Combining Pd nanoparticles on MOFs with cross-linked enzyme aggregates of lipase as powerful chemoenzymatic platform for one-pot dynamic kinetic resolution of amines

Incorporation of Metals and Enzymes with Porous Imine Molecule Cages for Highly Efficient Semiheterogeneous Chemoenzymatic Catalysis

“…Pd@CC3 (5 wt % Pd) showed a high activity even at 50 °C due to the improved solubility and completed the racemization within only 6 h under these conditions (Table , entry 12). It should be mentioned that the results obtained by Pd@CC3@CALB were better than previously reported results using insoluble supports such as alkaline earth salts, aluminum hydroxide, MOFs, and silica . These results verified our initial design that IMCs can endow the catalyst with partially homogeneous characteristics, which is responsible for the enhanced catalytic performance.…”

“…As a prototypical example of metal-enzyme catalysis in organic solvents, dynamic kinetic resolution (DKR) that combines the enzymatic kinetic resolution with metal-catalyzed racemization has proven to be a powerful method for the asymmetric synthesis of chiral amines . Although several MEICs have been found to efficiently catalyze the amine DKRs, , neither of them are tailor-made for this specific cascade system or to create an optimal microenvironment for catalytic sites, thus still leaving two major challenges in this field: (1) achieving the DKR process at low temperatures (<70 °C) and (2) suppressing undesired side reactions without the addition of alkalic salts . Herein, as a proof of concept, we report the synthesis of the IMC-based MEIC for highly efficient semiheterogeneous chemoenzymatic DKR of amines, in which the covalent immobilization of Candida antarctica lipase B (CALB) on MNP-embedded IMCs through direct utilization of imine bonds via the Ugi-type reaction was disclosed.…”

“…15 Although several MEICs have been found to efficiently catalyze the amine DKRs, 5,16 neither of them are tailor-made for this specific cascade system or to create an optimal microenvironment for catalytic sites, 10a thus still leaving two major challenges in this field: (1) achieving the DKR process at low temperatures (<70 °C) and (2) suppressing undesired side reactions without the addition of alkalic salts. 17 Herein, as a proof of concept, we report the synthesis of the IMC-based MEIC for highly efficient semiheterogeneous chemoenzymatic DKR of amines, in which the covalent immobilization of Candida antarctica lipase B (CALB) on MNP-embedded IMCs through direct utilization of imine bonds via the Ugi-type reaction was disclosed. The good solubility and hydrophobicity of IMC are responsible for the enhanced catalytic performance in organic solvents, and the basic microenvironment created by imine nitrogen atoms is essential for improved selectivity.…”

Confining enzymes in porous organic frameworks: from synthetic strategy and characterization to healthcare applications

“…Benefiting from these merits, enzyme–POF systems have been successfully applied in various areas, such as chemical synthesis, food processing, pollutant degradation, energy harvest, and healthcare. 32–38…”

Recent Advances in Emerging Metal– and Covalent–Organic Frameworks for Enzyme Encapsulation

“…Moreover, the dimensions of the enzyme molecule can be larger than the pore channel of MOFs, leading the enzymes to be surrounded by frameworks. In situ and pore encapsulation was employed in mesoporous MOFs and COFs (Fe-ZIF8, COF-43-B, Zn-MOF, PCN-222­(Fe), MIL-88B, H-MOF­(Zr), MIL-101­(Cr), Cu-BTC-based MOF, Pd@ED-MIL-10, PW@MIL-100­(Fe), Tb-MOF, meso-MIL-53­(Al), COF-OMe, etc. ), which is an efficient strategy to protect enzymes from harsh conditions by isolating enzyme molecules in the pores of the organic framework as well as preventing enzyme leakage from the supports.…”