DNA-Scaffolded Synergistic Catalysis.
DNA-Scaffolded Synergistic Catalysis.
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DOI：
10.1021/jacs.1c10757
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发表时间：
2021-12-22
影响因子：
15
通讯作者：
Martell, Jeffrey D.
中科院分区：
文献类型：
--
作者：
Pimentel, Edward B.;Peters-Clarke, Trenton M.;Coon, Joshua J.;Martell, Jeffrey D.
我们报告DNA支架协同催化，一个概念，结合了协同催化的不同反应范围与DNA的能力，以精确地预组织非生物基团，并进行刺激引发的构象变化。作为这一概念的初步论证，我们专注于Cu-TEMPO催化的有氧醇氧化，使用DNA作为支架，以保持铜助催化剂和有机自由基助催化剂（克里思）接近。DNA支架催化剂在稀释后保持高周转数，并表现出相对于未支架助催化剂的催化剂周转数提高190倍。通过将助催化剂纳入到含有DNA发夹的支架中，我们证明了协同催化反应的速率可以通过改变助催化剂之间的距离的可逆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。
We report DNA-scaffolded synergistic catalysis, a concept that combines the diverse reaction scope of synergistic catalysis with the ability of DNA to precisely pre-organize 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 co-catalyst and an organic radical co-catalyst (TEMPO) in proximity. The DNA-scaffolded catalyst maintained high turnover number upon dilution and exhibited 190-fold improvement in catalyst turnover number relative to the unscaffolded co-catalysts. By incorporating the co-catalysts 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 co-catalysts. This work demonstrates the compatibility of synergistic catalytic reactions with DNA scaffolding, opening future avenues in reaction discovery, sensing, responsive materials, and chemical biology.
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