锌离子在一氧化氮信号中的硫代亚硝酰基和过硫代亚硝酰基。
Thionitrite and Perthionitrite in NO Signaling at Zinc.
机构信息
Department of Chemistry, Georgetown University, Box 571227, Washington, DC, 20057-1227, USA.
出版信息
Angew Chem Int Ed Engl. 2021 Sep 20;60(39):21184-21188. doi: 10.1002/anie.202104906. Epub 2021 Aug 23.
NO and H S serve as signaling molecules in biology with intertwined reactivity. HSNO and HSSNO with their conjugate bases SNO and SSNO form in the reaction of H S with NO as well as S-nitrosothiols (RSNO) and nitrite (NO ) that serve as NO reservoirs. While HSNO and HSSNO are elusive, their conjugate bases form isolable zinc complexes TpZn(SNO) and TpZn(SSNO) supported by tris(pyrazolyl)borate ligands. Reaction of Na(15-C-5)SSNO with TpZn(ClO ) provides TpZn(SSNO) that undergoes S-atom removal by PEt to give TpZn(SNO) and S=PEt . Unexpectedly stable at room temperature, these Zn-SNO and Zn-SSNO complexes release NO upon heating. TpZn(SNO) and TpZn(SSNO) quickly react with acidic thiols such as C F SH to form N O and NO, respectively. Increasing the thiol basicity in p-substituted aromatic thiols ArSH in the reaction with TpZn(SNO) turns on competing S-nitrosation to form TpZn-SH and RSNO, the latter a known precursor for NO.
NO 和 H S 作为生物学中的信号分子，具有相互交织的反应性。HSNO 和 HSSNO 及其共轭碱 SNO 和 SSNO 形成于 H S 与 NO 以及 S-亚硝基硫醇 (RSNO) 和亚硝酸盐 (NO ) 的反应中，它们作为 NO 的储库。虽然 HSNO 和 HSSNO 难以捉摸，但它们的共轭碱形成可分离的锌配合物 TpZn(SNO)和 TpZn(SSNO)，由三(吡唑基)硼酸盐配体支持。Na(15-C-5)SSNO 与 TpZn(ClO )反应生成 TpZn(SSNO)，后者通过 PEt 脱除 S 原子，得到 TpZn(SNO)和 S=PEt 。这些 Zn-SNO 和 Zn-SSNO 配合物在室温下出乎意料地稳定，加热时会释放出 NO。TpZn(SNO)和 TpZn(SSNO) 迅速与酸性硫醇如 C F SH 反应，分别形成 N O 和 NO。在与 TpZn(SNO)的反应中，取代基为芳香族硫醇的 p-取代基的硫醇的碱性增加，会引发竞争的 S-亚硝化反应，形成 TpZn-SH 和 RSNO，后者是已知的 NO 前体。
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