Chang, Wei-chenLiu, PinghuaGuo, Yisong2019-10-252019-10-252018-07-04Wei-chen Chang, Pinghua Liu, Yisong Guo. 2018. "Mechanistic Elucidation of Two Catalytically Versatile Iron(II)- and α-Ketoglutarate-Dependent Enzymes: Cases Beyond Hydroxylation." Comments on Inorganic Chemistry, Volume 38, Issue 4, pp. 127 - 165. https://doi.org/10.1080/02603594.2018.15098560260-35941548-9574https://hdl.handle.net/2144/38378Iron(II)- and α-ketoglutarate-dependent (Fe/αKG) enzymes catalyze a large array of reactions. Although hydroxylation reaction catalyzed by these enzymes has been investigated in great details, involving the ferryl (FeIV=O) as a key reactive intermediate. The mechanisms of reactions other than hydroxylation are still largely unknown. By using a combined biochemical, bio-organic, and spectroscopic approach, we have studied the mechanisms of two newly discovered Fe/αKG enzymes, FtmOx1 (endoperoxidase) and AsqJ (desaturase/epoxidase), revealing their strategies in controlling reactivity, namely the effect of redox/polar residues near the iron center, the electronic properties of the substrate, and the intrinsic reactivity of the ferryl intermediate.127 - 165Inorganic chemistryInorganic & nuclear chemistryα-ketoglutarate-dependentenzymeFerryl intermediateEpoxidationEndoperoxidationDesaturationArticle10.1080/02603594.2018.1509856427271