Reaction of Nitroxyl (HNO) with Hydrogen Sulfide and Hydropersulfides
Reaction of Nitroxyl (HNO) with Hydrogen Sulfide and Hydropersulfides
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DOI：
10.1021/acs.joc.0c02412
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发表时间：
2021-01-01
影响因子：
3.6
通讯作者：
Toscano, John P.
中科院分区：
文献类型：
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作者：
Zarenkiewicz, Jessica;Khodade, Vinayak S.;Toscano, John P.
硝酰基（HNO）因其有前景的药理作用而受到广泛关注。 HNO 活性的生化机制与调节性硫醇蛋白的修饰有关。最近，一些研究表明，氢过硫化物 (RSSH)（推测为硫化氢 (H2S) 介导的硫醇 (RSH) 修饰的信号产物）是 HNO 的其他潜在靶标。然而，HNO 与硫醇以外的活性硫物质的相互作用仍然相对未经探索。在此，我们描述了 HNO 与 H2S 和 RSSH 的反应性。 H2S 与 HNO 的反应导致形成多硫化氢和硫 (S-8)，这表明其在硫烷硫稳态中具有潜在作用。此外，我们还发现，氢过硫化物比硫醇同类物更能有效捕获 HNO。通过观察到的各种二烷基多硫醚 (RSSnSR) 和其他含氮二烷基多硫醚 (RSS-NH-SnR) 的生成，研究了 HNO 与 RSSH 在不同化学计量下的反应。我们没有观察到磺基亚磺酰胺 (RS-S(O)-NH2) 形成的证据，这是与已知的 HNO 与硫醇反应性类似的预期途径。
Nitroxyl (HNO) has gained a considerable amount of attention because of its promising pharmacological effects. The biochemical mechanisms of HNO activity are associated with the modification of regulatory thiol proteins. Recently, several studies have suggested that hydropersulfides (RSSH), presumed signaling products of hydrogen sulfide (H2S)-mediated thiol (RSH) modification, are additional potential targets of HNO. However, the interaction of HNO with reactive sulfur species beyond thiols remains relatively unexplored. Herein, we present characterization of HNO reactivity with H2S and RSSH. The reaction of H2S with HNO leads to the formation of hydrogen polysulfides and sulfur (S-8), suggesting a potential role in sulfane sulfur homeostasis. Furthermore, we show that hydropersulfides are more efficient traps for HNO than their thiol counterparts. The reaction of HNO with RSSH at varied stoichiometries has been examined with the observed production of various dialkylpolysulfides (RSSnSR) and other nitrogen-containing dialkylpolysulfide species (RSS-NH-SnR). We do not observe evidence of sulfenylsulfinamide (RS-S(O)-NH2) formation, a pathway expected by analogy with the known reactivity of HNO with thiol.