Atom transfer radical polymerization (ATRP) has been considered to be an efficient strategy for constructing functional macromolecules owing to its simple operation and versatile monomers, and thus it is of great significance to develop ideal catalysts with higher activity and perfect reusability. We constructed a peroxidase mimic through the grafting of heme onto metal-organic frameworks UiO-66-NH₂ (ZrMOF), namely Heme-ZrMOF. After the systematic characterization of structure, the composite Heme-ZrMOF was demonstrated to possess high peroxidase activity using 2,2′-azinobis-(3-ethylbenzthiazoline-6-sulphonate) and 3,3′,5,5′-tetramethylbenzidine as substrates. The enzyme mimic was then used as catalysts in the ATRP reactions of different monomers, in which favorable monomer conversion (44.6–98.0%) and product molecular weight (8600–25,600 g/mol) could be obtained. Compared to free heme, Heme-ZrMOF could efficiently achieve the easy separation of heme from the catalytic system and facilitate the ATRP reaction in an aqueous environment to avoid the utilization of organic solvents. In conclusion, the enzyme mimic Heme-ZrMOF could be potentially used as an effective catalyst for preparing well-defined polymers with biomedical applications.

原子转移自由基聚合（ATRP）由于其简单的操作和通用的单体而被认为是构建功能性大分子的有效策略，因此开发具有更高活性和完美可重复使用性的理想催化剂具有重要意义。我们通过将血红素接枝到金属有机骨架UiO-66-NH ₂上构建了一个过氧化物酶模拟物（ZrMOF），即Heme-ZrMOF。对结构进行系统表征后，证明了以2,2'-叠氮基双-（3-乙基苯并噻唑啉-6-磺酸盐）和3,3'，5,5'-四甲基联苯胺为底物的复合血红素-ZrMOF具有较高的过氧化物酶活性。 。然后，该酶模拟物被用作不同单体的ATRP反应的催化剂，在其中可以获得良好的单体转化率（44.6–98.0％）和产物分子量（8600–25,600 g / mol）。与游离血红素相比，血红素-ZrMOF可以有效地实现血红素与催化体系的轻松分离，并有助于在水性环境中进行ATRP反应，从而避免了有机溶剂的利用。总之，模仿血红素-ZrMOF的酶可潜在地用作制备具有生物医学应用的明确聚合物的有效催化剂。