Adenosylmethionine-dependent iron-sulfur enzymes: versatile clusters in a radical new role.
Iron-sulfur clusters are widespread in biological systems and participate in a broad range of functions. These functions include electron transport, mediation of redox as well as non-redox catalysis, and regulation of gene expression. A new role for iron-sulfur clusters has emerged in recent years as a number of enzymes have been identified that utilize Fe-S clusters and S-adenosylmethionine (AdoMet) to initiate radical catalysis. This Fe-S cluster-mediated radical catalysis includes the generation of stable protein-centered radicals as well as generation of substrate radical intermediates, with evidence suggesting a common mechanism involving an intermediate adenosyl radical. Although the mechanism of generation of the adenosyl radical intermediate is currently not well understood, it likely represents novel chemistry for iron-sulfur clusters. The purpose of this review is to present the current state of knowledge of this newly emerging group of Fe-S/AdoMet enzymes.
Cheek
J
J
Department of Chemistry, Michigan State University, East Lansing, MI 48824, USA.
Broderick
J B
JB
D000123:Acetyltransferases; D000595:Amino Acid Sequence; D000693:Anaerobiosis; D001426:Bacterial Proteins; D019755:Carbon-Carbon Lyases / Q000378:metabolism; D004255:Deoxyribodipyrimidine Photo-Lyase / Q000737:chemistry / Q000378:metabolism; D004798:Enzymes / Q000737:chemistry* / Q000378:metabolism*; D005609:Free Radicals; D019751:Intramolecular Transferases / Q000378:metabolism; D007506:Iron-Sulfur Proteins / Q000737:chemistry* / Q000378:metabolism*; D008969:Molecular Sequence Data; D011506:Proteins; D012436:S-Adenosylmethionine / Q000378:metabolism*; D013466:Sulfurtransferases / Q000737:chemistry / Q000378:metabolism
D001426:Bacterial Proteins; D004798:Enzymes; D005609:Free Radicals; D007506:Iron-Sulfur Proteins; D011506:Proteins; C408542:nrdG protein, Lactococcus lactis; D012436:S-Adenosylmethionine; D000123:Acetyltransferases; C040285:pyruvate formate-lyase activating enzyme; D013466:Sulfurtransferases; C057985:biotin synthetase; D019755:Carbon-Carbon Lyases; C114354:benzylsuccinate synthase; C088014:spore photoproduct lyase; D004255:Deoxyribodipyrimidine Photo-Lyase; D019751:Intramolecular Transferases; C021518:lysine 2,3-aminomutase