Recent Trends in Metalloenzyme Chemistry: From Biochemistry to Electrochemistry to Spectroscopy

Metalloenzymes are among nature’s most sophisticated catalysts, enabling a remarkable range of chemical transformations that underpin biological function, global elemental cycles, and energy conversion. By combining the diverse reactivity of metal centers with the precisely controlled environment of a protein scaffold, these systems perform challenging reactions with exceptional efficiency and selectivity, often under mild conditions. Over the past decades, our understanding of metalloenzyme chemistry has progressed from identifying metal cofactors and establishing structure-function relationships toward interrogating catalytic mechanisms at increasingly fine spatial and temporal resolution. Advances in biochemistry, structural biology, spectroscopy, electrochemistry, kinetics, and computational chemistry now enable the characterization of transient intermediates, electronic structures, proton and electron transfer pathways, and dynamic changes occurring during catalysis. Importantly, the resulting mechanistic insights increasingly provide design principles for reproducing, and ultimately extending, nature’s catalytic strategies in synthetic systems.This Research Topic aims to highlight recent advances across the broad and increasingly interdisciplinary landscape of metalloenzyme chemistry, connecting fundamental biochemical understanding with mechanistic insight and emerging applications. Particular emphasis will be placed on studies that integrate complementary experimental and theoretical approaches to establish molecular-level descriptions of metalloenzyme function. At the same time, insights obtained from natural systems are increasingly inspiring chemistry beyond the native protein environment. Biomimetic molecular complexes provide platforms for reproducing and dissecting key elements of enzymatic active sites, while artificial metalloenzymes combine non-native metal centers (abiotic cofactors, non-native metal ions, or designed metal-binding sites) with natural, engineered, or de novo protein scaffolds to access natural and non-natural reactivity. Metalloenzyme-inspired concepts are also expanding into materials chemistry, where control of primary and secondary coordination spheres, confined reaction environments, and proton/electron-transfer pathways offers new opportunities for catalyst design. This collection seeks to bring these communities together and highlight how fundamental understanding of metalloenzymes can inspire new directions across chemical biology, catalysis, energy, and materials chemistry.We welcome Original Research, Reviews, Perspectives, and related contributions addressing areas including, but not limited to:Biochemistry, structure, and function of natural metalloenzymesMechanistic studies of metalloenzyme catalysis and catalytic intermediatesAdvanced spectroscopic, structural, kinetic, and electrochemical approachesComputational chemistry, molecular dynamics, and integrated experimental-theoretical studiesMetal-cofactor biosynthesis, assembly, maturation, and regulationBiomimetic and bioinspired molecular complexesArtificial metalloenzymes, protein engineering, and de novo metalloprotein designMetalloenzyme-inspired homogeneous and heterogeneous catalysisBioinspired functional materials and enzyme-like catalytic environmentsApplications of metalloenzymes and their mimics in biocatalysis, energy conversion, sustainability, sensing, and chemical synthesis Topic editors: Kushal Sengupta, Giorgio Caserta, Rahul Banerjee, Federica Arrigoni Source: https://www.frontiersin.org/research-topics/85672/recent-trends-in-metalloenzyme-chemistry-from-biochemistry-to-electrochemistry-to-spectroscopy