Metal-organic frameworks (MOFs) are rarely applied as solid supports in the enzymatic synthesis of oligosaccharides and polysaccharides, as glycosyltransferases are readily inactivated by traditional MOFs due to the poor compatibility and the limited mass transfer for complex carbohydrates in MOFs. Here, on the basis of the synthetic methods of zeolitic imidazolate framework-90 (ZIF-90), we prepared bimetal organic material (BMOM) microreactors that successfully encapsulated Pasteurella multocida heparosan synthase 2 (PmHS2), a critical glycosyltransferase in the enzymatic synthesis of heparin and heparan sulfate. The second metal ion introduced can increase the mesopores in the BMOM, stabilize the active pocket of glycosyltransferase, and facilitate the deprotonation of critical amino acid residues, Asp and Glu of PmHS2, to initiate the catalyzation. On the basis of this bimetallic microreactor, heparosan disaccharide, oligosaccharide, and polysaccharide are successfully prepared in quantitative yield, providing a viable BMOM-based immobilization strategy to simulate the physiological microenvironment for glycosyltransferase.
Keywords: bimetal organic materials; enzyme immobilization; glycosyltransferase; heparan sulfate.