Oxidoreductases containing transition metal ions are widespread in nature and are essential for living organisms. In these enzymes, transition metal ions are present either as mononuclear centers or organized into clusters, accomplishing two main roles. One is to be the core of active sites where the substrate is converted into product, and the other is to serve as electron transfer centers. Oxidoreductases containing multiple redox cofactors bind both the substrate and an external electron donor/acceptor at distant protein sites for them to exchange the electrons involved in the redox reaction. Intra-protein electron transfer occurs through specific pathways that link distant metal cofactors, which may additionally be magnetically coupled. Here we review the current understanding on the molecular properties of these long chemical pathways involved in metal coordination, intra − protein electron transfer processes, and transmitting magnetic interactions in Mo- and Cu-containing oxidoreductases.

含有过渡金属离子的氧化还原酶在自然界中广泛存在，对生物体至关重要。在这些酶中，过渡金属离子要么作为单核中心存在，要么以簇状存在，完成两个主要作用。一是作为底物转化为产物的活性位点的核心，二是作为电子传递中心。含有多种氧化还原辅因子的氧化还原酶在远处的蛋白质位点结合底物和外部电子供体/受体，以便它们交换参与氧化还原反应的电子。蛋白质内电子转移通过连接远处金属辅因子的特定途径发生，这些辅因子可能另外是磁耦合的。