Controlled Protonation of [2Fe–2S] Leading to MitoNEET Analogues and Concurrent Cluster Modification
Controlled Protonation of [2Fe–2S] Leading to MitoNEET Analogues and Concurrent Cluster Modification
复制标题
[2Fe-2S] 的受控质子化导致 MitoNEET 类似物和并发簇修饰
DOI：
10.1021/acs.inorgchem.1c02622
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发表时间：
2021
影响因子：
4.6
通讯作者：
Kim, Eunsuk
中科院分区：
文献类型：
--
作者：
Oakley, Kady;Sterling, Kevin;Shearer, Jason;Kim, Eunsuk
MitoNEET是线粒体能量代谢的关键调控蛋白，具有独特的[2Fe-2S]结构，由一个组氨酸和三个半胱氨酸组成。这种独特的簇已被假定为感测氧化还原环境和酸性pH下释放Fe-S辅因子。本文报道的是一个合成系统，显示[2Fe-2S]簇如何与质子反应并重新排列其配位几何形状。低温稳定的、位差簇合物[Fe 2S 2（SPh）3（CF 3COO）]2-和[Fe 2S 2（SPh）3（py）]−通过在-35 °C以下控制质子化制备，并通过NMR、UV-vis和X射线吸收光谱表征。这两种配合物都表现出阳极移动的氧化还原电位相比，[Fe 2S 2（SPh）4]2-，并转化为[Fe 4S 4（SPh）4]2-后升温至室温。目前的研究提供了对mitoNEET如何释放其[2Fe-2S]以响应高度调谐的酸性条件的深入了解，其化学可能对Fe-S生物成因有进一步的影响。
MitoNEET, a key regulatory protein in mitochondrial energy metabolism, exhibits a uniquely ligated [2Fe–2S] cluster with one histidine and three cysteines. This unique cluster has been postulated to sense the redox environment and release Fe–S cofactors under acidic pH. Reported herein is a synthetic system that shows how [2Fe–2S] clusters react with protons and rearrange their coordination geometry. The low-temperature stable, site-differentiated clusters [Fe2S2(SPh)3(CF3COO)]2–and [Fe2S2(SPh)3(py)]−have been prepared via controlled protonation below −35 °C and characterized by NMR, UV–vis, and X-ray absorption spectroscopy. Both complexes exhibit anodically shifted redox potentials compared to [Fe2S2(SPh)4]2–and convert to [Fe4S4(SPh)4]2–upon warming to room temperature. The current study provides insight into how mitoNEET releases its [2Fe–2S] in response to highly tuned acidic conditions, the chemistry of which may have further implications in Fe–S biogenesis.