School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, People's Republic of China.
Institute of Crystalline Materials, Shanxi University, Taiyuan 030006, People's Republic of China.
J Am Chem Soc. 2021 Oct 13;143(40):16641-16652. doi: 10.1021/jacs.1c07482. Epub 2021 Oct 4.
Enzymatic microarchitectures with spatially controlled reactivity, engineered molecular sieving ability, favorable interior environment, and industrial productivity show great potential in synthetic protocellular systems and practical biotechnology, but their construction remains a significant challenge. Here, we proposed a Pickering emulsion interface-directed synthesis method to fabricate such a microreactor, in which a robust and defect-free MOF layer was grown around silica emulsifier stabilized droplet surfaces. The compartmentalized interior droplets can provide a biomimetic microenvironment to host free enzymes, while the outer MOF layer secludes active species from the surroundings and endows the microreactor with size-selective permeability. Impressively, the thus-designed enzymatic microreactor exhibited excellent size selectivity and long-term stability, as demonstrated by a 1000 h continuous-flow reaction, while affording completely equal enantioselectivities to the free enzyme counterpart. Moreover, the catalytic efficiency of such enzymatic microreactors was conveniently regulated through engineering of the type or thickness of the outer MOF layer or interior environments for the enzymes, highlighting their superior customized specialties. This study provides new opportunities in designing MOF-based artificial cellular microreactors for practical applications.
具有空间控制反应性、工程分子筛分能力、有利的内部环境和工业生产效率的酶微结构在合成原细胞系统和实际生物技术中显示出巨大的潜力，但它们的构建仍然是一个重大挑战。在这里，我们提出了一种 Pickering 乳液界面导向合成方法来制造这种微反应器，其中在二氧化硅乳化剂稳定的液滴表面周围生长了一个坚固且无缺陷的 MOF 层。分隔的内部液滴可以提供仿生微环境来容纳游离酶，而外部的 MOF 层将活性物种与周围环境隔离，并赋予微反应器尺寸选择性渗透性。令人印象深刻的是，所设计的酶微反应器表现出优异的尺寸选择性和长期稳定性，在 1000 小时的连续流动反应中得到了证明，同时为游离酶提供了完全相等的对映选择性。此外，通过工程化外部 MOF 层或酶的内部环境的类型或厚度，可以方便地调节这种酶微反应器的催化效率，突出了其优越的定制特性。这项研究为设计基于 MOF 的人工细胞微反应器用于实际应用提供了新的机会。
