In 2010 it was found that cyclodextrin, together with an inorganic salt, can assemble into a Metal-Organic Framework (CD-MOF) with high crystalline order. CD-MOFs have a significant interest in biocatalysis, and drug delivery as cyclodextrin is biocompatible, has slow dissolution in water, and can be used as an additive to protect protein structures. Active proteins contained within CD-MOFs may extend their storage time, stability, and enzymatic activities even in non-aqueous mixtures. However, the encapsulation of biomolecules into CD-MOFs has not yet been realized, likely due to the harsh synthesis conditions (pH≥12) and long synthesis times (5-7 days) of CD-MOFs. We developed a rapid and biofriendly CD-MOF synthesis to achieve a bioencapsulation with minimal structure and activity loss. Using this method, we show the encapsulation of Bovine Serum Albumin, Catalase and Myoglobin. CD-MOFs crystal structures are studied using scanning electron microscopy, transmission electron microscopy, and x-ray diffraction. We found that CD-MOFs retain their crystalline structure with proteins of different Isoelectric points and molar mass. The proteins retain their activity after encapsulation which is demonstrated through catalytic studies. We also show that the catalysis can be performed in organic solvents that would typically denature the enzymes. We believe that encapsulation of proteins into CD-MOF will have a significant impact on the field of drug delivery for protein-MOFs as they will likely have no toxicity and should display protection against natural enzymatic and chemical degradation. Furthermore, we are confident that CD-MOFs may also serve as a platform for delivering other biomolecules, such as DNAs and RNAs, expanding even further their applicability in medicine.

Protein encapsulation of cyclodextrin-based metal-organic framework

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ACS Fall 2022

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