pelargonic acid anion | 3342-79-8

• 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: pelargonic acid anion
• 英文别名: nonate；nonanate；WH 86086 Devient Beloukha；pelargonate anion；Nonanoate
• CAS: 3342-79-8
• 化学式: C₉H₁₇O₂
• 分子量: 157.233
• InChiKey: FBUKVWPVBMHYJY-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  11
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  40.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  adenosine 5'-triphosphate 、 氢(+1)阳离子 、 pelargonic acid anion 生成 pyrophosphoric acid 、 nonanoyl-AMP
  参考文献：
  名称：

  现有蛔苷信息素的生物合成改变了它们在秀丽隐杆线虫中的生物学功能

  摘要：

  秀丽隐杆线虫产生蛔苷信息素来控制其发育和行为。即使蛔苷的微小结构差异也会对其生物活性产生巨大影响。在这里，我们确定了一种机制，使秀丽隐杆线虫能够动态定制它产生的吲哚-3-羰基 (IC) 修饰的蛔苷的脂肪酸侧链。为了应对饥饿，秀丽隐杆线虫使用过氧化物酶体酰基辅酶 A 合成酶 ACS-7 激活中链 IC-蛔苷的侧链，以进行涉及酰基辅酶 A 氧化酶 ACOX-1.1 和 ACOX-3 的 β-氧化。该途径迅速将诱导聚集的有利蛔苷信息素转化为诱导抗逆幼虫阶段的不利信息素。因此，该途径允许蠕虫对不断变化的环境条件做出反应并改变其化学信息，而无需从头合成新的蛔苷。我们建立了一种新的 IC-蛔苷生物合成模型，其中侧链 β-氧化对于控制产生的 IC-蛔苷的类型至关重要。

  DOI：

  10.7554/elife.33286
• 作为产物：
  描述：

  壬酸 在 sodium hydroxide 作用下， 以 乙醇 、 水 为溶剂， 反应 0.42h， 生成 pelargonic acid anion
  参考文献：
  名称：

  Lactones. 2. Enthalpies of hydrolysis, reduction, and formation of the C4-C13 monocyclic lactones. Strain energies and conformations

  摘要：

  The enthalpies of hydrolysis of the monocyclic lactones from gamma-butyrolactone to tridecanolactone were determined calorimetrically, and the acyclic ethyl esters having the same number of atoms were studied in the same fashion. The enthalpies of reduction of the lactones to the corresponding alpha,omega-alkanediols with lithium triethylborohydride also were determined. The enthalpies of formation of the lactones and the ethyl esters were derived from these data. They were converted to values for the gas phase by measuring the enthalpies of vaporization of ethyl esters and of lactones. In the cases of gamma-butyrolactone and delta-valerolactone, the enthalpies of formation were in good accord with the previously reported values determined via combustion calorimetry. The strain energies of the lactones were obtained via isodesmic reactions. Valerolactone had a strain energy of 11 kcal/mol, and the largest strain energy was found with octanolactone (13 kcal/mol). The conformations of gamma-butyrolactone and delta-valerolactone were studied via MP2/6-31G* geometry optimizations, and the conformations of the other lactones were studied with use of the molecular mechanics program MM3. The energies of the lactones estimated via molecular mechanics were compared with the experimental results.

  DOI：

  10.1021/ja00020a036

文献信息

• Jasmonates meet fatty acids: functional analysis of a new acyl-coenzyme A synthetase family from Arabidopsis thaliana
  作者：Lucie Kienow、Katja Schneider、Michael Bartsch、Hans-Peter Stuible、Hua Weng、Otto Miersch、Claus Wasternack、Erich Kombrink

  DOI：10.1093/jxb/erm325

  日期：2008.2

  Arabidopsis thaliana contains a large number of genes encoding carboxylic acid-activating enzymes, including long-chain fatty acyl-CoA synthetase (LACS), 4-coumarate:CoA ligases (4CL), and proteins closely related to 4CLs with unknown activities. The function of these 4CL-like proteins was systematically explored by applying an extensive substrate screen, and it was uncovered that activation of fatty acids is the common feature of all active members of this protein family, thereby defining a new group of fatty acyl-CoA synthetase, which is distinct from the known LACS family. Significantly, four family members also displayed activity towards different biosynthetic precursors of jasmonic acid (JA), including 12-oxo-phytodienoic acid (OPDA), dinor-OPDA, 3-oxo-2(2′-[Z]-pentenyl)cyclopentane-1-octanoic acid (OPC-8), and OPC-6. Detailed analysis of in vitro properties uncovered significant differences in substrate specificity for individual enzymes, but only one protein (At1g20510) showed OPC-8:CoA ligase activity. Its in vivo function was analysed by transcript and jasmonate profiling of Arabidopsis insertion mutants for the gene. OPC-8:CoA ligase expression was activated in response to wounding or infection in the wild type but was undetectable in the mutants, which also exhibited OPC-8 accumulation and reduced levels of JA. In addition, the developmental, tissue- and cell-type specific expression pattern of the gene, and regulatory properties of its promoter were monitored by analysing promoter::GUS reporter lines. Collectively, the results demonstrate that OPC-8:CoA ligase catalyses an essential step in JA biosynthesis by initiating the β-oxidative chain shortening of the carboxylic acid side chain of its precursors, and, in accordance with this function, the protein is localized in peroxisomes.

  拟南芥含有大量编码羧酸活化酶的基因，包括长链脂肪酰基-CoA 合成酶（LACS）、4-香豆酸：CoA 连接酶（4CL）以及与 4CL 密切相关但活性未知的蛋白。通过广泛的底物筛选，系统地探索了这些 4CL 类蛋白质的功能，发现脂肪酸的活化是该蛋白家族所有活性成员的共同特征，从而定义了一组新的脂肪酰基-CoA 合成酶，与已知的 LACS 家族不同。值得注意的是，四个家族成员还对茉莉酸（JA）的不同生物合成前体表现出活性，包括 12-氧代-2-(2′-[Z]-戊烯基)环戊烷-1-辛酸（OPC-8）和 OPC-6。对体外特性的详细分析发现，各酶的底物特异性存在显著差异，但只有一种蛋白质（At1g20510）显示出 OPC-8:CoA 连接酶活性。通过对拟南芥基因插入突变体进行转录本和茉莉酸酯分析，分析了其体内功能。在野生型中，OPC-8:CoA 连接酶的表达在受伤或感染时被激活，但在突变体中却检测不到，突变体也表现出 OPC-8 的积累和 JA 水平的降低。此外，还通过分析启动子：：GUS 报告基因系监测了该基因的发育、组织和细胞类型特异性表达模式及其启动子的调控特性。总之，研究结果表明，OPC-8:CoA 连接酶通过启动其前体羧酸侧链的 β-氧化链缩短作用，催化了 JA 生物合成过程中的一个重要步骤。
• Metabolomics annotates ABHD3 as a physiologic regulator of medium-chain phospholipids
  作者：Jonathan Z Long、Justin S Cisar、David Milliken、Sherry Niessen、Chu Wang、Sunia A Trauger、Gary Siuzdak、Benjamin F Cravatt

  DOI：10.1038/nchembio.659

  日期：2011.11

  An untargeted metabolomics approach identifies C14 phosphatidylcholines (PCs) as specific cellular medium-chain substrates of the lipase ABHD3, as well as C5–C8 short-chain PCs including oxidized pro-atherosclerotic and pro-apoptotic PC phospholipids. All organisms, including humans, possess a huge number of uncharacterized enzymes. Here we describe a general cell-based screen for enzyme substrate discovery by untargeted metabolomics and its application to identify the protein α/β-hydrolase domain–containing 3 (ABHD3) as a lipase that selectively cleaves medium-chain and oxidatively truncated phospholipids. Abhd3−/− mice possess elevated myristoyl (C14)-phospholipids, including the bioactive lipid C14-lysophosphatidylcholine, confirming the physiological relevance of our substrate assignments.

  一种非靶向代谢组学方法发现，C14磷脂酰胆碱（PC）是脂肪酶ABHD3的特异性细胞中链底物，还发现了C5âC8短链PC，包括氧化的促动脉粥样硬化和促凋亡PC磷脂。 包括人类在内的所有生物体都拥有大量未定性的酶。在这里，我们描述了一种通过非靶向代谢组学发现酶底物的通用细胞筛选方法，以及该方法在鉴定含δ/δ²-水解酶结构域的蛋白δ/δ²-水解酶结构域3（ABHD3）的应用，该蛋白δ/δ²-水解酶结构域3（ABHD3）是一种选择性裂解中链和氧化截短磷脂的脂肪酶。ABHD3â/â小鼠的肉豆蔻酰（C14）-磷脂含量升高，其中包括生物活性脂质C14-赖磷脂酰胆碱，这证实了我们底物分配的生理相关性。
• Identification of Key Residues for Enzymatic Carboxylate Reduction
  作者：Holly Stolterfoht、Georg Steinkellner、Daniel Schwendenwein、Tea Pavkov-Keller、Karl Gruber、Margit Winkler

  DOI：10.3389/fmicb.2018.00250

  日期：——

  Little is known about the structure of CARs and their catalytically important amino acid residues. The identification of key residues for carboxylate reduction provides a starting point to gain deeper understanding of enzymatic carboxylate reduction. A multiple sequence alignment of CARs with confirmed activity recently identified in our lab and from the literature revealed a fingerprint of conserved

  羧酸还原酶（CARs，EC 1.2.1.30）从其相应的羧酸中以高选择性生成醛。关于CAR的结构及其催化重要的氨基酸残基知之甚少。鉴定用于羧酸盐还原的关键残基为深入了解酶促羧酸盐还原提供了一个起点。最近在我们的实验室中从文献中鉴定出具有确定活性的CAR的多序列比对，揭示了保守氨基酸的指纹。我们通过这些残基的多个序列比对和突变替换研究了保守残基的功能。在这项研究中，研究了Neurospora crassa CAR的单部位丙氨酸变体，以确定保守残基对功能的贡献，酶的表达性或稳定性。通过在体内和体外分析变体的酶活性来研究氨基酸置换的作用。在分子建模的支持下，我们解释了这些残基中的五个对于催化活性或底物和共底物结合至关重要。我们鉴定出对CAR活性具有显着影响的氨基酸残基。用Ala替代His 237，Glu 433，Ser 595，Tyr 844和Lys 848废除了CAR活性，表明它们在减少酸中的
• Gadosy, Timothy A.; Tee, Oswald S., Journal of the Chemical Society. Perkin transactions II, 1994, # 4, p. 715 - 722
  作者：Gadosy, Timothy A.、Tee, Oswald S.

  DOI：——

  日期：——
• Lactones. 2. Enthalpies of hydrolysis, reduction, and formation of the C4-C13 monocyclic lactones. Strain energies and conformations
  作者：Kenneth B. Wiberg、Roy F. Waldron

  DOI：10.1021/ja00020a036

  日期：1991.9

  The enthalpies of hydrolysis of the monocyclic lactones from gamma-butyrolactone to tridecanolactone were determined calorimetrically, and the acyclic ethyl esters having the same number of atoms were studied in the same fashion. The enthalpies of reduction of the lactones to the corresponding alpha,omega-alkanediols with lithium triethylborohydride also were determined. The enthalpies of formation of the lactones and the ethyl esters were derived from these data. They were converted to values for the gas phase by measuring the enthalpies of vaporization of ethyl esters and of lactones. In the cases of gamma-butyrolactone and delta-valerolactone, the enthalpies of formation were in good accord with the previously reported values determined via combustion calorimetry. The strain energies of the lactones were obtained via isodesmic reactions. Valerolactone had a strain energy of 11 kcal/mol, and the largest strain energy was found with octanolactone (13 kcal/mol). The conformations of gamma-butyrolactone and delta-valerolactone were studied via MP2/6-31G* geometry optimizations, and the conformations of the other lactones were studied with use of the molecular mechanics program MM3. The energies of the lactones estimated via molecular mechanics were compared with the experimental results.