Iron-sulfur clusters – functions of an ancient metal site

Iron-sulfur clusters are ubiquitous and ancient prosthetic groups that are present in all kingdoms of life. In the 1960s, they were recognized to play a role in electron-transfer reactions, but since then several other functions were identified, which can be attributed to their flexible coordination and redox properties. In here, the canonical iron-sulfur clusters, as well as the ones with other coordinating ligands will be described. The chapter has also been updated to account for the advances in the knowledge of complex iron-sulfur clusters of nitrogenase and hydrogenases. In addition, the role of iron-sulfur clusters in metabolic regulation, as sensors of gases (nitric oxide, oxygen), iron and cellular content of iron-sulfur clusters, cellular redox status, and redox cycling compounds, as well as their role in DNA processing enzymes, and their involvement in catalysis of a wide range of reactions will be described. Iron-sulfur clusters also participate in their biosynthetic and repair pathways. The knowledge in this field as evolved tremendously in recent years, which would require a complete chapter devoted to it by itself, reason why the authors have decided not to include this subject in this chapter. The chapter is an update of the one published in the previous edition, focusing on the recent advances mostly on the iron-sulfur clusters involved in new catalytic functions, sensor mechanisms and DNA processing.