酶是一类具备优异催化活性和高区域选择性的天然催化剂,在工业催化领域具有广阔的应用前景。然而,酶促转化的应用受到酶在恶劣条件下的脆弱性的阻碍。幸运的是,固定化已被证明是改善酶不稳定性一种有前途的方法。由于物理化学特性可调,高结晶度,大比表面积、优越的吸附能力、可预先设计的结构和出色的稳定性等特性,共价有机框架(COFs)被认为是固定化酶的理想载体材料。与其他传统载体材料相比,COFs的高度多孔性使其具有更高的酶载量,表现出更优的催化效果。酶是通过物理吸附、直接共价连接或通过交联剂,实现与COFs的结合。首先介绍了COFs的合成方法与功能化,然后系统总结了COFs固定化酶的策略与最新研究进展,最后初步讨论了COFs在固定化酶领域面临的挑战与机遇。
Enzymes are natural catalysts with remarkable catalytic activity and high regioselectivity and have promising applications in industrial catalysis.However,the application of enzymatic conversion is hindered by the vulnerability of enzymes under harsh conditions.Fortunately,immobilization has been shown to be a promising approach to improve enzyme instability.Covalent organic frameworks (COFs) are considered as ideal carrier materials for immobilizing enzymes due to their tunable physicochemical properties,high crystallinity,large specific surface area,superior adsorption capacity,pre-designable structure and excellent stability.Compared with other conventional carrier materials,the highly porous nature of COFs allows them to have higher enzyme loading capacity and exhibit superior catalytic effects.The binding of enzymes to COFs is achieved by physical adsorption,direct covalent linkage,or by cross-linking agents.In this paper,we firstly introduced the synthesis methods and functionalization of COFs,then systematically summarized the strategies and recent research progress in COFs immobilizing enzymes,and finally,we initially discussed the challenges and opportunities of COFs in the field of enzyme immobilization.
[1] Liu D M,Chen J,Shi Y P.Advances on methods and easy separated support materials for enzymes immobilization[J].TrAC Trends in Analytical Chemistry,2018,102:332-342.
[2] Sheldon R A,Van Pelt S.Enzyme immobilisation in biocatalysis:why,what and how[J].Chemical Society Reviews,2013,42(15):6223-6235.
[3] Cao S,Xu P,Ma Y,et al.Recent advances in immobilized enzymes on nanocarriers[J].Chinese Journal of Catalysis,2016,37(11):1814-1823.
[4] Xia H,Li N,Zhong X,et al.Metal-organic frameworks:a potential platform for enzyme immobilization and related applications[J].Front Bioeng Biotechnol,2020,8:695.
[5] Sheldon R A.Enzyme immobilization:the quest for optimum performance[J].Advanced Synthesis & Catalysis,2007,349(8-9):1289-1307.
[6] Jan$\dot{c}$ek S T.Strategies for obtaining stable enzymes[J].Process Biochemistry,1993,28(7):435-445.
[7] Kuchner O,Arnold F H.Directed evolution of enzyme catalysts[J].Trends in Biotechnology,1997,15(12):523-530.
[8] Oliveira F L,De S França A,De Castro A M,et al.Enzyme immobilization in covalent organic frameworks:strategies and applications in biocatalysis[J].Chempluschem,2020,85(9):2051-2066.
[9] Veronese F M.Peptide and protein PEGylation:a review of problems and solutions[J].Biomaterials,2001,22(5):405-417.
[10] Lee E S,Kwon M J,Lee H,et al.Stabilization of protein encapsulated in poly(lactide-co-glycolide) microspheres by novel viscous S/W/O/W method[J].International Journal of Pharmaceutics,2007,331(1):27-37.
[11] Magner E.Immobilisation of enzymes on mesoporous silicate materials[J].Chemical Society Reviews,2013,42(15):6213-6222.
[12] Diercks C S,Yaghi O M.The atom,the molecule,and the covalent organic framework[J].Science,2017,355(6328),DOI:10.1126/science.aal1585.
[13] Yusran Y,Fang Q,Qiu S.Postsynthetic covalent modification in covalent organic frameworks[J].Israel Journal of Chemistry,2018,58(9-10):971-984.
[14] Kang Z,Peng Y,Qian Y,et al.Mixed matrix membranes (MMMs) comprising exfoliated 2D covalent organic frameworks (COFs) for efficient CO2 separation[J].Chemistry of Materials,2016,28(5):1277-1285.
[15] Zhi Y,Li Z,Feng X,et al.Covalent organic frameworks as metal-free heterogeneous photocatalysts for organic transformations[J].Journal of Materials Chemistry A,2017,5(44):22933-22938.
[16] Mitra S,Sasmal H S,Kundu T,et al.Targeted drug delivery in covalent organic nanosheets (CONs) via sequential postsynthetic modification[J].Journal of the American Chemical Society,2017,139(12):4513-4520.
[17] Du Y,Yang H,Whiteley J M,et al.Ionic covalent organic frameworks with spiroborate linkage[J].Angewandte Chemie Internationa,2016,55(5):1737-1741.
[18] Li Z,Zhang Z,Nie R,et al.Construction of stable donor-acceptor type covalent organic frameworks as functional platform for effective perovskite solar cell enhancement[J].Advanced Functional Materials,2022,32(21):2112553.
[19] Campbell N L,Clowes R,Ritchie L K,et al.Rapid microwave synthesis and purification of porous covalent organic frameworks[J].Chemistry of Materials,2009,21(2):204-206.
[20] Yang S T,Kim J,Cho H Y,et al.Facile synthesis of covalent organic frameworks COF-1 and COF-5 by sonochemical method[J].RSC Advances,2012,2(27):10179-10181.
[21] Guan X,Ma Y,Li H,et al.Fast,ambient temperature and pressure ionothermal synthesis of three-dimensional covalent organic frameworks[J].Journal of the American Chemical Society,140(13):4494-4498.
[22] Biswal B P,Chandra S,Kandambeth S,et al.Mechanochemical synthesis of chemically stable isoreticular covalent organic frameworks[J].Journal of the American Chemical Society,2013,135(14):5328-5331.
[23] Peng Y,Wong W K,Hu Z,et al.Room temperature batch and continuous flow synthesis of water-stable covalent organic frameworks (COFs)[J].Chemistry of Materials,2016,28(14):5095-5101.
[24] Mukhtar A,Saqib S,Mellon N B,et al.CO2 capturing,thermo-kinetic principles,synthesis and amine functionalization of covalent organic polymers for CO2 separation from natural gas:a review[J].Journal of Natural Gas Science and Engineering,2020,77:103203.
[25] Yusran Y,Guan X,Li H,et al.Postsynthetic functionalization of covalent organic frameworks[J].National Science Review,2020,7(1):170-190.
[26] Kandambeth S,Venkatesh V,Shinde D B,et al.Self-templated chemically stable hollow spherical covalent organic framework[J].Nature Communications,2015,6:6786.
[27] Sun Q,Fu C W,AguilaA B,et al.Pore environment control and enhanced performance of enzymes infiltrated in covalent organic frameworks[J].Journal of the American Chemical Society,2018,140(3):984-992.
[28] Sun Q,Aguila B,Lan P C,et al.Tuning pore heterogeneity in covalent organic frameworks for enhanced enzyme accessibility and resistance against denaturants[J].Accelerated Materials,2019,31(19):e1900008.
[29] Samui A,Happy,Sahu S K.Integration ofα-amylase into covalent organic framework for highly efficient biocatalyst[J].Microporous and Mesoporous Materials,2020,291:109700.
[30] Zhong C,Ma W,He Y,et al.Controllable synthesis of hollow microtubular covalent organic frameworks as an enzyme-immobilized platform for enhancing catalytic activity[J].ACS Applied Materials & Interfaces,2021,13(44):52417-52424.
[31] Wang H,Jiao F,Gao F,et al.Covalent organic framework-coated magnetic graphene as a novel support for trypsin immobilization[J].Analytical and Bioanalytical Chemistry,2017,409(8):2179-2187.
[32] Zhang S,Zheng Y,An H,et al.Covalent organic frameworks with chirality enriched by biomolecules for efficient chiral separation[J].Angewandte Chemie International Edition,2018,57(51):16754-16759.
[33] Oliveira F L,De Souza S P,Bassut J,et al.Enzyme-decorated covalent organic frameworks as nanoporous platforms for heterogeneous biocatalysis[J].Chemistry,2019,25(69):15863-15870.
[34] Li M,Qiao S,Zheng Y,et al.Fabricating covalent organic framework capsules with commodious microenvironment for enzymes[J].Journal of the American Chemical Society,2020,142(14):6675-6681.
PDF
