The formation of biofunctionalized metal–organic frameworks (MOFs) by growing them on a variety of macromolecular biological species, particularly on enzymes and living cells, offers exciting opportunities for a wide range of applications, including biocatalysis, biosensing, and diagnoses. MOFs are commonly subjected to biofunctionalization and biomimetic mineralization, owing to their good chemical and thermal stabilities and easy preparation in aqueous medium under ambient conditions. The functionalization of MOFs with biological substances, such as enzymes, nonenzymatic proteins, and living cells promotes the formation of MOF‐based biocomposites which retain the biological functions of the embedded biological substances. The most common method to construct these biofunctionalized MOFs is either by directly growing the MOF on the biological moiety or by postsynthetic modification of the exterior surface of the MOF with the desired biological species. In particular, hierarchically porous MOFs (containing both mesopores and micropores) are ideal candidates for hosting enzymes and for the translocation of nonenzymatic proteins. This review covers various advanced strategies for developing MOF‐based biocomposites for a wide range of bioapplications, such as biomedical storage, tumor cell targeting, and drug delivery. The influence of MOFs on the biological activity of living cells and future prospects for developing novel MOF‐based biorefinery are discussed.

A new borate fluoride, BaBOF·0.5HO, has been synthesized by high-temperature, high-pressure hydrothermal method, characterized by a combination of techniques and its structure determined by single-crystal X-ray diffraction. The compound crystallizes in the noncentrosymmetric space group P4̅ n2 (No. 118) and powder SHG measurements were performed to confirm the absence of a center of symmetry. Its crystal structure is formed of a new fundamental building block which shares oxygen atoms with neighboring blocks to form a 3D borate framework with 12- and 8-ring channels where the Ba cations, F anions, and water molecules are located. The structure is compared with those of minerals and synthetic borate fluoride and chlorides with similar framework compositions. The B MAS NMR experimental results are in accord with those from crystal structure analysis and the resonances in the spectrum are assigned. The presence of water was confirmed by IR spectroscopy, and its content and the thermal decomposition products were determined by thermogravimetric analysis and powder X-ray diffraction.