日本語フィールド
著者:Horitani, Masaki; Shisler, Krista; Broderick, William E.; Hutcheson, Rachel U.; Duschene, Kaitlin S.; Marts, Amy R.; Hoffman, Brian M.; Broderick, Joan B.題名:Metalloproteins: Radical SAM catalysis via an organometallic intermediate with an Fe-[5′-C]-deoxyadenosyl bond発表情報:Science 巻: 352 号: 6287 ページ: 822-825キーワード:概要:Radical S-adenosylmethionine (SAM) enzymes use a [4Fe-4S] cluster to cleave SAM to initiate diverse radical reactions. These reactions are thought to involve the 5′-deoxyadenosyl radical intermediate, which has not yet been detected. We used rapid freeze-quenching to trap a catalytically competent intermediate in the reaction catalyzed by the radical SAM enzyme pyruvate formate-lyase activating enzyme. Characterization of the intermediate by electron paramagnetic resonance and 13C, 57Fe electron nuclear double-resonance spectroscopies reveals that it contains an organometallic center in which the 5′ carbon of a SAM-derived deoxyadenosyl moiety forms a bond with the unique iron site of the [4Fe-4S] cluster. Discovery of this intermediate extends the list of enzymatic bioorganometallic centers to the radical SAM enzymes, the largest enzyme superfamily known, and reveals intriguing parallels to B12 radical enzymes.抄録:英語フィールド
Author:Horitani, Masaki; Shisler, Krista; Broderick, William E.; Hutcheson, Rachel U.; Duschene, Kaitlin S.; Marts, Amy R.; Hoffman, Brian M.; Broderick, Joan B.Title:Metalloproteins: Radical SAM catalysis via an organometallic intermediate with an Fe-[5′-C]-deoxyadenosyl bondAnnouncement information:Science Vol: 352 Issue: 6287 Page: 822-825An abstract:Radical S-adenosylmethionine (SAM) enzymes use a [4Fe-4S] cluster to cleave SAM to initiate diverse radical reactions. These reactions are thought to involve the 5′-deoxyadenosyl radical intermediate, which has not yet been detected. We used rapid freeze-quenching to trap a catalytically competent intermediate in the reaction catalyzed by the radical SAM enzyme pyruvate formate-lyase activating enzyme. Characterization of the intermediate by electron paramagnetic resonance and 13C, 57Fe electron nuclear double-resonance spectroscopies reveals that it contains an organometallic center in which the 5′ carbon of a SAM-derived deoxyadenosyl moiety forms a bond with the unique iron site of the [4Fe-4S] cluster. Discovery of this intermediate extends the list of enzymatic bioorganometallic centers to the radical SAM enzymes, the largest enzyme superfamily known, and reveals intriguing parallels to B12 radical enzymes.