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Novel Approaches for Elongation of Fish Oils into Very-Long-Chain Polyunsaturated Fatty Acids and Their Enzymatic Interesterification into Glycerolipids
Journal of Agricultural and Food Chemistry ( IF 5.7 ) Pub Date : 2023-11-10 , DOI: 10.1021/acs.jafc.3c05355 Tereza Honzíková 1 , Martin-Paul Agbaga , Robert Eugene Anderson , Richard Brush , Mohiuddin Ahmad , Lenka Musílková 2 , Karolína Šejstalová 2 , Katsiaryna Alishevich 1 , Radek Beneš 1 , Petra Šimicová 1 , Markéta Berčíková 1 , Vladimír Filip 1 , Jan Kyselka 1
Journal of Agricultural and Food Chemistry ( IF 5.7 ) Pub Date : 2023-11-10 , DOI: 10.1021/acs.jafc.3c05355 Tereza Honzíková 1 , Martin-Paul Agbaga , Robert Eugene Anderson , Richard Brush , Mohiuddin Ahmad , Lenka Musílková 2 , Karolína Šejstalová 2 , Katsiaryna Alishevich 1 , Radek Beneš 1 , Petra Šimicová 1 , Markéta Berčíková 1 , Vladimír Filip 1 , Jan Kyselka 1
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Elongation of the Very-Long-Chain Fatty Acids-4 (ELOVL4) enzyme that is expressed in neuronal tissues, sperm, and testes mediates biosynthesis of very-long-chain polyunsaturated fatty acids (VLC-PUFAs) from dietary long chain PUFAs (LC-PUFAs). The VLC-PUFAs are critical for neuronal and reproductive function. Therefore, mutations in ELOVL4 that affect VLC-PUFA biosynthesis contribute to retinal degenerative diseases including Autosomal Dominant Stargardt-like Macular Dystrophy (STGD3). Recent studies have also shown not only a depletion of retinal VLC-PUFAs with normal aging but also a more significant loss of VLC-PUFAs in donor eyes of patients with age-related macular degeneration (AMD). However, currently, there are no natural sources of VLC-PUFAs to be evaluated as dietary supplements for the attenuation of retinal degeneration in animal models of STGD3. Here, we report the development of a novel chemical approach for elongation of eicosapentaenoic (C20:5 n-3) and docosahexaenoic (C22:6 n-3) acids from fish oils by 6 carbon atoms to make a unique group of VLC-PUFAs, namely all-cis-hexacosa-11,14,17,20,23-pentaenoic acids (C26:5 n-3) and all-cis-octacosa-10,13,16,19,22,25-hexaenoic acids (C28:6 n-3). The three-step elongation approach that we report herein resulted in a good overall yield of up to 20.2%. This more sustainable approach also resulted in improved functional group compatibility and minimal impact on the geometrical integrity of the all-cis double bond system of the VLC-PUFAs. In addition, we also successfully used commercial deep-sea fish oil concentrate as an inexpensive material for the C6 elongation of fish oil LC-PUFAs into VLC-PUFAs, which resulted in the making of gram scales of VLC-PUFAs with an even higher isolation yield of 31.0%. The quality of fish oils and the content of oxidized lipids were key since both strongly affected the activity of the PEPPSI-IPr catalyst and ultimately the yield of coupling reactions. Downstream enzymatic interesterification was used for the first time to prepare structured glycerolipids enriched with VLC-PUFAs that could be evaluated in vivo to determine absorption and transport to target tissues relative to those of the free fatty acid forms. It turned out that in the synthesis of structured triacylglycerols and glycerophospholipids with VLC-PUFAs, the polarity of the immobilized lipase carrier and its humidity were essential.
中文翻译：
将鱼油延伸为长链多不饱和脂肪酸及其酶促酯交换成甘油脂的新方法
在神经元组织、精子和睾丸中表达的极长链脂肪酸 4 (ELOVL4) 酶的延长介导从膳食长链多不饱和脂肪酸 (LC) 中生物合成极长链多不饱和脂肪酸 (VLC-PUFA) -PUFA）。VLC-PUFA 对于神经元和生殖功能至关重要。因此，影响 VLC-PUFA 生物合成的 ELOVL4 突变会导致视网膜退行性疾病，包括常染色体显性遗传性 Stargardt 样黄斑营养不良 (STGD3)。最近的研究还表明，不仅正常衰老过程中视网膜 VLC-PUFA 会减少，而且年龄相关性黄斑变性 (AMD) 患者供体眼中 VLC-PUFA 的损失也更为显着。然而，目前还没有天然来源的 VLC-PUFA 可以作为膳食补充剂来评估，以减轻 STGD3 动物模型中的视网膜变性。在这里，我们报告了一种新的化学方法的开发，用于将鱼油中的二十碳五烯酸 (C20:5 n -3) 和二十二碳六烯酸 (C22:6 n -3) 酸延长 6 个碳原子，以制造一组独特的 VLC-PUFA ，即全顺式-六碳-11,14,17,20,23-五烯酸（C26:5 n -3）和全顺式-八碳-10,13,16,19,22,25-六烯酸（ C28:6 n -3)。我们在此报告的三步延伸方法获得了高达 20.2% 的良好总产率。这种更可持续的方法还提高了官能团相容性，并对 VLC-PUFA 的全顺式双键系统的几何完整性影响最小。此外，我们还成功使用商业深海鱼油浓缩物作为廉价材料，将鱼油LC-PUFA C6延伸成VLC-PUFA，从而制备出具有更高隔离度的克级VLC-PUFA收率31.0%。鱼油的质量和氧化脂质的含量是关键，因为两者都会强烈影响 PEPPSI-IPr 催化剂的活性并最终影响偶联反应的产率。首次使用下游酶促酯交换来制备富含 VLC-PUFA 的结构化甘油脂，可以在体内对其进行评估，以确定相对于游离脂肪酸形式的吸收和转运到靶组织的情况。事实证明，在用VLC-PUFA合成结构化三酰甘油和甘油磷脂时，固定化脂肪酶载体的极性及其湿度至关重要。
更新日期：2023-11-10
中文翻译：
将鱼油延伸为长链多不饱和脂肪酸及其酶促酯交换成甘油脂的新方法
在神经元组织、精子和睾丸中表达的极长链脂肪酸 4 (ELOVL4) 酶的延长介导从膳食长链多不饱和脂肪酸 (LC) 中生物合成极长链多不饱和脂肪酸 (VLC-PUFA) -PUFA）。VLC-PUFA 对于神经元和生殖功能至关重要。因此，影响 VLC-PUFA 生物合成的 ELOVL4 突变会导致视网膜退行性疾病，包括常染色体显性遗传性 Stargardt 样黄斑营养不良 (STGD3)。最近的研究还表明，不仅正常衰老过程中视网膜 VLC-PUFA 会减少，而且年龄相关性黄斑变性 (AMD) 患者供体眼中 VLC-PUFA 的损失也更为显着。然而，目前还没有天然来源的 VLC-PUFA 可以作为膳食补充剂来评估，以减轻 STGD3 动物模型中的视网膜变性。在这里，我们报告了一种新的化学方法的开发，用于将鱼油中的二十碳五烯酸 (C20:5 n -3) 和二十二碳六烯酸 (C22:6 n -3) 酸延长 6 个碳原子，以制造一组独特的 VLC-PUFA ，即全顺式-六碳-11,14,17,20,23-五烯酸（C26:5 n -3）和全顺式-八碳-10,13,16,19,22,25-六烯酸（ C28:6 n -3)。我们在此报告的三步延伸方法获得了高达 20.2% 的良好总产率。这种更可持续的方法还提高了官能团相容性，并对 VLC-PUFA 的全顺式双键系统的几何完整性影响最小。此外，我们还成功使用商业深海鱼油浓缩物作为廉价材料，将鱼油LC-PUFA C6延伸成VLC-PUFA，从而制备出具有更高隔离度的克级VLC-PUFA收率31.0%。鱼油的质量和氧化脂质的含量是关键，因为两者都会强烈影响 PEPPSI-IPr 催化剂的活性并最终影响偶联反应的产率。首次使用下游酶促酯交换来制备富含 VLC-PUFA 的结构化甘油脂，可以在体内对其进行评估，以确定相对于游离脂肪酸形式的吸收和转运到靶组织的情况。事实证明，在用VLC-PUFA合成结构化三酰甘油和甘油磷脂时，固定化脂肪酶载体的极性及其湿度至关重要。
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