硫化氢与二硫化物的反应：稳定的三硫化物的形成及其对生物系统的影响。
The reaction of hydrogen sulfide with disulfides: formation of a stable trisulfide and implications for biological systems.
机构信息
Department of Chemistry, Johns Hopkins University, Baltimore, MD, USA.
Department of Environmental Health Sciences and Molecular Toxicology, Tohoku University Graduate School of Medicine, Sendai, Japan.
出版信息
Br J Pharmacol. 2019 Feb;176(4):671-683. doi: 10.1111/bph.14372. Epub 2018 Jun 28.
BACKGROUND AND PURPOSE
The signalling associated with hydrogen sulfide (H S) remains to be established, and recent studies have alluded to the possibility that H S-derived species play important roles. Of particular interest are hydropersulfides (RSSH) and related polysulfides (RSS R, n > 1). This work elucidates the fundamental chemical relationship between these sulfur species as well as examines their biological effects.
EXPERIMENTAL APPROACH
Using standard analytical techniques ( H-NMR and MS), the equilibrium reactions between H S, disulfides (RSSR), RSSH, dialkyltrisulfides (RSSSR) and thiols (RSH) were examined. Their ability to protect cells from electrophilic and/or oxidative stress was also examined using cell culture.
KEY RESULTS
H S, RSSR, RSSH, RSSSR and RSH are all in a dynamic equilibrium. In a biological system, these species can exist simultaneously, and thus, it is difficult to discern which species is (are) the biological effector(s). Treatment of cells with the dialkyl trisulfide cysteine trisulfide (Cys-SSS-Cys) resulted in high intracellular levels of hydropersulfides and protection from electrophilic stress.
CONCLUSIONS AND IMPLICATIONS
In aqueous systems, the reaction between H S and RSSR results in the formation of equilibria whereby H S, RSH, RSSR, RSSH and RSSSR are present. In a biological system, any of these species can be responsible for the observed biological activity. These equilibrium species can also be generated via the reaction of RSH with RSSSR. Due to these equilibria, Cys-SSS-Cys can be a method for generating any of the other species. Importantly, HEK293T cells treated with Cys-SSS-Cys results in increased levels of hydropersulfides, allowing examination of the biological effects of RSSH.
LINKED ARTICLES
This article is part of a themed section on Chemical Biology of Reactive Sulfur Species. To view the other articles in this section visit http://onlinelibrary.wiley.com/doi/10.1111/bph.v176.4/issuetoc.
背景与目的
与硫化氢（H 2 S）相关的信号转导仍有待确定，最近的研究暗示 H 2 S 衍生的物质可能发挥重要作用。特别有趣的是氢过硫化物（RSSH）和相关的多硫化物（RSSR，n＞1）。这项工作阐明了这些硫物种之间的基本化学关系，并研究了它们的生物学效应。
实验方法
使用标准分析技术（ 1 H-NMR 和 MS），考察了 H 2 S、二硫化物（RSSR）、氢过硫化物（RSSH）、二烷基三硫化物（RSSSR）和硫醇（RSH）之间的平衡反应。还使用细胞培养研究了它们保护细胞免受亲电和/或氧化应激的能力。
主要结果
H 2 S、RSSR、RSSH、RSSSR 和 RSH 都处于动态平衡中。在生物系统中，这些物质可以同时存在，因此，很难确定哪种物质是（是）生物效应物。用二烷基三硫代半胱氨酸三硫代（Cys-SSS-Cys）处理细胞会导致细胞内高水平的氢过硫化物，并能抵抗亲电应激。
结论与意义
在水相体系中，H 2 S 与 RSSR 的反应导致形成平衡，其中存在 H 2 S、RSH、RSSR、RSSH 和 RSSSR。在生物系统中，观察到的生物学活性可以由任何一种物质引起。这些平衡物质也可以通过 RSH 与 RSSSR 的反应生成。由于这些平衡，Cys-SSS-Cys 可以作为生成其他任何物质的方法。重要的是，用 Cys-SSS-Cys 处理的 HEK293T 细胞导致氢过硫化物水平升高，从而可以检查 RSSH 的生物学效应。
链接文章
本文是关于活性硫物种的化学生物学的专题部分的一部分。要查看该部分中的其他文章，请访问 http://onlinelibrary.wiley.com/doi/10.1111/bph.v176.4/issuetoc。
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