Intermolecular cross‐linking is one of the most important techniques that can be used to fundamentally alter the material properties of a polymer. The introduction of covalent bonds between individual polymer chains creates 3D macromolecular assemblies with enhanced mechanical properties and greater chemical or thermal tolerances. In contrast to many chemical cross‐linking reactions, which are the basis of thermoset plastics, enzyme catalysed processes offer a complimentary paradigm for the assembly of cross‐linked polymer networks through their predictability and high levels of control. Additionally, enzyme catalysed reactions offer an inherently ‘greener’ and more biocompatible approach to covalent bond formation, which could include the use of aqueous solvents, ambient temperatures, and heavy metal‐free reagents. Here, we review recent progress in the development of biocatalytic methods for polymer cross‐linking, with a specific focus on the most promising candidate enzyme classes and their underlying catalytic mechanisms. We also provide exemplars of the use of enzyme catalysed cross‐linking reactions in industrially relevant applications, noting the limitations of these approaches and outlining strategies to mitigate reported deficiencies.

中文翻译：

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酶催化聚合物交联：用于化学生物学、材料科学及其他领域的生物催化工具

分子间交联是最重要的技术之一，可用于从根本上改变聚合物的材料特性。在单个聚合物链之间引入共价键可创建具有增强的机械性能和更大的化学或热耐受性的 3D 大分子组件。与作为热固性塑料基础的许多化学交联反应相比，酶催化过程通过其可预测性和高度控制为交联聚合物网络的组装提供了补充范例。此外，酶催化反应为共价键形成提供了一种固有的“更环保”和更生物相容性的方法，其中可能包括使用水性溶剂、环境温度和不含重金属的试剂。这里，我们回顾了聚合物交联生物催化方法的最新进展，特别关注最有前途的候选酶类及其潜在的催化机制。我们还提供了在工业相关应用中使用酶催化交联反应的示例，并指出了这些方法的局限性并概述了减轻报告缺陷的策略。