Humeniuk Heorhii V, Gini Andrea, Hao Xiaoyu, Coelho Filipe, Sakai Naomi, Matile Stefan
Department of Organic Chemistry, University of Geneva, 1211 Geneva, Switzerland.
JACS Au. 2021 Sep 28;1(10):1588-1593. doi: 10.1021/jacsau.1c00345. eCollection 2021 Oct 25.
The combination of catalysis and transport across lipid bilayer membranes promises directional access to a solvent-free and structured nanospace that could accelerate, modulate, and, at best, enable new chemical reactions. To elaborate on these expectations, anion transport and catalysis with pnictogen and tetrel bonds are combined with polyether cascade cyclizations into bioinspired cation transporters. Characterized separately, synergistic anion and cation transporters of very high activity are identified. Combined for catalysis in membranes, cascade cyclizations are found to occur with a formal rate enhancement beyond one million compared to bulk solution and product formation is detected in situ as an increase in transport activity. With this operational system in place, intriguing perspectives open up to exploit all aspects of this unique nanospace for important chemical transformations.
催化作用与跨脂质双分子层膜的运输相结合，有望定向进入无溶剂且结构化的纳米空间，从而加速、调节并在最佳情况下实现新的化学反应。为详细阐述这些期望，将阴离子运输以及与氮族元素和碳族元素键相关的催化作用与聚醚级联环化反应相结合，构建受生物启发的阳离子转运体。分别对其进行表征时，可识别出具有极高活性的协同阴离子和阳离子转运体。将它们组合用于膜中的催化反应时，发现级联环化反应的形式速率比本体溶液提高了超过一百万倍，并且原位检测到产物形成表现为运输活性的增加。有了这个运行系统，利用这个独特纳米空间的各个方面进行重要化学转化便开启了引人入胜的前景。
