トランスエステル化のためのスピロリゴ酵素:構造と活性との関係の設計と関係
Mahboubeh Kheirabadi1, Nihan Çelebi-Ölçüm, Matthew F L Parker
1Department of Chemistry, Temple University, 1901 North 13th Street, Philadelphia, Pennsylvania 19122, USA.
Journal of the American Chemical Society
|September 21, 2012
まとめ
研究者らは,新種のスピロリゴ酵素触媒をトランスエステル化のために設計した. これらの分子触媒は,最高の三機能スピロリゴ酵素が複数のターンバーと効率的なアシル転送を達成し,触媒設計の新たな道を示し,大幅な速度向上を示した.
科学分野:
- 超分子化学 超分子化学
- カタリシス カタリシス カタリシス
- オーガニック・シンセシス オーガニック・シンセシス
背景:
- 効率的で選択的な触媒の開発は,化学合成に不可欠です.
- 梯子-分子の支架は,触媒設計のためのユニークな構造制御を提供します.
- スピロリゴージームは,機能化された分子構造の新しいクラスを表しています.
研究 の 目的:
- トランスエステル化反応のための新型スピロリゴ酵素の設計と合成.
- 合成変異と機能群配列を通じて触媒の性能を最適化するために.
- 計算的方法を用いて触媒機構を解明する.
主な方法:
- ステレオ化学的に定義された二機能性および三機能性スピロリゴジームの設計と合成.
- ビニルトリフオロアセテートを電化体として,メタノールを受容体として使用した運動学的研究.
- 移行状態と反応経路を特定するための量子力学的計算.
主要な成果:
- 二機能スピロリゴ酵素は,背景反応と比較して最大2.7×10^3倍までアシル転移を加速した.
- オキシアニオンホール形成のための尿素分子を組み込んだ三機能スピロリゴ酵素は,複数の触媒回転を可能にしました.
- 最良の三機能スピロリゴ酵素は,トランスエステル化のための速度の向上を示した (k ^ 1) / k ^ 1) = 2.2 × 10 ^ 3,k ^ 2) / k ^ 2) = 1.3 × 10 ^ 2).
- 計算分析により,触媒循環の移行状態に関する詳細な洞察が得られた.
結論:
- 立体化学的に定義されたスピロリゴジームは,強力なトランスエステル化触媒として効果的に設計することができます.
- "インサイド・アウト"設計戦略と合成変異は,触媒性能の最適化に有効です.
- 開発されたスピロリゴ酵素は,アシル移転反応のための有望な新種の触媒を代表しています.
![Solid-phase Synthesis of [4.4] Spirocyclic Oximes](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F58508.jpg&w=3840&q=50)
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