Embedding Functional Biomacromolecules within Peptide‐Directed Metal–Organic Framework (MOF) Nanoarchitectures Enables Activity Enhancement

Abstract Rationally tailoring a robust artificial coating can enhance the life‐time of fragile biomacromolecules. However, the coating also can restrain the activity of the guest because of the decreased substrate accessibility. Herein, we report a peptide‐directed strategy that enables in situ tailoring of the MOF‐shrouded biohybrids into controllable nanoarchitectures. The MOF biohybrid can be shaped from different 3D microporous architectures into a 2D mesoporous layer by a peptide modulator. Using this mild strategy, we show that the nanoarchitectures of the MOF coatings significantly affect the biological functions of the contained biomacromolecules. The biomacromolecules entrapped within the novel 2D mesoporous spindle‐shaped MOFs (2D MSMOFs) have significantly increased bioactivity compared to when encased within the hitherto explored 3D microporous MOFs. The improvement results from the shortened diffusion path and enlarged pore channel in 2D MSMOFs. Meanwhile, the thin 2D MSMOF layer also can provide excellent protection of the hosted biomacromolecules or protein‐scaffolded biominerals through structural confinement.