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FeFeヒドロゲネーゼのH群とハリドの相互作用
Melisa Del Barrio1, Matteo Sensi1, Laura Fradale1
1Aix Marseille Université , CNRS, Bioénergétique et Ingénierie des Protéines , Marseille , France.
Journal of the American Chemical Society
|March 29, 2018
まとめ
FeFeヒドロゲナーゼは酸化条件下では逆活性化するが,塩化物またはブロミドイオンが存在する場合にのみ活性化される. これらのハリドは触媒介質と結合し,安定した不活性な酵素状態に導きます.
科学分野:
- 生物化学
- 酵素学
- バイオ有機化学
背景:
- FeFeヒドロゲナーゼは,H2代謝に不可欠な酵素である.
- 特定の条件下での酵素の可逆不活性化については,十分に理解されていません.
- 以前の仮説は,adtリガンド結合または非生産的なH2結合を含んでいた.
研究 の 目的:
- FeFeヒドロゲネーゼの無酸素,酸化,H2依存の不活性化のメカニズムを解明する.
- 酵素不活性化における ハリドの役割を調査する.
- 抑制された酵素状態の構造モデルを提案する.
主な方法:
- 抑制の種類を決定する酵素運動の研究.
- 酵素構造をモデル化するための密度機能理論 (DFT) の計算.
- スペクトル検査 (提案)
主要な成果:
- 不活性化は,Cl-またはBr-の存在に厳密に依存する.
- 塩化物は非競争的阻害剤として作用し,触媒介質に結合する.
- 酸化により,酵素はハライド結合時に安定した非活性状態に閉じ込められる.
- ハリドは,鉄と直接ではなく,adtリガンドのアミン群と相互作用する.
結論:
- 以前提案された無効化メカニズムは不十分です.
- ハリドイオンはFeFeヒドロゲネーゼの可逆不活性化において重要な役割を果たします.
- 触媒介質へのハライド結合を含む新しいメカニズムが提案されています.
- この発見により 抑制状態を安定させ 更に研究が進められます
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