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Reductive Cleavage of Sulfoxide and Sulfone by Two Radical S-Adenosyl-l-methionine Enzymes
Biochemistry ( IF 2.9 ) Pub Date : 2018-11-06 00:00:00 , DOI: 10.1021/acs.biochem.8b00844 Dhanaraju Mandalapu 1 , Xinjian Ji 1 , Qi Zhang 1
Biochemistry ( IF 2.9 ) Pub Date : 2018-11-06 00:00:00 , DOI: 10.1021/acs.biochem.8b00844 Dhanaraju Mandalapu 1 , Xinjian Ji 1 , Qi Zhang 1
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Sulfoxides and sulfones are commonly found in nature as a result of thioether oxidation, whereas only a very few enzymes have been found to metabolize these compounds. Utilizing the strong reduction potential of the [4Fe-4S] cluster of radical S-adenosyl-l-methionine (SAM) enzymes, we herein report the first enzyme-catalyzed reductive cleavage of sulfoxide and sulfone. We show two radical SAM enzymes, tryptophan lyase NosL and the class C radical SAM methyltransferase NosN, are able to act on a sulfoxide SAHO and a sulfone SAHO2, both of which are structurally similar to SAM. NosL cleaves all of the three bonds (i.e., S–C(5′), S–C(γ), and S–O) connecting the sulfur center of SAHO, with a preference for S–C(5′) bond cleavage. Similar S–C cleavage activity was also found for SHAO2, but no S–O cleavage was observed. In contrast to NosL, NosN almost exclusively cleaves the S–C(5′) bonds of SAHO and SAHO2 with much higher efficiencies. Our study provides valuable insights into the [4Fe-4S] cluster-mediated reduction reactions and highlights the remarkable catalytic promiscuity of radical SAM enzymes.
中文翻译：
两种自由基S-腺苷-1-蛋氨酸酶对亚砜和砜的还原裂解
由于硫醚氧化作用，自然界中普遍发现亚砜和砜，而仅发现极少数的酶可代谢这些化合物。利用自由基S-腺苷-1-甲硫氨酸（SAM）的[4Fe-4S]簇的强还原电位，我们在本文中报道了第一酶催化的亚砜和砜的还原裂解。我们显示了两个自由基SAM酶，色氨酸裂解酶NosL和C类自由基SAM甲基转移酶NosN，能够作用于亚砜SAHO和砜SAHO 2，两者在结构上都与SAM类似。NosL裂解连接SAHO硫中心的所有三个键（即，S–C（5'），S–C（γ）和S–O），优先选择S–C（5'）键裂解。SHAO也发现了类似的S–C裂解活性2，但未观察到S–O裂解。与NosL相反，NosN几乎完全以更高的效率裂解SAHO和SAHO 2的S–C（5'）键。我们的研究为[4Fe-4S]团簇介导的还原反应提供了有价值的见解，并突出了自由基SAM酶的显着催化混杂性。
更新日期：2018-11-06
中文翻译：
两种自由基S-腺苷-1-蛋氨酸酶对亚砜和砜的还原裂解
由于硫醚氧化作用，自然界中普遍发现亚砜和砜，而仅发现极少数的酶可代谢这些化合物。利用自由基S-腺苷-1-甲硫氨酸（SAM）的[4Fe-4S]簇的强还原电位，我们在本文中报道了第一酶催化的亚砜和砜的还原裂解。我们显示了两个自由基SAM酶，色氨酸裂解酶NosL和C类自由基SAM甲基转移酶NosN，能够作用于亚砜SAHO和砜SAHO 2，两者在结构上都与SAM类似。NosL裂解连接SAHO硫中心的所有三个键（即，S–C（5'），S–C（γ）和S–O），优先选择S–C（5'）键裂解。SHAO也发现了类似的S–C裂解活性2，但未观察到S–O裂解。与NosL相反，NosN几乎完全以更高的效率裂解SAHO和SAHO 2的S–C（5'）键。我们的研究为[4Fe-4S]团簇介导的还原反应提供了有价值的见解，并突出了自由基SAM酶的显着催化混杂性。
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