モリブデン・コッパー人工ヒドロゲネーゼによって触媒化された光駆動水素進化反応
Raphaël J Labidi1, Bruno Faivre1, Philippe Carpentier2
1Laboratoire de Chimie des Processus Biologiques, UMR 8229, Collège de France/CNRS/Sorbonne Université, 11 place Marcellin-Berthelot, 75231 Paris, France.
Journal of the American Chemical Society
|June 12, 2023
まとめ
独特のモリブデン/銅のクラスターを持つオレンジのタンパク質 (Orp) は,陽子から水素の生成を触媒化する. 改造されたOrpの変種,特にMo/Fe-Orpは,可視光の下の人工水素化として記録的な効率を示しています.
科学分野:
- 生物化学
- バイオ有機化学
- 光触媒
背景:
- オレンジタンパク質 (Orp) は,未知の機能のユニークなヘテロメタリッククラスタを持つ細菌の金属タンパク質である.
- メタロプロテインは複雑な活性部位があるため,新しい触媒的応用の可能性があります.
研究 の 目的:
- 水素進化のためのオレンジタンパク質 (Orp) の光触媒活性を調査する.
- Orp内のモリブデン/銅 (Mo/Cu) ヘテロメタリッククラスタを特徴づけ,その触媒メカニズムを探求する.
- 改良されたOrpの変種を設計し,評価する.
主な方法:
- ホロオルプの生化学とスペクトル解析
- アクティブサイトを特定するためのドッキングと分子動力学シミュレーション
- アスコルベートと光敏感剤を用いた光触媒水素進化実験
- 反応メカニズムを解明するための密度関数理論 (DFT) の計算.
- Orpのエスカフォード内の様々な二核金属クラスター (M/M'-Orp) の組み立てと試験.
主要な成果:
- [S2MoS2CuS2MoS2]3-クラスターを含むホロオルプは,水素進化のための重要な光触媒活性を示した.
- ホロオルプは4時間の照射後に最大回転数 (TON) 890を達成した.
- DFTの計算は,H2形成における末端硫黄原子を含むメカニズムを提案した.
- エンジニアリングされたMo/Fe-Orpのバリエーションは,顕著なTON1150と初期ターンオーバー周波数 (TOF°) 800h-1を示し,人工水素化物の新記録を樹立した.
結論:
- オレンジタンパク質 (Orp) は,水素進化の効果的な光触媒である.
- オルプの独特のMo/Cuクラスターと特定のアミノ酸残留は,その触媒活性に不可欠です.
- エンジニアリングされたOrpの変種,特にMo/Fe-Orpは,持続的な水素生産の可能性のある高効率の人工水素化剤を表しています.
関連する概念動画
Reduction of Alkenes: Catalytic Hydrogenation
12.2K
Alkenes undergo reduction by the addition of molecular hydrogen to give alkanes. Because the process generally occurs in the presence of a transition-metal catalyst, the reaction is called catalytic hydrogenation.
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the...
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the...
12.2K
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
3.4K
Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
3.4K
Catalysis
27.1K
The presence of a catalyst affects the rate of a chemical reaction. A catalyst is a substance that can increase the reaction rate without being consumed during the process. A basic comprehension of a catalysts’ role during chemical reactions can be understood from the concept of reaction mechanisms and energy diagrams.
27.1K
Hydrogen Bonds
121.5K
Hydrogen bonds are weak attractions between atoms that have formed other chemical bonds. One of these atoms is electronegative, like oxygen, and has a partial negative charge. The other is a hydrogen atom that has bonded with another electronegative atom and has a partial positive charge.
Hydrogen Bonds Control the World!
Because hydrogen has very weak electronegativity when it binds with a strongly electronegative atom, such as oxygen or nitrogen, electrons in the bond are unequally shared....
Hydrogen Bonds Control the World!
Because hydrogen has very weak electronegativity when it binds with a strongly electronegative atom, such as oxygen or nitrogen, electrons in the bond are unequally shared....
121.5K
Chemiosmosis
100.1K
Oxidative phosphorylation is a highly efficient process that generates large amounts of adenosine triphosphate (ATP), the basic unit of energy that drives many cellular processes. Oxidative phosphorylation involves two processes— the electron transport chain and chemiosmosis.
Electron Transport Chain
The electron transport chain involves a series of protein complexes on the inner mitochondrial membrane that undergo a series of redox reactions. At the end of this chain, the electrons...
Electron Transport Chain
The electron transport chain involves a series of protein complexes on the inner mitochondrial membrane that undergo a series of redox reactions. At the end of this chain, the electrons...
100.1K
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
10.4K
Alkenes are converted to 1,2-diols or glycols through a process called dihydroxylation. It involves the addition of two hydroxyl groups across the double bond with two different stereochemical approaches, namely anti and syn. Dihydroxylation using osmium tetroxide progresses with syn stereochemistry.
10.4K


