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構造を超えて: [NiFe]ヒドロゲネーゼのメカニズムモデルとしてのニッケル置換ラブレドキシン
Jeffrey W Slater1, Sean C Marguet1, Haleigh A Monaco1
1The Ohio State University , 100 West 18th Avenue , Columbus , Ohio 43210 , United States.
Journal of the American Chemical Society
|July 19, 2018
まとめ
ニッケル置換のラブレドキシン (NiRd) は[NiFe]ヒドロゲネーゼに似たメカニズムで水素生成を触媒化する. 燃料電池と水素の進化に 利点をもたらします
科学分野:
- バイオ有機化学
- カタリシス
- バイオ物理学
背景:
- 温和な環境下での触媒性水素生成のための頑丈な分子システムを開発することは困難です.
- ニッケル置換のラブレドキシン (NiRd) は[NiFe]ヒドロゲネーゼの活性部位を模倣し,同様の触媒活性を示します.
- NiRdの触媒メカニズムは以前は解明されていなかった.
研究 の 目的:
- NiRdによって触媒化された水素の進化のメカニズムを調査する.
- NiRdメカニズムとネイティブ[NiFe]ヒドロゲナーゼを比較する.
- タンパク質工学による NiRd 活動の最適化のための戦略を特定する.
主な方法:
- 定量タンパク質膜の電気化学
- 光学および振動スペクトル
- 密度関数理論 (DFT) の計算
- 分子動力学 (MD) シミュレーション
主要な成果:
- 陽子と結合した電子の移転は,NiRd触媒に不可欠です.
- チオラートリガンドは,ニッケル中心の還元に先行するプロトネーションサイトとして作用する.
- 速度を制限するステップは,チオル逆転経由で分子内プロトン移転を行い,Ni (III) -ヒドリド種を形成する.
- NiRd触媒は,原生水素酸とは異なり,酸素に無感性である.
- タンパク質の変異は活動と速度を決定するステップを変化させ,外部の調整球の役割を強調します.
結論:
- NiRdは,チオラートプロトネーションを含む[NiFe]ヒドロゲナーゼに類似するメカニズムを使用しています.
- この発見は,原生ヒドロゲネーゼ機能におけるチオラートプロトネーションの潜在的な役割を示唆している.
- NiRdの酸素無感性と調節可能な活動は,燃料電池と有酸素水素の進化におけるアプリケーションの機会を提供します.
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