Department of Health Science and Technology, ETH Zurich, Schmelzbergstrasse 9, 8092 Zürich, Switzerland.
Nanoscale. 2019 Mar 28;11(13):5891-5895. doi: 10.1039/c8nr09671f.
Biocatalytic self-assembly in a nanoconfined environment is widely used in nature to construct complex structures that endow special characteristics to life. There is tremendous interest in mimicking such bottom-up processes to fabricate functional materials. In this study, we have investigated a novel biomimetic scaffold based on lipidic cubic mesophases (LCMs), which provide a special nanoconfined environment for biocatalytic self-assembly and subsequent formation of organic crystals. (R)-Benzoin generated in situ from benzaldehyde in a reaction catalyzed by the enzyme benzaldehyde lyase (BAL) exhibits - when confined within LCMs - enhanced chirality compared to (R)-benzoin in solution or (R)-benzoin-doped LCMs. We infer that a metastable state is formed under kinetic control that displays enhanced supramolecular chirality. As they age, these metastable structures can further grow into thermodynamically stable crystals. The biomimetic, nanoconfined environment provided by the LCMs plays a key role in the development of supramolecular chirality and subsequent crystallization.
在纳米受限环境中进行生物催化自组装在自然界中被广泛用于构建赋予生命特殊特性的复杂结构。人们对模仿这种自下而上的过程来制造功能性材料有着浓厚的兴趣。在这项研究中，我们研究了一种基于脂质立方相 (LCM) 的新型仿生支架，它为生物催化自组装和随后的有机晶体形成提供了一个特殊的纳米受限环境。在酶苯甲醛裂解酶 (BAL) 催化的反应中，由苯甲醛原位生成的 (R)-安息香与溶液中的 (R)-安息香或 (R)-安息香掺杂的 LCM 相比，在受限于 LCM 内时表现出增强的手性。我们推断，在动力学控制下形成了一种亚稳状态，显示出增强的超分子手性。随着时间的推移，这些亚稳结构可以进一步生长成热力学稳定的晶体。LCM 提供的仿生纳米受限环境在手性和随后的结晶过程中起着关键作用。
