混杂的生物合成机制,并将光解确定为该过程的关键事件.
- 光激发的FeGP辅因子对外部的CO产生了更大的亲和力,这表明对酶调节和功能的影响.
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