glutathione radical | 40055-99-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: glutathione radical
• CAS: 40055-99-0
• 化学式: C₁₀H₁₆N₃O₆S
• 分子量: 306.32
• InChiKey: WDICOIQYEIXETK-WDSKDSINSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -4.5
• 重原子数：
  20
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  160
• 氢给体数：
  5
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  glutathione radical 在 氧气 作用下， 以 水 为溶剂， 生成 (2R)-2-(4-amino-4-carboxybutanamido)-3-((carboxymethyl)amino)-3-oxopropane-1-sulfinate
  参考文献：
  名称：

  Tamba, Maurizio; O'Neill, Peter, Journal of the Chemical Society. Perkin transactions II, 1991, # 11, p. 1681 - 1685

  摘要：

  DOI：
• 作为产物：
  描述：

  (R)-2-((S)-4-Amino-4-carboxy-butyrylamino)-2-(carboxymethyl-carbamoyl)-ethanethiol anion 在 azide radical 作用下， 以 水 为溶剂， 生成 glutathione radical
  参考文献：
  名称：

  Kinetics of One-Electron Oxidation of Thiols and Hydrogen Abstraction by Thiyl Radicals from .alpha.-Amino C-H Bonds

  摘要：

  One-electron oxidation of cysteine, homocysteine, and glutathione by azide radical in alkaline solution (pH 10.5), where both the amino and the SH groups are deprotonated, has been investigated by pulse radiolysis. Reducing alpha-aminoalkyl radicals ((.)CR), which are formed via intramolecular rearrangement of thiyl radicals, were detected using methylviologen as oxidant in the kinetic analysis. The general scheme of the reactions is sketched. Thiyl radicals either equilibrate with RSSR(.-) in reaction 5, RS(.) + RS(-) = RSSR(.-), or undergo intramolecular transformation via equilibrium 6, RS(.) = (.)CR. At pH 10.5, equilibrium 6 is completely shifted to the right, resulting in alpha-aminoalkyl radical formation. The rate constants in the reaction scheme for cysteine, homocysteine, and glutathione were measured. With the rate constants obtained, the decay kinetics of RSSR(.-) into (.)CR was simulated, and it agreed with that measured at 420 nm. At pH 10.5, the first-order rate constants for the transformation (k(6)) were determined to be 2.5 x 10(4), 1.8 x 10(5) and 2.2 x 10(5) s(-1) for cysteine, homocysteine, and glutathione, respectively. The rate constants for intermolecular hydrogen abstraction by thiyl radicals from alpha-amino C-H bonds of alanine and glycine were determined at the same pH to be 7.7 x 10(5) and 3.2 x 10(5) M(-1) s(-1), respectively. Thermodynamic estimation places the reduction potential E degrees(H2NC(CO2-)CH3)(.), H+/H2NCH(CO2-)CH3) at ca. 1.22 V, which implies a rather weak tertiary C-H bond in the anion of alpha-amino acids. Thus, an intramolecular hydrogen abstraction mechanism for the transformation of thiyl radical to alpha-amino carbon-centered radical is postulated. Molecular geometry plays an important part in deciding the transformation rates (k(6)) of different thiyl radicals.

  DOI：

  10.1021/ja00105a048

文献信息

• Reversible Reactions of Thiols and Thiyl Radicals with Nitrone Spin Traps
  作者：Dmitrii I. Potapenko、Elena G. Bagryanskaya、Yuri P. Tsentalovich、Vladimir A. Reznikov、Thomas L. Clanton、Valery V. Khramtsov

  DOI：10.1021/jp049026t

  日期：2004.7.1

  The reactions of the reversible addition of thiols and thiyl radicals to the nitrone spin traps DMPO (5,5-dimethyl-1-pyrroline N-oxide) and DEPMPO (5-diethoxyphosphoryl-5-methyl-1-pyrroline N-oxide) are described. Addition of the thiols to the double CN bond of the nitrones results in the formation of the corresponding hydroxylamines, measured using 31P NMR and the phosphorus-containing trap DEPMPO

  硫醇和硫基自由基可逆加成到硝酮自旋陷阱 DMPO（5,5-二甲基-1-吡咯啉 N-氧化物）和 DEPMPO（5-二乙氧基磷酰基-5-甲基-1-吡咯啉 N-氧化物）的反应是描述。将硫醇添加到硝酮的双 CN 键会导致形成相应的羟胺，使用 31P NMR 和含磷陷阱 DEPMPO 进行测量。随后将这些羟胺轻度氧化成顺磁性加合物可能会干扰代表 Forrester-Hepburn 机制的硫基自由基的真正自旋捕获。首次观察到羟胺逆分解为母体硝酮和硫醇，顺磁性加合物逆分解为硝酮和硫基自由基。硝酮从硫基自由基中回收还原的硫醇可能包括它们在体内有效抗氧化活性的机制。顺磁性加合物分解后释放的硫基自由基可能不仅会显着影响定量...
• Electron spin resonance spin trapping of thiyl, radicals from the decomposition of thionitrites
  作者：P.David Josephy、Detlef Rehorek、Edward G. Janzen

  DOI：10.1016/s0040-4039(01)81144-8

  日期：1984.1

  Alkyl thiyl radicals produced by the homolytic decomposition of thionitrites are detected by ESR spin trapping using 5,5-dimethyl-1-Δ-pyrroline-N-oxide (DMPO).

  使用5，5-二甲基-1-Δ-吡咯啉-N-氧化物（DMPO）通过ESR自旋捕集检测由亚硫氰酸盐的均相分解产生的烷基噻吩基。
• REGENERATION OF VITAMIN E FROM α-CHROMANOXYL RADICAL BY GLUTATHIONE AND VITAMIN C
  作者：Etsuo Niki、Jyunichi Tsuchiya、Ritsuko Tanimura、Yoshio Kamiya

  DOI：10.1246/cl.1982.789

  日期：1982.6.5

  α-Chromanoxyl radical formed by the interaction of α-tocopherol (vitamin E) with alkoxyl radical or DPPH was found by electron spin resonance spectroscopy to react with glutathione and vitamin C to regenerate α-tocopherol.

  α-Chromanoxyl自由基是由α-生育酚（维生素E）与烷氧基自由基或DPPH相互作用形成的，通过电子自旋共振光谱法发现，它能够与谷胱甘肽和维生素C反应，从而再生α-生育酚。
• Photochemically Generated Thiyl Free Radicals Observed by X-ray Absorption Spectroscopy
  作者：Eileen Y. Sneeden、Mark J. Hackett、Julien J. H. Cotelesage、Roger C. Prince、Monica Barney、Kei Goto、Eric Block、Ingrid J. Pickering、Graham N. George

  DOI：10.1021/jacs.7b05116

  日期：2017.8.23

  Sulfur-based thiyl radicals are known to be involved in a wide range of chemical and biological processes, but they are often highly reactive, which makes them difficult to observe directly. We report herein X-ray absorption spectra and analysis that support the direct observation of two different thiyl species generated photochemically by X-ray irradiation. The thiyl radical sulfur K-edge X-ray absorption

  众所周知，硫基硫基自由基涉及广泛的化学和生物过程，但它们通常具有很高的反应性，这使得它们难以直接观察。我们在此报告了 X 射线吸收光谱和分析，这些光谱和分析支持直接观察由 X 射线照射光化学产生的两种不同的硫基物种。两种物质的硫基自由基硫 K 边 X 射线吸收光谱的特征是在约 2465 eV 处发生独特的低能量跃迁，其发生的能量低于之前在硫 K 边处观察到的任何特征，对应于 1s →3p 跃迁到自由基的单占分子轨道。
• Reaction between nitric oxide, glutathione, and oxygen in the presence and absence of protein: How are S-nitrosothiols formed?
  作者：Agnes Keszler、Yanhong Zhang、Neil Hogg

  DOI：10.1016/j.freeradbiomed.2009.10.026

  日期：2010.1

  study we have reinvestigated this reaction using both experiment and simulation and conclude that: (i) S-nitrosation through radical and nonradical pathways is occurring simultaneously, (ii) S-nitrosation through direct addition of NO to thiol does not occur to any meaningful extent, and (iii) protein hydrophobic environments do not catalyze or enhance S-nitrosation of either themselves or of glutathione

  由于 NO、硫醇和氧之间的反应在 NO 依赖性信号转导机制中的重要性，已经在体外进行了一些详细的研究。S-亚硝基硫醇和硫醇二硫化物的形成已被认为是 NO 生物化学的重要组成部分，这种随后的硫醇修饰可能导致细胞功能和表型的变化。在这项研究中，我们使用实验和模拟重新研究了该反应，并得出结论：（i）通过自由基和非自由基途径的 S-亚硝化同时发生，（ii）通过直接将 NO 添加到硫醇中的 S-亚硝化不会发生在任何有意义的程度，以及 (iii) 蛋白质疏水环境不会催化或增强自身或谷胱甘肽的 S-亚硝化。