13(S)-HpODE

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 13(S)-HpODE
• 英文别名: (9Z,13S)-13-hydroperoxyoctadeca-9,11-dienoic acid
• 化学式: C₁₈H₃₂O₄
• 分子量: 312.45
• InChiKey: JDSRHVWSAMTSSN-FTICKIBQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  22
• 可旋转键数：
  15
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.72
• 拓扑面积：
  66.8
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  13(S)-HpODE 在 吡啶 、 乙酸酐 作用下， 生成 (9Z,11E)-13-氧代-9,11-十八碳二烯酸
  参考文献：
  名称：

  Inhibitory and mechanistic investigations of oxo-lipids with human lipoxygenase isozymes

  摘要：

  Oxo-lipids, a large family of oxidized human lipoxygenase (hLOX) products, are of increasing interest to researchers due to their involvement in different inflammatory responses in the cell. Oxo-lipids are unique because they contain electrophilic sites that can potentially form covalent bonds through a Michael addition mechanism with nucleophilic residues in protein active sites and thus increase inhibitor potency. Due to the resemblance of oxo-lipids to LOX substrates, the inhibitor potency of 4 different oxo-lipids; 5-oxo-6,8,11,14-(E,Z,Z,Z)-eicosatetraenoic acid (5-oxo-ETE), 15-oxo-5,8,11,13-(Z,Z,Z,E)-eicosatetraenoic acid (15-oxo-ETE), 12-oxo-5,8,10,14-(Z,Z,E,Z)-eicosatetraenoic acid (12-oxo-ETE), and 13-oxo-9,11-(Z,E)-octadecadienoic acid (13-oxo-ODE) were determined against a library of LOX isozymes; leukocyte 5-lipoxygenase (h5-LOX), human reticulocyte 15-lipoxygenase-1 (h15-LOX-1), human platelet 12-lipoxygenase (h12-LOX), human epithelial 15-lipoxygenase-2 (h15-LOX-2), soybean 15-lipoxygenase-1 (s15-LOX-1), and rabbit reticulocyte 15-LOX (r15-LOX). 15-Oxo-ETE exhibited the highest potency against h12-LOX, with an IC50 = 1 +/- 0.1 mu M and was highly selective. Steady state inhibition kinetic experiments determined 15-oxo-ETE to be a mixed inhibitor against h12-LOX, with a K-ic value of 0.087 +/- 0.008 mu M and a K-iu value of 2.10 +/- 0.8 mu M. Time-dependent studies demonstrated irreversible inhibition with 12-oxo-ETE and h15-LOX-1, however, the concentration of 12-oxo-ETE required (K-i = 36.8 +/- 13.2 mu M) and the time frame (k(2) = 0.0019 +/- 0.00032 s(-1)) were not biologically relevant. These data are the first observations that oxo-lipids can inhibit LOX isozymes and may be another mechanism in which LOX products regulate LOX activity. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmc.2014.05.025
• 作为产物：
  描述：

  (Z,Z)-9,12-十八烷二烯酸二聚物 在 氧气 、 soybean type I lipoxygenase 作用下， 以 aq. phosphate buffer 、 乙醇 为溶剂， 反应 5.0h， 以72%的产率得到13(S)-HpODE
  参考文献：
  名称：

  Stereostructural analysis of flexible oxidized fatty acids by VCD spectroscopy

  摘要：

  使用VCD光谱学阐明羟基脂肪酸、脂肪环氧化物和脂质过氧化物的绝对构型和构象偏好。

  DOI：

  10.1039/d2cc01337a

文献信息

• Tritylation, methoxymethylation, and silylation of allylic hydroperoxides via stannyl peroxide intermediates. Allylic rearrangement of a stannyl peroxide
  作者：Richard K. Haynes、Simone C. Vonwiller

  DOI：10.1039/c39900000448

  日期：——

  hydroperoxides are quantitatively converted by tributyltin methoxide into stannyl peroxides, whose treatment with trityl chloride, chloromethyl methyl ether, and t-butyldimethylsilyl trifluoromethane-sulphonate give the corresponding trityl, methoxymethyl, and silyl peroxides, a tertiary allylic hydroperoxide gives rearrangement products on stannylation and treatment with trityl chloride.

  甲基三丁基锡将伯和仲烯丙基氢过氧化物定量地转化成过氧化甲锡，用三苯甲基氯，氯甲基甲基醚和叔丁基二甲基甲硅烷基三氟甲烷磺酸酯处理可得到相应的三苯甲基，甲氧基甲基和甲硅烷基过氧化物，叔烯丙基氢过氧化物则可进行重排甲磺酰化并用三苯甲基氯处理的产品。
• Synthesis of 13R,20-dihydroxy-docosahexaenoic acid by site-directed mutagenesis of lipoxygenase derived from Oscillatoria nigro-viridis PCC 7112
  作者：Jong-Jae Yi、Sun-Yeon Heo、Jung-Hyun Ju、Baek-Rock Oh、Woo Sung Son、Jeong-Woo Seo

  DOI：10.1016/j.bbrc.2020.09.079

  日期：2020.12

  Lipoxygenases (LOXs) are implicated in the biosynthesis of pro- and anti-inflammatory lipid mediators involved in immune cell signaling, most of which catalyze peroxidation of polyunsaturated fatty acids by distinct regio- and stereoselectivity. Current reports suggested that conserved amino acid, Gly in R-LOXs and Ala in S-LOXs, in the catalytic domain play an important role in determining the position as well as the stereochemistry of the functional group. Recently, we have confirmed that the catalytic specificity of cyanobacterial lipoxygenase, named Osc-LOX, with alanine at 296 was 13S-type toward linoleic acid, and producing a 17S- hydroxy-docosahexaenoic acid from docosahexaenoic acid (DHA). Here, we aimed to change the catalytic property of LOX from13S-LOX to 9R-LOX by replacing Ala with Gly and to produce a lipid mediators different from the wild-type using DHA. Finally, we succeeded in generating human endogenous a 13R-hydroxy-docosahexaenoic acid and a 13R,20-dihydroxy-docosahexaenoic acid from DHA through an enzymatic reaction using the Osc-LOX-A296G. Our study could enable physiological studies and pharmaceutical research for the 13R,20-dihydroxy-docosahexaenoic acid.
• Inhibitory and mechanistic investigations of oxo-lipids with human lipoxygenase isozymes
  作者：Michelle M. Armstrong、Giovanni Diaz、Victor Kenyon、Theodore R. Holman

  DOI：10.1016/j.bmc.2014.05.025

  日期：2014.8

  Oxo-lipids, a large family of oxidized human lipoxygenase (hLOX) products, are of increasing interest to researchers due to their involvement in different inflammatory responses in the cell. Oxo-lipids are unique because they contain electrophilic sites that can potentially form covalent bonds through a Michael addition mechanism with nucleophilic residues in protein active sites and thus increase inhibitor potency. Due to the resemblance of oxo-lipids to LOX substrates, the inhibitor potency of 4 different oxo-lipids; 5-oxo-6,8,11,14-(E,Z,Z,Z)-eicosatetraenoic acid (5-oxo-ETE), 15-oxo-5,8,11,13-(Z,Z,Z,E)-eicosatetraenoic acid (15-oxo-ETE), 12-oxo-5,8,10,14-(Z,Z,E,Z)-eicosatetraenoic acid (12-oxo-ETE), and 13-oxo-9,11-(Z,E)-octadecadienoic acid (13-oxo-ODE) were determined against a library of LOX isozymes; leukocyte 5-lipoxygenase (h5-LOX), human reticulocyte 15-lipoxygenase-1 (h15-LOX-1), human platelet 12-lipoxygenase (h12-LOX), human epithelial 15-lipoxygenase-2 (h15-LOX-2), soybean 15-lipoxygenase-1 (s15-LOX-1), and rabbit reticulocyte 15-LOX (r15-LOX). 15-Oxo-ETE exhibited the highest potency against h12-LOX, with an IC50 = 1 +/- 0.1 mu M and was highly selective. Steady state inhibition kinetic experiments determined 15-oxo-ETE to be a mixed inhibitor against h12-LOX, with a K-ic value of 0.087 +/- 0.008 mu M and a K-iu value of 2.10 +/- 0.8 mu M. Time-dependent studies demonstrated irreversible inhibition with 12-oxo-ETE and h15-LOX-1, however, the concentration of 12-oxo-ETE required (K-i = 36.8 +/- 13.2 mu M) and the time frame (k(2) = 0.0019 +/- 0.00032 s(-1)) were not biologically relevant. These data are the first observations that oxo-lipids can inhibit LOX isozymes and may be another mechanism in which LOX products regulate LOX activity. (C) 2014 Elsevier Ltd. All rights reserved.
• Stereostructural analysis of flexible oxidized fatty acids by VCD spectroscopy
  作者：Tohru Taniguchi、Naka Ida、Takuya Kitahara、Davidson Obinna Agbo、Kenji Monde

  DOI：10.1039/d2cc01337a

  日期：——

  Using VCD spectroscopy to elucidate absolute configuration and conformational preferences of hydroxy fatty acids, lipid epoxides, and lipid hydroperoxides.

  使用VCD光谱学阐明羟基脂肪酸、脂肪环氧化物和脂质过氧化物的绝对构型和构象偏好。