气相色谱法测定鱼油中的二十碳五烯酸、 二十二碳六烯酸和二十二碳五烯酸

目的通过优化鱼油中二十碳五烯酸(eicosapentaenoic acid,EPA)、二十二碳六烯酸(docosahexaenoic acid,DHA)和二十二碳五烯酸(docosapentaenoic acid,DPA)的测定条件,建立鱼油中EPA、DHA和DPA气相色谱定量检测分析方法。方法采用正己烷处理样品,经色谱柱(Agilent,Elite-WAX,30 m×0.25 mm,0.25μm)分离鱼油中的EPA、DHA、DPA甲酯标准品,并进行定量检测。结果 EPA浓度在0.36~3.6 mg/m L、DHA浓度在0.37~3.7 mg/m L、DPA浓度在0.16~1.62 mg/m L的范围内与峰面积的线性良好,相关系数r0.999。在80%、100%、120%添加水平下,EPA、DHA和DPA的检出限分别为0.01%、0.03%、0.009%,EPA、DHA和DPA的回收率分别为96.2%、96.4%、95.7%。结论气相色谱法灵敏度高、准确、重现性好,适用于鱼油中EPA、DHA和DPA的含量测定。     

Evaluation of the potential use of discard species for fish silage and assessment of its oils for human consumption

Waste or by-products contains a substantial amount of nutrients. Fish silage is an alternative way for assessment of fish discards and waste generated in the fish processing industries. The aim of the study was to evaluate the potential use of discard species (Equulites klunzingeri, marine fish and Carassius gibelio, freshwater fish) for fish silage and chemical quality of fish oil extracted from fish silages prepared with acid and fermented methods. Lipid quality of fish oils extracted from fish silages with LAB strains was evaluated in terms of thiobarbituric acid (TBA), peroxide value (PV), p-Anisidine (AV), totox values and fatty acid composition. The results showed that PV, TBA, AV and totox values of all extracted fish oils were within the acceptable limits for edible oils. Recovered fish oils from silage contained high level of polyunsaturated fatty acids (PUFAs), especially eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA), serving as a source of good quality fish oil for human consumption.     

Stabilizing Oils from Smoked Pink Salmon (Oncorhynchus gorbuscha)

ABSTRACT:  Smoking of meats and fish is one of the earliest preservation technologies developed by humans. In this study, the smoking process was evaluated as a method for reducing oxidation of pink salmon ( Oncorhynchus gorbuscha ) oils and also maintaining the quality of oil in aged fish prior to oil extraction. Salmon heads that were subjected to high temperatures (95 °C) during smoking unexpectedly produced oils with fewer products of oxidation than their unprocessed counterparts, as measured by peroxide value (PV), thiobarbituric acid reactive substances (TBARS), and fatty acids (FA). Higher temperatures and longer smoking times resulted in correspondingly lower quantities of oxidative products in the oils. Fatty acid methyl ester (FAME) analysis of smoke-processed oils confirmed that polyunsaturated fatty acids (PUFA) were not being destroyed. Smoke-processing also imparted antioxidant potential to the extracted oils. Even when antioxidants, such as ethoxyquin or butylated hydroxytoluene, were added to raw oils, the smoke-processed oils still maintained lower levels of oxidation after 14 d of storage. However, decreased antioxidant capacity of smoke-processed oils was noted when they were heated above 75 °C. Vitamin studies supported the antioxidant results, with smoke-processed oils displaying higher levels of α-tocopherol than raw oils. Results suggest that smoking salmon prior to oil extraction can protect valuable PUFA-rich oils from oxidation. Improved preservation methods for marine oils may extend their usefulness when added as a supplement to enhance levels of eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) in foods.     

海洋鱼油的生产与应用

全面回顾了国内外海洋鱼油生产与应用的历史与现状,指出海洋鱼油作为二十碳五烯酸(EPA)、二十二碳六烯酸(DHA)等ω-3多不饱和脂肪酸的重要来源,正在饲料、食品以及药品等领域展示其良好的应用前景.     

Comparison of sulfuric acid treatment and multi-layer silica gel column chromatography in cleanup methods for determination of PCDDs,PCDFs and dioxin-like PCBs in foods

Two typical cleanup methods, sulfuric acid treatment and multi-layer silica gel column chromatography, for the determination of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dioxin-like PCBs) in seventeen food samples were examined and compared. Vegetables, fruits, cereals, fish, meat and dairy foods were extracted by conventional methods (shaking with acetone/n-hexane or with n-hexane after alkaline treatment). The extracts were cleaned up by sulfuric acid treatment or multi-layer silica gel column chromatography, followed by several column chromatographic steps. Of the samples treated, the vegetable, fruit and cereal samples could be directly applied to the multi-layer silica gel column after extraction. However, the samples containing fats and oils such as fish, meat and dairy foods needed to be treated several times with concentrated sulfuric acid before multi-layer column chromatography, because these samples plugged the column with oily residues. Both cleanup methods gave similar values of isomeric concentrations and showed similar efficiency of purification, and the recoveries ranged from 40 to 120%. These results are considered to provide useful data for the efficient analysis of dioxins in foods which have wide-ranging compositions.     

A process for the synthesis of PUFA-enriched triglycerides from high-acid crude fish oil

This paper reports a research interest, that aims to establish a feasible industrial process, for the enzymatic production of glycerides with highly concentrated n-3 polyunsaturated fatty acids (eicosapentaenoic acid and docosahexaenoic acid), from high-acid crude fish oils. The process covers enzymatic deacidification of crude fish oil, alkaline-based synthesis of polyunsaturated fatty acids ethyl esters, concentration of polyunsaturated fatty acids ethyl esters, and enzyme catalyzed synthesis of polyunsaturated fatty acids glycerides. Commercial available immobilized lipase, Novozym 435, was used as the catalyst. The synthesized glycerides contained 5.5% of eicosapentaenoic acid and 74.6% of docosahexaenoic acid, which was 1.21 and 2.71 times more than that in the original fish oil, respectively. The application of the designed process was successfully proved by a 100-fold scale-up reaction.     

Mercury and omega-3 fatty acids in retail fish sandwiches

Mercury and fatty acids were measured in fish sandwiches from six retail restaurant chains. Average mercury concentrations ranged from 5 to 132 ppb and were well below the Food and Drug Administration action level (1,000 ppb). The average concentrations of eicosapentaenoic acid plus docosahexaenoic acid ranged from 91 to 620 mg per sandwich. Consuming one or two fish sandwiches per week could result in the consumption of 2 to 40% of the reference dose for mercury for a 60-kg individual and would provide 18 to 126% of the adequate intake for eicosapentaenoic acid plus docosahexaenoic acid as recommended for a pregnant or lactating woman.     

Determination of boric acid in foods: Comparative study of three methods

Three methods for the determination of boric acid in foods were studied in detail, namely the titrimetric method using mannitol, and two colorimetric procedures using carminic acid or curcumin. Agar-agar strips, pickled mango, noodles and prawns were analysed and the repeatability, sensitivity and recovery of the methods compared. The titrimetric and curcumin methods gave mean values for boric acid which were significantly (P < 0·05) higher than those of the carminic acid method. Results with the titrimetric method did not differ from those with the curcumin method; the latter method gave good recoveries (～ 100%) for all four foods at all levels of addition. Analyses carried out on NBS Standard Material showed that the curcumin method gave the most accurate results. This method was also found to show the least internal variation both in terms of mean boric acid content and recovery. Furthermore, the method possessed practical advantages over the other two techniques. Based on the results obtained from the comparative studies, the curcumin method was found to be the most reliable and hence would be the method of choice for boric acid determination in foods.     

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.     

气相色谱法测定海豹油中EPA、DPA、DHA含量的方法学研究

目的：建立气相色谱检测海豹油中EPA、DPA和DHA的方法。方法：采用氢氧化钾-甲醇酯化法将海豹油中的脂肪酸快速、有效的转化成脂肪酸甲酯,并通过方法学实验验证其可行性。结果：EPA、DPA和DHA甲酯含量在10～2000μg/mL范围内,峰面积与EPA、DPA和DHA甲酯含量呈良好线性关系;加样回收率在96.93%～103.38%之间,相对标准偏差小于2%;结论：该方法可以快速、准确地同时测定EPA、DPA和DHA含量。     

Activity of caffeic acid in different fish lipid matrices: A review

Caffeic acid, a hydroxycinnamic acid common in different vegetable sources, has been employed as a natural antioxidant for inhibiting oxidation of fish lipids present in different food matrices. The aim of this review is to discuss the mechanisms involved in the antioxidative and prooxidative effects of caffeic acid found in different model systems containing fish lipids. These model systems include bulk fish oils, liposomes from cod roe phospholipids, fish oil emulsions, washed cod mince, regular horse mackerel mince and a fish oil fortified fitness bar. The data reported show that the antioxidant activity depends on the physical state of the lipids and the composition of the intrinsic matrix in which they are situated. Caffeic acid significantly prevented rancidity in both unwashed and washed fish mince, the latter which was fortified with haemoglobin. In the unwashed mince, the activity was however clearly dependent on the lipid to antioxidant ratio. In these systems, an important redox cycle between caffeic acid and the endogenous reducing agents ascorbic acid and tocopherol were further thought to play an important role for the protective effects. The effect of caffeic acid was also highly dependent on the storage temperature, showing higher effectiveness above than below 0 °C. Caffeic acid was not able to inhibit oxidation of bulk fish oils, fish oil in water emulsions and the fish-oil enriched fitness bar. In the liposome system, caffeic acid inhibited haemoglobin (Hb)-promoted oxidation but strongly mediated Fe²⁺ mediated oxidation. In conclusion, caffeic acid can significantly prevent Hb-mediated oxidation in fish muscle foods but its activity in food emulsions and liposomes is highly dependent on the pH, the emulsifier used and the prooxidants present.     

食品中全氟辛酸、全氟辛基磺酸的检测技术研究进展

全氟化合物(Perfluorinated compounds,PFCs)是一类含碳-氟键的高度稳定的极性有机化合物,全氟辛酸(Pentadecafluorooctanoic acid,PFOA)和全氟辛烷磺酸(Sperfluorooctanesulphonate,PFOS)是环境中广泛存在得两种典型全氟化合污染物,这两种典型的全氟化合物广泛应用于化工领域。此类全氟化合物因为具有持久的稳定性、生物积累性和多种毒性等,严重危害到了人类健康和其生存环境,多国政府纷纷颁布法令法规限制PFOA、PFOS的使用。因此食品基体中PFOA、PFOS的检测分析成为了当下分析科学研究的热点。本文首先对全氟化合物的结构、类型、极性等理化性质和全氟污染物的危害毒性进行概述,其次根据其化学性质以及参考国标等方法,梳理了国内外各种前处理方法,如：液液萃取、液固萃取、固相萃取、超声辅助萃取、QuEChERs等。其中QuEChERs方法结合多步净化方法能够最大程度降低食品中的基质效应。此外比较了气相色谱、液相色谱等方法在分离检测方面的优缺点,比较了已有文献中不同前处理方法和检测方法下的检出限、回收率、RSD等数据,结果发现UPLC-MS/MS法由于低检出限,方法稳定,检测快速,结果准确确等优点,仍为当下主流的检测手段。本文对于制定相应食品中全氟化合物质量安全标准,确保消费者食用安全具有重要意义,并总结了当下全氟化合物所遇检测的瓶颈,期望能为当下国内外全氟化合物污染防治和制定标准提供参考依据。     

涡旋振荡提取-高效液相色谱-紫外检测法测定铁叶酸片中的叶酸含量

摘要：目的建立涡旋振荡提取-高效液相色谱-紫外检测法（high performance liquid chromatography-ultraviolet, HPLC-UV）快速测定保健食品铁叶酸片中叶酸含量的分析方法。方法样品研磨成粉后,取样0.1 g, 加入0.3%的氨溶液25 mL,之后立即在旋涡混合器中涡旋振荡提取3 min。静置3 min后取上清液,滤膜过滤后,结合HPLC-UV方法进行含量检测。结果改进后的涡旋振荡提取法相比于常规的超声及加热提取法,前处理时间更短,提取效率更高,而且能够良好的避免基质中亚铁离子对含量测定的影响。叶酸在0.0054~0.2143 mg/mL浓度范围内线性良好（r2=0.9999）,实际样品平均回收率为98.18%~99.88%,相对标准偏差为0.89%~1.12%（n=6）。结论此改进后的方法准确、高效、简便、重现性良好,适用于保健食品铁叶酸片中叶酸含量的测定。     

超临界二氧化碳富集提纯鱼油中EPA和DHA的研究进展（Ⅰ）──超临界二氧化碳与鱼油脂肪酸的相平衡研究

鱼油中的特征脂肪酚ＥＰＡ（廿碳五烯酸）和ＤＨＡ（廿二碳六烯酸）对人体的医疗保健作用受到越来越广泛的重视。综述了近年来人们对超临界二氧化碳（ＳＣ－Ｃ０２）与鱼油脂肪酸相平衡的研究概况，分析了温度、压力、夹带剂等对ＳＣ－ＣＯ２从鱼油脂肪酸混合物中萃取提纯ＥＰＡ和ＤＨＡ的影响。     

UPLC-MS/MS法快速测定乳酸菌发酵食品中的苯乳酸

建立一种超高效液相色谱-串联质谱(ultra performance liquid chromatography-tandem mass spectrometry,UPLC-MS/MS)快速测定发酵食品中苯乳酸的方法,并利用此方法对45种乳酸菌发酵食品中苯乳酸的含量进行测定。样品经甲醇提取,采用UPLC-MS/MS法,色谱柱为Shim-pack XR-ODS C₁₈(3.0 mm×75.0 mm,2.2μm),流动相为0.3%甲酸-水和0.3%甲酸-乙腈,梯度洗脱,流速为0.4 mL/min。苯乳酸在1~500 ng/mL范围内线性关系良好(R²=0.9999),检出限和定量限分别为0.3和1 ng/mL,回收率为90.5%~105.0%,相对标准偏差为1.2%~4.4%。采用此方法对16种市售乳酸菌饮料、8种发酵乳、11种黄酒样品、发酵豆制品、米酒、奶酪、发酵香肠、馒头、面包等食品中苯乳酸的含量进行测定,结果显示所有样品中均含有苯乳酸。该研究所建立的方法前处理简单、分析时间短、灵敏度高、准确性好,适用于发酵食品中苯乳酸的测定。可以为高产苯乳酸菌株资源的挖掘以及发酵食品品质与营养功能的进一步研究提供科学依据。     

Development of an analytical method for the simultaneous analysis of MCPD esters and glycidyl esters in oil-based foodstuffs

Substantial progress has been recently made in the development and optimisation of analytical methods for the quantification of 2-MCPD, 3-MCPD and glycidyl esters in oils and fats, and there are a few methods currently available that allow a reliable quantification of these contaminants in bulk oils and fats. On the other hand, no standard method for the analysis of foodstuffs has yet been established. The aim of this study was the development and validation of a new method for the simultaneous quantification of 2-MCPD, 3-MCPD and glycidyl esters in oil-based food products. The developed protocol includes a first step of liquid–liquid extraction and purification of the lipophilic substances of the sample, followed by the application of a previously developed procedure based on acid transesterification, for the indirect quantification of these contaminants in oils and fats. The method validation was carried out on food products (fat-based spreads, creams, margarine, mayonnaise) manufactured in-house, in order to control the manufacturing process and account for any food matrix–analyte interactions (the sample spiking was carried out on the single components used for the formulations rather than the final products). The method showed good accuracy (the recoveries ranged from 97% to 106% for bound 3-MCPD and 2-MCPD and from 88% to 115% for bound glycidol) and sensitivity (the LOD was 0.04 and 0.05 mg kg^?1 for bound MCPD and glycidol, respectively). Repeatability and reproducibility were satisfactory (RSD below 2% and 5%, respectively) for all analytes. The levels of salts and surface-active compounds in the formulation were found to have no impact on the accuracy and the other parameters of the method.     

气相色谱法测定保健食品中二十碳五烯酸的不确定度评定

目的评定气相色谱法测定保健食品中二十碳五烯酸的不确定度。方法样品用正己烷溶解,经皂化、甲酯化后用气相色谱法检测,外标法定量,对保健食品中的二十碳五烯酸进行测定。建立数学模型对测量不确定度的来源进行分析和评定,合成不确定度。结果二十碳五烯酸含量测定的合成不确定度为4.2%,扩展不确定度为19 mg/g,测量结果为(2.2±0.2)×10~2 mg/g,k=2,置信区间为95%。通过对各不确定度分量进行分析,不确定度主要由标准系列溶液配制和样品制备过程引入。结论对气相色谱法测定保健食品中二十碳五烯酸的过程进行不确定度评定与分析,有利于检测结果准确性的提高和实验室的质量控制。     

Supercritical fluid extraction of fish oil from fish by-products: A comparison with other extraction methods

Fish and fish by-products are the main natural source of omega-3 polyunsaturated fatty acids, especially EPA (eicosapentaenoic acid) and DHA (docosahexaenoic acid), both of them with a great importance in the food and pharmaceutical industries. Comparing to conventional fish oil extraction processes such as cold extraction, wet reduction or enzymatic extraction, supercritical fluid extraction with carbon dioxide under moderate conditions (25 MPa and 313 K) may be useful for reducing fish oil oxidation, especially when fish oil is rich in omega-3 such as salmon oil, and the amount of certain impurities, such as some species of arsenic. Furthermore, taking profit of the advantages of supercritical carbon dioxide as extractive solvent, a coupled extraction-fractionation process is proposed as a way to remove free fatty acids and improve fish oil quality, alternatively to physical and chemical refining procedures.     

Stability of docosahexaenoic acid and eicosapentaenoic acid in breads after baking and upon storage

Wholemeal bread and white bread were prepared by substituting shortening with refined menhaden fish oil (0.5%, 1.0% and 1.5% w/w). The stability of eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) were evaluated over 5 days of storage through gas chromatography (GC) analysis along with peroxide and anisidine value determinations. Sensory analysis was also performed by evaluating the fishy flavour, palatability and palatability differences compared to the control bread upon storage. The recoveries of EPA and DHA in breads after baking were 68.7%–72.8% with no further significant changes (P < 0.05) upon storage for both types of breads. Results from GC analyses correlated well with peroxide and anisidine value analyses, which showed relatively low values throughout the storage time. Omega‐3‐fatty acids from Menhaden fish oil can be incorporated into breads by substituting the shortening at a fish oil level of 0.5% (w/w) with acceptable palatability even after a 3‐day storage period.