The global research progress of enzymatic processing of oils with Omega 3 polyunsaturated fatty acids（网络首发、推荐阅读）

综述ω-3多不饱和脂肪酸（polyunsaturated fatty acids,PUFA）作为一类必需脂肪酸（essential fatty acids,EFAs）,主要来源为海产品中的鱼油,对多种人体疾病治疗和/或预防具有的积极作用。梳理了酶法制备富含ω-3多不饱和脂肪酸油脂的研究最新进展（截至2019年）,讨论很多不同产品的营养功效、不同脂肪酸组成的结构脂质、ω-3多不饱和脂肪酸浓缩液、磷脂的酶促酯交换制备技术及应用,历年研究发现,可以通过改善油脂中ω-3多不饱和脂肪酸含量的方式提高其在饮食中的摄入量。由于酶法反应条件温和,尤其是脂肪酶特异性强,且从生物利用度角度ω-3多不饱和脂肪酸在脂质分子上的位置与其含量同等重要,因此相对于化学法,酶法制备含ω-3多不饱和脂肪酸的油脂因安全高效而更受青睐。     

酶法改性微藻油脂制备功能性油脂的研究进展

多不饱和脂肪酸是一类对人体健康有益的生物活性物质,微藻油脂富含多不饱和脂肪酸,是天然可食用的潜在油源。利用微藻油脂开发制备型功能性油脂,替代动植物天然功能性油脂,不仅可提高天然功能性油脂的品质,解决供应问题,而且有望得到新的功能性油脂制品。对酶法制备功能性油脂的方法、常见微藻的油脂含量及其油脂的脂肪酸组成进行综述,并对酶法改性微藻油脂制备富含多不饱和脂肪酸的单酰甘油酯、结构三酰甘油酯、功能性磷脂等功能性油脂的研究进展进行了介绍。酶法改性微藻油脂制备功能性油脂是高值化利用微藻油脂的新途径。     

Different specificity of two types of Pseudomonas lipases for C20 fatty acids with a Delta5 unsaturated double bond and their application for selective concentration of fatty acids

Two kinds of lipases, AK-lipase and HU-lipase, produced by two different Pseudomonas fluorescens strains, AK102 and HU380, respectively, were evaluated as to fatty acid hydrolysis specificity using six types of oil containing higher amounts of C20 fatty acids such as arachidonic acid (5,8,11,14-eicosatetraenoic acid, AA, or 20:4omega6), dihomo-gamma-linolenic acid (8,11,14-eicosatrienoic acid, DGLA, or 20:3omega6), 5,8,11,14,17-eicosapentaenoic acid (EPA or 20:5omega3), mead acid (5,8,11-eicosatrienoic acid, MA, or 20:3omega9), 8,11-eicosadienoic acid (20:2omega9) and 8,11,14,17-eicosatetraenoic acid (20:4omega3). Although HU-lipase did not show any specificity for C20 fatty acids with respect to the presence or absence of a Delta5 unsaturated bond, it exhibited comparatively low reactivity for 4,7,10,13,16,19-docosahexaenoic acid (DHA or 22:6omega3). In contrast, AK-lipase was less reactive for C20 fatty acids with a Delta5 unsaturated bond. However, the specificity of hydrolysis of AK-lipase gradually decreased as the reaction proceeded. Utilizing this fatty acid specificity, we concentrated either EPA or DHA from fish oils containing both EPA and DHA by means of lipase-catalyzed hydrolysis and urea adduction. Hydrolysis and urea adduction of refined cod oil including 12.2% EPA and 6.9% DHA with HU-lipase provided free fatty acids with 43.1% EPA and 7% DHA, respectively. The resulting yield of concentrated total fatty acids comprised 2.6% of the fatty acids from the cod oil. Thus, EPA was particularly concentrated in the fatty acids derived from refined cod oil on partial hydrolysis with HU-lipase followed by urea adduction. On the other hand, hydrolysis of cuttlefish oil with AK-lipase followed by urea adduction increase slightly the EPA composition from 14.2% to 16.8%, and markedly enhanced the composition of DHA from 16.3% to 44.6% in the hydrolyzed fatty acids. The yield of purified total fatty acids by urea concentrate was 9.4% of the fatty acids from the cuttlefish oil. Thus, DHA was particularly concentrated in the fatty acids derived from on partial hydrolysis with AK-lipase followed by urea adduction. We concluded that EPA and DHA concentrates can be easily and inexpensively obtained using HU-lipase and AK-lipase, respectively. Furthermore, it might be possible to separate and concentrate C20 polyunsaturated fatty acids (PUFAs) with or without a Delta5 double bond from PUFAs rich oils including both fatty acids.     

Enzymatic purification of polyunsaturated fatty acids

Polyunsaturated fatty acids (PUFAs) have various physiological functions. Of these, ethyl eicosapentaenoate is industrially purified and used as a medicine. Other PUFAs, such as docosahexaenoic acid (DHA), gamma-linolenic acid (GLA), and arachidonic acid (AA), are also expected to be used as pharmaceutical agents; however, their industrial purification processes have not been established. Because PUFAs are highly unstable against heat and oxidation, we attempted to purify them by taking advantage of their enzymatic reactions. When free fatty acids (FFAs) originating from PUFA-containing oil were selectively esterified with lauryl alcohol (LauOH) using a lipase acting on a desired PUFA very weakly, the PUFA was efficiently enriched in the FFA fraction. In addition, when selective alcoholysis of ethyl esters originating from PUFA-containing oil with LauOH was carried out, the PUFA ethyl ester (EtPUFA) was enriched to a desired purity in the unreacted ethyl ester fraction. These reaction mixtures contain LauOH, PUFA (EtPUFA), and lauryl esters, and their molecular weights are different from one another. Hence, PUFA or EtPUFA can be easily separated by conventional distillation. Selective esterification increased the purity of DHA, GLA, and n-6 PUFAs rich in AA to 91, 98, and 96 wt%, respectively. Selective alcoholysis was also effective for increasing the purity of ethyl docosahexaenoate to 90 wt%.     

Children's daily exposure to polychlorinated biphenyls from dietary supplements containing fish oils

In children, omega-3 polyunsaturated fatty acids (PUFAs) may elicit a suite of health benefits including enhancement of cognitive development. Subsequently, dietary supplements containing omega-3 PUFAs have become increasingly popular. Often, the largest source of beneficial PUFAs in these supplements is fish oil, which may contain significant levels of contaminants such as polychlorinated biphenyls (PCBs). The objectives of this study were to evaluate congener-specific PCB concentrations in 13 over-the-counter children's dietary supplements containing fish oils/powders and assess potential PCB exposures through ingestion of these products on a daily basis. Every supplement analysed contained PCBs, with a mean concentration of 9?±?8?ng PCBs/g supplement. When following serving size suggestions, mean daily exposure values ranged from 2.5 to 50.3?ng PCBs/day. Daily exposures for children's supplements were significantly lower than those previously reported for adult supplements and may be explained, in part, by the variability in the amount of fish oil (and PUFA content) in a serving size. Based on this study, factors such as fish oil purification methods (e.g., molecular distillation) and the trophic level of the fish species used to make the fish oil cannot be used as indicators of PCB levels within children's supplements. Fish supplements may decrease or increase daily PCB exposure compared with ingestion of fresh fish. However, eating fish high in omega-3 PUFAs and low in PCBs may reduce PCB exposure compared with daily supplementation with fish oils for some products studied.     

28种功能性食用油脂肪酸组成研究

目的研究28种功能性食用油脂的脂肪酸组成,包括8种国家新食品原料(新资源食品)目录油脂。方法采用气相色谱-氢火焰离子化检测器(gas chromatography-flame ionization detection,GC-FID)方法对28种油脂的脂肪酸组成进行研究。在GC-FID图谱基础上,得出了所测的28种植物油脂中37种脂肪酸的指纹图谱。根据脂肪酸的保留时间和峰面积进行定性和相对定量,进而分析饱和脂肪酸(saturated fatty acid,SFA)、不饱和脂肪酸(unsaturated fatty acid,UFA)、多不饱和脂肪酸(polyunsaturated fatty acid,PUFA)、单不饱和脂肪酸(monounsaturated fatty acid,MUFA)组成,从而分析样品的脂肪酸组成。结果在28种功能性油脂中,芍药籽油、芥花油、美藤果油、文冠果油、星油藤种子、翅果油等10种油脂UFA含量都在90%以上;MUFA含量最高为澳洲坚果油80.3%,其中,PUFA含量以美藤果油最多,达到82.0%,星油藤种子油次之,为81.1%,二者亚油酸(C18:2)和亚麻酸(C18:3)均含量高达40%;漆树种仁油、毗黎勒油、秋葵籽油、油瓜油的SFA含量均超过30%。结论该研究对探讨利用脂肪酸指标评价新型功能性油脂的营养价值及其开发利用具有指导意义。     

饲喂不同配比油脂饲料对肉鸡肉品质及肌肉中脂肪酸组成的影响

研究日粮中添加不同配比油脂对肉鸡肉品质、肌肉胆固醇含量及脂肪酸组成的影响。选取648只1日龄AA肉鸡,随机分成6组,CON为对照组(饲喂基础日粮),SO为正对照组(日粮中添加豆油),LO为负对照组(日粮中添加猪油),COP、COC、COV组分别在日粮中添加以棕榈油为主的配比油脂、以椰子油为主的配比油脂、多种植物油组成的配比油脂,实验期为42d。结果表明：COP组胸肌24h的滴水损失显著升高(P＜0.05);COC组腿肌烹饪损失显著降低(P＜0.05)。LO组胸肌不饱和脂肪酸/饱和脂肪酸得到提高(P＜0.05);SO、LO、COP、COC组n-3多不饱和脂肪酸含量均得到提高(P＜0.05);SO、COC组n-6多不饱和脂肪酸含量高于CON组(P＜0.05);除COV组外,各组n-6/n-3低于CON组(P＜0.05)。SO组胸肌胆固醇含量低于除LO组外的各组(P＜0.05)。结论：配比油脂组提高了肉鸡肌肉中多不饱和脂肪酸(PUFA)含量,对肉鸡肉品质没有产生不良的影响,豆油组改善了胸肌中脂肪酸比例并降低胆固醇含量,以椰子油为主的配比油脂次之。     

Characterisation of yoghurt enriched with polyunsaturated fatty acids by using walnut slurry

This study aimed to evaluate the physicochemical, chemical, rheological, sensorial and microbiological properties of yoghurt enriched with polyunsaturated fatty acids (PUFAs). The PUFA‐enriched yoghurt was prepared with walnut slurry (10%?50%) and skimmed milk (50%?90%). Compared with the control yoghurt, it contained a lower content of protein, potassium, sodium and phosphorus, and a higher content of fat, iron, magnesium and zinc. Moreover, it exhibited a lower syneresis value and a higher water‐holding capacity value. Its fat was rich in omega fatty acids, mainly linoleic and linolenic acids. These research findings revealed that walnut slurry could be used in yoghurt manufacture to develop fermented milk products as functional foods, especially when enriched with omega fatty acids.     

Repeated hydrolysis process is effective for enrichment of omega 3 polyunsaturated fatty acids in salmon oil by Candida rugosa lipase

Enrichment of omega 3 polyunsaturated fatty acids (PUFA) in the glyceride fraction of salmon oil was performed by Candida rugosa lipase (CRL)-catalysed hydrolysis. Total omega 3 PUFA content in the product was 38.71% (mol.%), more than double of the initial level. The hydrolysis reaction was scaled up to 1 l in a stirred tank reactor without any decrease in the selectivity of the reaction. Moreover, non-steroselectivity and acyl chain specificity of CRL-catalysed hydrolysis, as well as CRL’s recognition of the whole triacylglycerol molecule, were proved. The product was purified by short path distillation, which was also shown to contribute to the recovery of omega 3 PUFA in residue. After the removal of free fatty acids, the final product was subjected to a second round of hydrolysis to concentrate omega 3 PUFA further to 50.58%. Recoveries of eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) decreased slightly after the second round of hydrolysis, while oleic acid (OA) content was not affected.     

Essential fatty acids and trans contents of some oils,margarine and other food fats

Levels of polyunsaturated fatty acids (PUFA), cis, cis-methylene interrupted polyunsaturated fatty acids (i.e. essential fatty acids—EFA) and isolated trans double bonds in six crude vegetable oils, seven commercial oils, eighteen margarines, two butter fats and fats from two types each of crisps and butter biscuits have been determined. The ratios between the PUFA or EFA and the saturated fatty acids of various samples have been tabulated. Normal (i.e. high linoleic) safflower seed oil gave the highest ratio. Margarines which were estimated to contain partially hydrogenated fish oils (45–90%, on fat basis) gave high values of trans double bonds. Butter fat having a similar EFA level to that present in a ‘hydrogenated fish oil’ margarine contained a much lower level of trans isomers. Almost all the PUFA in the oils of crips, and about half the PUFA content of butter biscuits, existed as ‘true’ essential fatty acids.     

Omega 3 polyunsaturated fatty acids and the treatment of depression

Depression is a common, recurrent, and debilitating illness that has become more prevalent over the past 100 years. This report reviews the etiology and pathophysiology of depression, and explores the role of omega 3 polyunsaturated fatty acids (n-3 PUFA) as a possible treatment. In seeking to understand depression, genetic factors and environmental influences have been extensively investigated. Research has led to several hypotheses for the pathophysiological basis of depression but a definitive pathogenic mechanism, or group thereof, has hitherto remained equivocal. To date, treatment has been based on the monoamine hypothesis and hence, selective serotonin reuptake inhibitors have been the most widely used class of medication. In the last decade, there has been considerable interest in n-3 PUFAs and their role in depression. These fatty acids are critical for development and function of the central nervous system. Increasing evidence from epidemiological, laboratory, and randomized placebo-controlled trials suggests deficiency of dietary n-3 PUFAs may contribute to development of mood disorders, and supplementation with n-3 PUFAs may provide a new treatment option. Conclusions based on systematic reviews and meta-analyses of published trials to date vary. Research into the effects of n-3 PUFAs on depressed mood is limited. Furthermore, results from such have led to conflicting conclusions regarding the efficacy of n-3 PUFAs in affecting reduction in symptoms of depression. PUFAs are generally well tolerated by adults and children although mild gastrointestinal effects are reported. There is mounting evidence to suggest that n-3 PUFAs play a role in depression and deserve greater research efforts.     

Stability,sensory quality,texture properties and nutritional value of fish oil‐enriched spreadable fat

A Correction has been published for this article in Journal of the Science of Food and Agriculture 84(15):2142 (2004). The intake of omega‐3 long‐chain polyunsaturated fatty acids (PUFAs) in the typical Western diet is usually below the recommended level. Without radical changes of eating patterns the diet may be enhanced by enrichment of foods with unhydrogenated fish oil, which is the richest source of the long‐chain omega‐3s, eicosapentaenoicacid (EPA) and docosahexaenoicacid (DHA). The aims of the study were to establish the sensorily acceptable fish oil enrichment level of a reduced‐fat spread, to enhance the omega‐3 long‐chain PUFA content and to evaluate the enriched spread's stability during 3 months of storage (6°C, limited exposure to light and air). Samples were prepared in an industrial pilot plant. Overall sensory quality, intensity of fishy flavour, texture properties (sensory and instrumental), peroxide value, acid number and fatty acids composition were measured. A spread enriched by addition of 30.0 g kg^?1 of unhydrogenated fish oil could be stored for up to 3 months without significant decrease of the measured stability indicators. A daily portion of this enriched spread (30 g) would provide 0.25 g of EPA and DHA, significantly increasing long‐chain omega‐3 levels in the average diet. Copyright © 2004 Society of Chemical Industry     

Dietary omega‐3 PUFA and health: Stearidonic acid‐containing seed oils as effective and sustainable alternatives to traditional marine oils

The daily consumption of dietary omega‐3 PUFA is recommended by governmental agencies in several countries and by a number of health organizations. The molecular mechanisms by which these dietary PUFA affect health involve the enrichment of cellular membranes with long‐chain 20‐ and 22‐carbon omega‐3 PUFA that impacts tissues by altering membrane protein functions, cell signaling, and gene expression profiles. These changes are recognized to have health benefits in humans, especially relating to cardiovascular outcomes. Cellular membrane enrichment and health benefits are associated with the consumption of long‐chain omega‐3 PUFA found in marine oils, but are not generally linked with the consumption of alpha‐linolenic acid, the 18‐carbon omega‐3 PUFA found in plant seed oils. However, the supply of omega‐3 PUFA from marine sources is limited and may not be sustainable. New plant‐derived sources of omega‐3 PUFA like stearidonic acid‐soy oil from genetically modified soybeans and Ahiflower oil from Buglossoides arvensis seeds that are enriched in the 18‐carbon omega‐3 PUFA stearidonic acid are being developed and show promise to become effective as well as sustainable sources of omega‐3 PUFA. An example of changes in tissue lipid profiles associated with the consumption of Ahiflower oil is presented in a mouse feeding study.     

Characterization of lipids and antioxidant capacity of novel nutraceutical egg products developed with omega‐3‐rich oils

BACKGROUND: Cardiovascular disease has had an unquestioned status of the number one cause of death in the US since 1921. Omega‐3 polyunsaturated fatty acids (ω‐3 PUFAs) have cardio‐protective benefits. However, egg is typically a poor source of ω‐3 PUFAs and, in general, the American diet is low in these cardio‐protective fatty acids. Novel, nutritionally enhanced egg products were developed by substituting yolk with ω‐3 PUFA‐rich flaxseed, menhaden, algae, or krill oil. Experimental egg products matched composition of hen egg (whole egg). The experimental egg products, mixed whole egg, and a liquid egg product (Egg Beaters^?) were microwave‐cooked and compared. RESULTS: Although fat, protein, and moisture contents of experimental egg products matched (P > 0.05) mixed whole egg, experimental egg products had more (P < 0.05) ω‐3 PUFAs, lower (P < 0.05) ω‐6/ω‐3 ratio, and depending on oil added, a higher (P < 0.05) unsaturated/saturated fatty acids ratio compared to mixed whole egg. Triglycerides were the main lipid class in all experimental egg products except those developed with krill oil, which had even more phospholipids than mixed whole egg. Analysis of thiobarbituric acid reactive substances showed that lipid oxidation of experimental egg products was lower (P < 0.05) or similar (P > 0.05) to mixed whole egg, except for experimental egg products with krill oil. However, peroxide value showed that all egg samples had minimal oxidation. Experimental egg products developed with menhaden or flaxseed oil had the highest (P < 0.05) concentration of the antioxidant, ethyoxquin compared to all other egg samples. However, experimental egg products with krill oil likely contained a natural antioxidant, astaxanthin. CONCLUSION: This study demonstrated an alternative approach to developing novel, nutraceutical egg products. Instead of dietary modification of chicken feed, yolk substitution with ω‐3 PUFAs oils resulted in enhancement of ω‐3 PUFAs beyond levels possible to achieve by modifying chicken feed. Copyright © 2011 Society of Chemical Industry     

Characterization of liver oils from three species of sharks collected in Tunisian coasts: In vitro digestibility by pancreatic lipase

The increase in world fish lipid request has made necessary the search for new fish species rich in polyunsaturated fatty acid (PUFA) that could be used as raw material for oil production. In this study, liver oils from the deep‐sea sharks Mustelus mustelus, Squalus acanthias, and Rhinobatos cemiculus were extracted and analyzed to describe their lipids characteristics. Lipid contents of shark livers ranged from 64.245 to 69.57%. Among minerals, potassium and sodium were the most abundant while unsaturated fatty acids (FAs) were dominant exceeding 55% of the total FAs. Omega‐3 PUFA (ω‐3 PUFA) profiles exhibited a dominance of eicosapentaenoic acid and docosahexaenoic acid. This study suggests that shark livers, actually considered as waste, may be an attractive source of ω‐3 PUFAs and a good source of carotenoids and phenolic compounds.

Practical applications

The production of EPA and DHA concentrates from residual sources of marine oils has unexplored potential of use in food industry and oil‐based nutraceutical production for obtaining health benefits can be achieved. The economic activities of fish residues can reduce inappropriate excessive fishing, reducing imports of fish oils while contributing to the ecosystem balance.     

Encapsulation of vegetable oils as source of omega-3 fatty acids for enriched functional foods

Polyunsaturated omega-3 fatty acids (PUFAs), a functional component present in vegetable oils, are generally recognized as being beneficial to health. Omega-3 PUFAs are rich in double bonds and unsaturated in nature; this attribute makes them highly susceptible to lipid oxidation and unfit for incorporation into long shelf life foods. The microencapsulation of oils in a polymeric matrix (mainly polysaccharides) offers the possibility of controlled release of the lipophilic functional ingredient and can be useful for the supplementation of foods with PUFAs. The present paper provides a literature review of different vegetable sources of omega-3 fatty acids, the functional effects of omega-3 fatty acids, different microencapsulation methods that can possibly be used for the encapsulation of oils, the properties of vegetable oil microcapsules, the effect of encapsulation on oxidation stability and fatty acid composition of vegetable oils, and the incorporation of long-chain omega-3 polyunsaturated fatty acids in foods.     

常用食用油的营养特点和作用研究进展

常用食用油有橄榄油、花生油、大豆油、茶油、芝麻油等。不同食用油的脂肪酸组成和含量不同,特别是一些重要的脂肪酸如油酸、亚油酸、亚麻酸等不饱和脂肪酸含量不近相同。橄榄油和茶油的油酸含量高达70％以上;花生油中油酸约占40％;大豆油的多不饱和脂肪酸含量较高,主要为亚麻酸;芝麻油中亚油酸含量占到40％以上。食用油除提供能量和必需脂肪酸外,还有脂溶性维生素和一些植物化合物,一些食用油对控制脂代谢异常具有一定的作用。     

The bioavailability of an omega‐3‐rich algal oil is improved by nanoemulsion technology using yogurt as a food vehicle

Global trends show that habitual omega‐3 intakes are short of recommended guidelines, particularly among vegetarians. Subsequently, alternative dietary sources of long‐chain omega‐3 polyunsaturated fatty acids (LC3PUFA) from vegetarian sources are needed. Food technology methods are advancing, and nanoemulsion technologies have improved the bioavailability of certain lipid‐based nutrients. This study examined whether ingestion of an omega‐3 algal oil nanoemulsion led to improved bioavailability compared to the bulk oil. Eleven subjects completed a single‐blind, randomised crossover trial, with a 21‐day washout between interventions. Results demonstrated that LC3PUFA absorption from the nanoemulsion was significantly higher than the bulk oil. Percentage blood fatty acids were significantly increased for docosahexaenoic acid (DHA; P ≤ 0.05) while LC3PUFA: PUFA ratios increased (P ≤ 0.05) and omega‐6:omega‐3 ratios were reduced (P = 0.028). Larger and longer intervention studies are now needed, but these preliminary findings demonstrate that nanoemulsion technology may improve the absorption of omega‐3 fatty acids.     

GC-MS法分析蚕蛾油与蚕蛹油的脂肪酸组成

采用超临界CO2 萃取雄蚕蛾与蚕蛹中的油脂,经甲酯化处理用气相色谱- 质谱联用仪进行分析,在雄蚕蛾油中分离鉴定出15 种脂肪酸,含量最高的是α- 亚麻酸(36.71%),其中直链饱和脂肪酸(SFA)54.52%;单不饱和脂肪酸(MUFA)6.89%;多不饱和脂肪酸(PUFA)38.63%。在蚕蛹油中共分离鉴定出14 种脂肪酸成分,含量最高的是亚油酸(39.03%),其次是α- 亚麻酸(33.22%),其中直链饱和脂肪酸(SFA)占25.73%;单不饱和脂肪酸(MUFA)占2.12%;多不饱和脂肪酸(PUFA)占72.25%。