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生物系统中的硫自由基:重要还是微不足道?

Thiyl radicals in biological systems: significant or trivial?

作者信息

Kalyanaraman B

机构信息

Biophysics Research Institute, Medical College of Wisconsin, Milwaukee 53226-06059, USA.

出版信息

Biochem Soc Symp. 1995;61:55-63. doi: 10.1042/bss0610055.

DOI:10.1042/bss0610055
PMID:8660403
Abstract

Thiyl radicals are formed from one-electron oxidation of thiols. Thiyl radicals participate in a number of reactions including electron transfer, hydrogen abstraction and addition reactions with several biological constituents and xenobiotics. Thiyl radicals can be detected by optical spectroscopy or by electron spin resonance (ESR) spectroscopy. Thiyl radicals appear to play a role in the nitrosylation of thiols and protein thiols. The exact mechanism of thiol-induced enhancement of oxidative modification of low-density lipoprotein remains questionable. The proposed role of thiyl radicals in lipid peroxidation needs to be re-examined. It has been proposed that thiyl radicals are detoxified by superoxide dismutase in mammalian cells and by a thiol-specific enzyme in bacterial systems. We propose that thiols or protein thiols act as potent antioxidants in radical-induced damage via formation of thiyl radicals.

摘要

硫自由基由硫醇的单电子氧化形成。硫自由基参与许多反应,包括电子转移、氢原子提取以及与多种生物成分和外源性物质的加成反应。硫自由基可通过光学光谱法或电子自旋共振(ESR)光谱法检测。硫自由基似乎在硫醇和蛋白质硫醇的亚硝基化中起作用。硫醇诱导的低密度脂蛋白氧化修饰增强的确切机制仍存在疑问。硫自由基在脂质过氧化中所提出的作用需要重新审视。有人提出,硫自由基在哺乳动物细胞中由超氧化物歧化酶解毒,在细菌系统中由一种硫醇特异性酶解毒。我们提出,硫醇或蛋白质硫醇通过形成硫自由基在自由基诱导的损伤中作为有效的抗氧化剂。

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1
Thiyl radicals in biological systems: significant or trivial?生物系统中的硫自由基:重要还是微不足道?
Biochem Soc Symp. 1995;61:55-63. doi: 10.1042/bss0610055.
2
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Free Radic Res. 2000 Dec;33(6):719-29. doi: 10.1080/10715760000301241.
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Beneficial and harmful effects of thiols.硫醇的有益和有害影响。
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The reactivity of thiols and disulfides with different redox states of myoglobin. Redox and addition reactions and formation of thiyl radical intermediates.硫醇和二硫化物与不同氧化还原状态的肌红蛋白的反应性。氧化还原与加成反应以及硫自由基中间体的形成。
J Biol Chem. 1992 Jan 25;267(3):1680-8.
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Thiyl radical reaction with amino acid side chains: rate constants for hydrogen transfer and relevance for posttranslational protein modification.硫自由基与氨基酸侧链的反应:氢转移的速率常数及与蛋白质翻译后修饰的相关性
Chem Res Toxicol. 2004 Oct;17(10):1323-8. doi: 10.1021/tx049856y.
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Antioxidant and pro-oxidant effect of the thiolic compounds N-acetyl-L-cysteine and glutathione against free radical-induced lipid peroxidation.硫醇类化合物N-乙酰-L-半胱氨酸和谷胱甘肽对自由基诱导的脂质过氧化的抗氧化和促氧化作用。
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Protein thiyl radical reactions and product formation: a kinetic simulation.蛋白质硫基自由基反应与产物形成:动力学模拟
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Kinetics of the reaction between nitroxide and thiyl radicals: nitroxides as antioxidants in the presence of thiols.氮氧化物与硫自由基之间反应的动力学:在硫醇存在下作为抗氧化剂的氮氧化物。
J Phys Chem A. 2008 Sep 18;112(37):8600-5. doi: 10.1021/jp804743g. Epub 2008 Aug 27.

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