二十二碳六烯酸甘油三酯(CIS-4,7,10,13,16,19) | 11094-59-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 甘油脂
• 中文名称: 二十二碳六烯酸甘油三酯(CIS-4,7,10,13,16,19)
• 中文别名: DHA三甘油酯；二十二碳六烯酸甘油三酯(CIS-4,7,1,13,16,19)
• 英文名称: tridocosahexaenoyl glycerol
• 英文别名: Glyceryl tridocosahexaenoate；2,3-bis[[(4Z,7Z,10Z,13Z,16Z,19Z)-docosa-4,7,10,13,16,19-hexaenoyl]oxy]propyl (4Z,7Z,10Z,13Z,16Z,19Z)-docosa-4,7,10,13,16,19-hexaenoate
• CAS: 11094-59-0
• 化学式: C₆₉H₉₈O₆
• 分子量: 1023.53
• InChiKey: SOFMPBOQLPVEQZ-LBUXZKOBSA-N

物化性质

• 溶解度：
  氯仿：可混溶

计算性质

• 辛醇/水分配系数(LogP)：
  19.2
• 重原子数：
  75
• 可旋转键数：
  50
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  78.9
• 氢给体数：
  0
• 氢受体数：
  6

安全信息

• 储存条件：
  -20°C

制备方法与用途

三十六碳三烯酸是一种三酰基甘油，具备较强的抗氧化能力。

反应信息

• 作为反应物：
  描述：

  辛酸乙酯 、 二十二碳六烯酸甘油三酯(CIS-4,7,10,13,16,19) 在 Novozym 435 、 Lipozyme-IM 乙醇 作用下， 反应 7.5h， 以85.4%的产率得到1,3-dicapryloyl-2-docosahexaenoylglycerol
  参考文献：
  名称：

  利用反应介质依赖性南极假丝酵母脂肪酶（Novozym 435）的区域特异性合成1,3-二辛基酰基-2-十二碳六烯酰基（或二十碳五烯酰基）甘油

  摘要：

  AbstractA highly efficient enzymatic method for the synthesis of regioisomerically pure 1,3‐dicapryloyl‐2‐docosahexaenoyl glycerol (CDC) in two steps was established. 2‐Monoglyceride (2‐MG) formation by ethanolysis of tridocosahexaenoylglycerol (DDD) with immobilized Candida antarctica lipase (Novozym 435) as catalyst was the key step of the synthesis. CDC was finally obtained by reesterification of 2‐MG with ethylcaprylate (EtC) catalyzed by Rhizomucor miehei lipase (Lipozyme IM). The regiospecificity of Novozym 435 depended on the type of reaction and the initial composition of the reaction medium. It displayed strict 1,3‐regiospecificity for ethanolysis at a high excess of ethanol in the reaction mixture although it displayed no regiospecificity in transesterification and esterification reactions. The highest yield of CDC (85.4%) was obtained by ethanolysis at a 4∶1 weight ratio of ethanol/DDD for 6 h followed by reesterification at a 20∶1 molar ratio of EtC/initial DDD for 1.5 h. The regioisomeric purity of CDC was 100%. Good results were obtained also for the synthesis of 1,3‐dicapryloyl‐eicosapentaenoylglycerol (CEC) by the same method: 84.2% yield and 99.8% regioisomeric purity at the same reactant ratios as above. The yield of the reesterification step and the regioisomeric purity of the product were influenced by the molar ratio of the reactants for both CDC and CEC syntheses: higher excess of EtC favored higher yields and regioisomeric purity of the products.

  DOI：

  10.1007/s11746-001-0258-3
• 作为产物：
  描述：

  (4Z,7Z,10Z,13Z,16Z,19Z)-4,7,10,13,16,19-二十二碳六烯酸乙酯 在 乙二胺四乙酸 、 immobilized lipase from Candida Antarctica 、 edetate disodium 作用下， 以 乙醇 、 水 为溶剂， 60.0~65.0 ℃ 、13.33 Pa 条件下， 反应 76.0h， 生成 二十二碳六烯酸甘油三酯(CIS-4,7,10,13,16,19)
  参考文献：
  名称：

  脂肪酶合成二十碳五烯酸和二十二碳六烯酸均相甘油三酸酯

  摘要：

  通过固定化的南极假丝酵母的非区域特异性酵母脂肪酶高效合成纯二十碳五烯酸1或二十二碳六烯酸2的均质甘油三酸酯描述。使用了两种方法：三丁酸甘油酯的酯交换和分别以化学计量的99％EPA或DHA的乙基酯和游离脂肪酸的甘油直接酯化。两种方法均在真空下于65°C且无任何溶剂的条件下进行。将挥发性副产物冷凝到冷却的阱中，从而使平衡朝着完成方向移动。在所有情况下，都可以在不到72小时的时间内完成完全掺入，但是发现直接酯化比酯交换要快得多，这两个过程都涉及EPA和DHA。高场11 H NMR光谱分析提供了在直接酯化反应过程中对中间甘油酯的详细研究。以优异的产率提供的所得粗产物的纯度非常高。

  DOI：

  10.1016/0040-4020(94)00983-2

文献信息

• Synthesis of triacylglycerol from polyunsaturated fatty acid by immobilized lipase
  作者：Yoshitsugu Kosugi、Naoki Azuma

  DOI：10.1007/bf02541362

  日期：1994.12

  More than 95% of polyunsaturated acid (PUFA) was converted to triacylglycerol by immobilized lipase fromCandida antarctica orRhizomucor miehei. The esterification was carried out at 50–60°C with shaking and dehydration for 24 h. The substrates consisted of glycerol and free fatty acid or ethyl esters of the fatty acid at a 1∶3 molar ratio. The docosahexaenoic acid (DHA) or eicosapentaenoic acid (EPA) in the substrate polymerized during the reaction, and they required 5–10% more than the stoichiometric amount to compensate for the PUFA loss. On the contrary, ethyl esters of DHA and EPA were not polymerized. Pure tridocosahexaenoyl, trieicosapentaenoly and triarachidonoyl glycerol were isolated after passing the product through a basic aluminum oxide column. Industrial feasibility of this process was discussed for the ethyl ester as substrate.

  摘要 利用固定化脂肪酶将95%以上的多不饱和脂肪酸（PUFA）转化为三酰甘油。底物包括甘油和游离脂肪酸或脂肪酸乙酯，摩尔比为 1∶3。底物中的二十二碳六烯酸（DHA）或二十碳五烯酸（EPA）在反应过程中聚合，它们需要比化学计量量多 5-10% 的量来补偿 PUFA 的损失。相反，DHA 和 EPA 的乙酯没有聚合。产品通过碱性氧化铝柱后，分离出了纯净的三二十六烯酰、三二十五烯酰和三丙烯酰甘油。讨论了以乙酯为底物进行该工艺的工业可行性。
• Enzymatic synthesis of triacylglycerols of docosahexaenoic acid: Transesterification of its ethyl esters with glycerol
  作者：S. Moreno-Perez、P. Luna、F.J. Señorans、J.M. Guisan、G. Fernandez-Lorente

  DOI：10.1016/j.foodchem.2015.04.095

  日期：2015.11

  The synthesis of docosahexaenoyl triacylglycerides at low temperature (e.g., 50 °C) using biocatalysts of 6 commercial lipases adsorbed on hydrophobic supports was studied. In general, the triacylglyceride yields were very low with the exceptions of those produced with the enzymes from Candida antarctica fraction B, CALB (82%), and those produced with the enzyme from Pseudomonas fluorescens, PFL (57%)

  研究了在低温（例如50°C）下使用吸附在疏水性载体上的6种商业脂肪酶的生物催化剂合成二十二碳六烯酰基甘油三酯的方法。通常，除了用南极假丝酵母组分B的酶CALB（82％）和用荧光假单胞菌PFL的酶（57％）生产的那些外，甘油三酸酯的收率都非常低。反应在真空下进行以除去释放的乙醇。当使用不同的CALB衍生物时，收率差异很大，而当CALB吸附在疏水性载体上时，收率更高（82％）。一种有趣的副产品（占锡的18％在合成过程的最后保留了-2 DHA单酰基甘油酯。与商业衍生物Novozym 435相比，吸附在Sepabeads上的CALB具有更好的活性和稳定性。在反应条件下30天后，最好的CALB生物催化剂保留了90％的活性。
• The preparation of homogeneous triglycerides of eicosapentaenoic acid and docosahexaenoic acid by lipase
  作者：Gudmundur G. Haraldsson、Birgir Ö. Gudmundsson、Örn Almarsson

  DOI：10.1016/s0040-4039(00)73862-7

  日期：1993.9

  The highly efficient generation of homogeneous triglycerides of either pure eicosapentaenoic acid, 1, or docosahexaenoic acid, 2, by an immobilized nonregiospecific yeast lipase from Candida antarctica is described.
• DAGL-Beta Functions as a PUFA-Specific Triacylglycerol Lipase in Macrophages
  作者：Myungsun Shin、Timothy B. Ware、Ku-Lung Hsu

  DOI：10.1016/j.chembiol.2020.01.005

  日期：2020.3

  Here, we apply quantitative chemical proteomics and untargeted lipidomics to assign a polyunsaturated fatty acid (PUFA)-specific triacylglycerol (TAG) lipase activity for diacylglycerol lipase-beta (DAGL beta) in macrophages. We demonstrate that DAGL beta but not DAGL alpha is expressed and active in bone marrow-erived macrophages (BMDMs) as determined by activity-based protein profiling analysis of SILAC BMDMs. Genetic disruption of DAGL beta resulted in accumulation of cellular TAGs composed of PUFA but not saturated/low unsaturated fatty acid counterparts, which is recapitulated in wild-type macrophages treated with a DAGL beta-selective inhibitor. Biochemical assays with synthetic substrates confirm PUFA-TAGs as authentic DAGL beta substrates. In summary, our findings identify DAGL beta as a PUFA-Specific TAG lipase in primary macrophages.
• Utilization of reaction medium-dependent regiospecificity of Candida antarctica lipase (Novozym 435) for the synthesis of 1,3-dicapryloyl-2-docosahexaenoyl (or eicosapentaenoyl) glycerol
  作者：Roxana Irimescu、Kiyomi Furihata、Kazuhiko Hata、Yugo Iwasaki、Tsuneo Yamane

  DOI：10.1007/s11746-001-0258-3

  日期：2001.3

  AbstractA highly efficient enzymatic method for the synthesis of regioisomerically pure 1,3‐dicapryloyl‐2‐docosahexaenoyl glycerol (CDC) in two steps was established. 2‐Monoglyceride (2‐MG) formation by ethanolysis of tridocosahexaenoylglycerol (DDD) with immobilized Candida antarctica lipase (Novozym 435) as catalyst was the key step of the synthesis. CDC was finally obtained by reesterification of 2‐MG with ethylcaprylate (EtC) catalyzed by Rhizomucor miehei lipase (Lipozyme IM). The regiospecificity of Novozym 435 depended on the type of reaction and the initial composition of the reaction medium. It displayed strict 1,3‐regiospecificity for ethanolysis at a high excess of ethanol in the reaction mixture although it displayed no regiospecificity in transesterification and esterification reactions. The highest yield of CDC (85.4%) was obtained by ethanolysis at a 4∶1 weight ratio of ethanol/DDD for 6 h followed by reesterification at a 20∶1 molar ratio of EtC/initial DDD for 1.5 h. The regioisomeric purity of CDC was 100%. Good results were obtained also for the synthesis of 1,3‐dicapryloyl‐eicosapentaenoylglycerol (CEC) by the same method: 84.2% yield and 99.8% regioisomeric purity at the same reactant ratios as above. The yield of the reesterification step and the regioisomeric purity of the product were influenced by the molar ratio of the reactants for both CDC and CEC syntheses: higher excess of EtC favored higher yields and regioisomeric purity of the products.