Metal‐organic frameworks (MOFs) have recently emerged as excellent hosting matrices for enzyme immobilization, offering superior physical and chemical protection for biocatalytic reactions. However, for multienzyme and cofactor‐dependent biocatalysis, the subtle orchestration of enzymes and cofactors is largely disrupted upon immobilizing in the rigid crystalline MOF network, which leads to a much reduced biocatalytic efficiency. Herein, we constructed hierarchically porous MOFs by controlled structural etching to enhance multienzyme and cofactor‐dependent enzyme biocatalysis. The expanded size of the pores can provide sufficient space for accommodated enzymes to reorientate and spread within MOFs in their lower surface energy state as well as to decrease the inherent barriers to accelerate the diffusion rate of reactants and intermediates. Moreover, the developed hierarchically porous MOFs demonstrated outstanding tolerance to inhospitable surroundings and recyclability.

中文翻译：

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分层多孔生物催化MOF微反应器可作为增强多酶和辅因子依赖性生物催化的多功能平台

金属有机框架（MOFs）最近已成为固定化酶的优良宿主基质，为生物催化反应提供了出色的物理和化学保护。但是，对于多酶和依赖辅因子的生物催化，固定在刚性结晶MOF网络中后，酶和辅因子的微妙配伍就被大大破坏，这导致生物催化效率大大降低。本文中，我们通过控制结构刻蚀构建了层次多孔的MOF，以增强多酶和辅因子依赖性酶的生物催化作用。孔的扩大尺寸可以为容纳的酶以较低的表面能状态在MOF中重新定向和扩散提供足够的空间，并减少固有的障碍以加快反应物和中间体的扩散速度。