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DNA 支架协同催化。

DNA-Scaffolded Synergistic Catalysis.

机构信息

Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706, United States.

Department of Biomolecular Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706, United States.

出版信息

J Am Chem Soc. 2021 Dec 22;143(50):21402-21409. doi: 10.1021/jacs.1c10757. Epub 2021 Dec 13.

Abstract

We report DNA-scaffolded synergistic catalysis, a concept that combines the diverse reaction scope of synergistic catalysis with the ability of DNA to precisely preorganize abiotic groups and undergo stimuli-triggered conformational changes. As an initial demonstration of this concept, we focus on Cu-TEMPO-catalyzed aerobic alcohol oxidation, using DNA as a scaffold to hold a copper cocatalyst and an organic radical cocatalyst (TEMPO) in proximity. The DNA-scaffolded catalyst maintained a high turnover number upon dilution and exhibited 190-fold improvement in catalyst turnover number relative to the unscaffolded cocatalysts. By incorporating the cocatalysts into a DNA hairpin-containing scaffold, we demonstrate that the rate of the synergistic catalytic reaction can be controlled through a reversible DNA conformational change that alters the distance between the cocatalysts. This work demonstrates the compatibility of synergistic catalytic reactions with DNA scaffolding, opening future avenues in reaction discovery, sensing, responsive materials, and chemical biology.

摘要

我们报告了 DNA 支架协同催化,这一概念将协同催化的广泛反应范围与 DNA 精确预组织非生物基团和进行刺激触发构象变化的能力结合起来。作为这一概念的初步展示,我们专注于 Cu-TEMPO 催化的有氧醇氧化,使用 DNA 作为支架将铜助催化剂和有机自由基助催化剂(TEMPO)保持在接近状态。DNA 支架催化剂在稀释后仍保持高转化率,与未支架的共催化剂相比,催化剂的转化率提高了 190 倍。通过将共催化剂纳入含有发夹 DNA 的支架中,我们证明协同催化反应的速率可以通过改变共催化剂之间距离的可逆 DNA 构象变化来控制。这项工作证明了协同催化反应与 DNA 支架的兼容性,为反应发现、传感、响应材料和化学生物学开辟了未来的途径。

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