CN101098629B

CN101098629B - High PUFA oil compositions

Info

Publication number: CN101098629B
Application number: CN2005800459416A
Authority: CN
Inventors: J·D·海斯; V·马卡迪亚; J·P·阿兰塞特; D·A·莫根斯特恩
Original assignee: Monsanto Co
Current assignee: Monsanto Co; Monsanto Technology LLC
Priority date: 2004-11-04
Filing date: 2005-11-04
Publication date: 2010-10-13
Anticipated expiration: 2025-11-04
Also published as: CN101098629A; CN101098628A; CN101098628B

Abstract

The present invention is directed to seed oil compositions that can be used for cooking and frying applications. These oil compositions of the present invention have advantageous stability characteristics. In some embodiments, the oil compositions have a low concentration of a-linolenic acid.

Description

High pufa oil compositions

Invention field

The present invention relates to unhydrided or partially hydrogenated non-animal oil, it has the trans-fatty acid of low content and the local flavor that is particularly suitable for field of food and the Performance Characteristics of improvement, with and preparation method thereof.

Because the consumer becomes and more notes the lipid nutrients to health affected, edible undersaturated and polyunsaturated fat content height and the low oil of trans-fat levels are desirable.

The oil that contains long-chain polyunsaturated fatty acid (PUFAs) can be used as food composition.Important PUFAs comprises DHA (DHA), eicosapentaenoic acid (EPA), alpha-linolenic acid (ALA), gamma-Linolenic acid (GLA), clupanodonic acid (DPA), arachidonic acid (all-cis formula-5,8,11,14-eicosatetraenoic acid; AA) and parinaric acid (cis-6,9,12,15-parinaric acid; SDA).Many being present in marine oil (marine oil) and the vegetable seeds among these PUFAs.PUFAs is the important component of the phosphatide that exists in the plasmalemma of cell, and is the precursor of other important molecule among the human and animal, comprises prostacyclin, leukotrienes (leukotriene) and prostaglandin.In addition, PUFAs is essential in normal development, particularly the baby's brain development, and is that tissue forms and repairs necessary.

PUFAs can be from natural origin extraction or synthetic by multiple organism.Yet, exist some and PUFAs from the relevant shortcoming of the industrial production of natural origin.The natural origin of PUFAs such as animal and plant, tends to have very impure oil and forms.The oil that obtains from these sources can need large-scale purifying to isolate the oil that one or more PUFA are rich in one or more required PUFAs or generation.The fish oil that contains quite a large amount of EPA and DHA can have taste beastly and smell, and this can make them become undesirable food composition or food supplement.In addition, in some cases, fish-oil capsule can comprise the required composition of low content and other compositions that keep not wishing content, comprises impurity.

PUFAs is considered to can be used for nutrition, medicine, industry and other purposes.Therefore, it is interested extracting the high oil of PUFAs content from transgenic seed; Made these seed modifications to contain the SDA that compares higher concentration with corresponding naturally occurring seed.

Summary of the invention

A kind of embodiment of the present invention relates to fluid composition, gross weight based on aliphatic acid or derivatives thereof in the described composition, it comprises at least a polyunsaturated fatty acid or derivatives thereof with 4 or more carbon-to-carbon double bonds of 0.4wt% at least, and described composition has following any feature: peroxide value is less than about 1meq/kg and be derived from source except that marine oil; Anisidine value is less than about 3 and be derived from source except that marine oil; At least a other polyunsaturated fatty acid or derivatives thereof with 4 or more carbon-to-carbon double bonds, and anisidine value is less than about 3; Tocopherol at least about 400ppm; Or less than the trans-fatty acid of 1wt%.

Another embodiment of the present invention relates to fluid composition, gross weight based on aliphatic acid or derivatives thereof in the described composition, it comprises at least a polyunsaturated fatty acid or derivatives thereof with 4 or more carbon-to-carbon double bonds of 0.4wt% at least, described source is from the transgenosis seed, and it is selected from arabidopsis (Arabidopsis), rape (canola), carrot, coconut, cereal, cotton, flax, flaxseed, cereal, palm kernel, peanut, potato, rapeseed (rapeseed), safflower, soybean, sunflower, tobacco and its mixture.

Another aspect of the present invention relates to the method that is used for keeping the storage stability of oil between transportation or storage life, described method is included under the about 45 ℃ temperature of about 4-and oil of the present invention was stored in the container at least 1 month, and wherein said oil has the anisidine value less than 3 after storage.

Another aspect of the present invention relates to the method that is used for keeping the storage stability of oil between transportation or storage life, described method is included under the about 45 ℃ temperature of about 4-and oil of the present invention was stored in the container at least 1 month, and wherein the absolute change of the anisidine value of described oil is not more than about 20 between the storage life.

Another aspect of the present invention relates to the method that is used for keeping the storage stability of oil between transportation or storage life, and described method comprises oil of the present invention is stored in the container; With freezing (freezing) described container.

Another aspect of the present invention relates to the method that is used for keeping the storage stability of oil between transportation or storage life, and described method comprises oil of the present invention is encapsulated in the encapsulating material.

Another aspect of the present invention relates to food compositions, beverage, nutritional supplement or the edible oil that comprises oil of the present invention.

The accompanying drawing summary

Figure 1A is the figure of peroxide value (PV) relative time of fluid composition that contains the stabilizing agent of 20wt% parinaric acid (SDA) and multiple interpolation.The curve map of Fig. 1 is presented at the accelerated ageing result of experiment of carrying out under 55 ℃.

Figure 1B is the figure of anisidine value (AV) relative time of fluid composition that contains the stabilizing agent of 20wt% parinaric acid (SDA) and multiple interpolation.The curve map of Fig. 1 is presented at the accelerated ageing result of experiment of carrying out under 55 ℃.

Fig. 2 A is 20%SDA, 4%SDA blend, have the figure of PV relative time of the soya-bean oil composition of the 20%SDA of citric acid and contrast.The curve map of Fig. 2 is presented at the accelerated ageing result of experiment of carrying out under 55 ℃.

Fig. 2 B is 20%SDA, 4%SDA blend, have the figure of AV relative time of the soya-bean oil composition of the 20%SDA of citric acid and contrast.The curve map of Fig. 2 is presented at the accelerated ageing result of experiment of carrying out under 55 ℃.

Fig. 3 A is 20%SDA, 4%SDA blend, have the figure of PV relative time of the soya-bean oil composition of the 20%SDA of citric acid and contrast.The curve map of Fig. 3 is presented at the aged at room temperature result of experiment of carrying out under 25 ℃.

Fig. 3 B is 20%SDA, 4%SDA blend, have the figure of AV relative time of the soya-bean oil composition of the 20%SDA of citric acid and contrast.The curve map of Fig. 3 is presented at the aged at room temperature result of experiment of carrying out under 25 ℃.

Fig. 4 is the figure of the AV relative time of 20%SDA, 20%SDA and citric acid, commercially available fish oil and bioequivalent SDA blend fluid composition.The curve map of Fig. 4 is presented at the accelerated ageing result of experiment of carrying out under 55 ℃.

Fig. 5 contains 200ppm ascorbyl palmitate and 0,30,60 and the figure of peroxide value (PV) relative time of the 20%SDA fluid composition of 120ppm n-propyl gallate.The curve map of Fig. 5 is presented at 60 ℃ of accelerated ageing result of experiment of carrying out with film IR method down.

Fig. 6 A contains (i) ascorbyl palmitate (AP) and TBHQ, (ii) citric acid (CA) and ascorbyl palmitate (AP) and the (iii) figure of peroxide value (PV) relative time of the 20%SDA fluid composition of citric acid (CA), TBHQ and ascorbyl palmitate (AP).

Fig. 6 B contains (i) ascorbyl palmitate (AP) and TBHQ, (ii) citric acid (CA) and ascorbyl palmitate (AP) and the (iii) figure of anisidine value (AV) relative time of the 20%SDA fluid composition of citric acid (CA), TBHQ and ascorbyl palmitate (AP).

Detailed Description Of The Invention

Oil of the present invention is at the trans-fatty acid that has improved stability and have low content aspect taste and the smell.In one embodiment, owing to the health advantages of edible highly undersaturated fat, can be with some oil of the present invention as food composition.Known edible saturated fat has negative effect to cardiovascular health.Yet edible aliphatic acid with 4 or more pairs of keys is desirable.Owing to unsaturated (4 or more two key) of height, the oil phase of some oil of the present invention and unsaturated level lower (being less than 4 two keys) is so more stable than not.The low stability of some oil of the present invention causes the decomposition of fatty acids reaction, and it forms undesirable peroxide and hydroperoxides.The decomposition subsequently of those oxidation products can form volatile and nonvolatile aldehyde and/or ketone.Nonvolatile component can the described oil of catalysis further oxidation and volatile component causes undesirable taste and smell.

One aspect of the invention is fluid composition, gross weight based on aliphatic acid in the described composition, it has polyunsaturated fatty acid or derivatives thereof (for example SDA) content that has 4 or more carbon-to-carbon double bonds at least about 0.4wt%, and described composition has less than about 3 anisidine value and is derived from source except that marine oil.

Developed the method for preparation oil of the present invention by the many factor optimizations that make the described oxidizing process speed of influence, described factor comprises the exposure of temperature, seed meat or oil of concentration, system of seed storage and processing, prooxidant (pro-oxidants) (as oxygen, chlorophyll and metal) and natural existence the (as tocopherol) or the other stabilizing agent or the concentration of antioxidant.Concern complexity between these factors.Method of the present invention can provide and compare the fluid composition with the improved seed oil stability that characterizes by sense organ and flavor data by the seed oil of conventional method preparation.

I. fluid composition

A. oxidation stability

Different fluid composition of the present invention is the oil that extracts from multiple non-animal origin.Advantageously, composition of the present invention is compared with known fluid composition and is had higher stability.

Generally speaking, You stability is important for determining its purposes.For example, known oil with high concentration omega-fatty acid can provide positive health advantages and can be advantageously used for food composition.Especially, known omega-fatty acid is of value to cardiovascular health, cognitive formation (cognitivedevelopment), infant nutrition and helps to prevent cancer, rheumatoid disease and arthritis and mental disease.At present, omega-fatty acid main source is a fish oil.Because a large amount of (3 or more) the two keys in the described aliphatic acid, omega-fatty acid has more reactivity.Therefore, owing to the taste and the smell of ω-3 oil of processing from fish oil, find that omega-fatty acid has become a kind of challenge as the good source of food composition (for example being added into bread, biscuit, salad flavoring, mayonnaise, margarine and coating, pet food, beverage etc.).Correspondingly, one aspect of the present invention provides a kind of omega-fatty acid source, and it has taste and the odor characteristics that helps being used as food composition and/or have the goods of potential health advantages.

Generally speaking, the lower oil of oil ratio olefinic number of functionalities that the olefinic number of functionalities is bigger has higher oxidation rate.The reaction process of describing unrighted acid (UFAs) oxidation comprises the radical chain reaction that shows as initiation, growth and cessation reaction.The example of initiation reaction comprises captures hydrogen atom has free radical with generation aliphatic acid from aliphatic acid.Have more than two keys and to have a UFAs of pi-allyl carbon more active than the polyunsaturated fatty acid with other structures because described allylic hydrogen easier captured and described allyl radical more stable than other free radicals.In propagation process, the UFA with allyl radical can react to generate peroxide with molecular oxygen.This peroxide can react to capture hydrogen atom and to generate another fatty acid profile with another UFA in growth steps.As selection, in stopping step, allyl radical can with another radical reaction to generate the non-activity product.

Influencing the factor that oxidation has the oil of one or more unrighted acids is following function: cause from UFA capture the reagent of hydrogen atom concentration, molecule keto concentration, with radical reaction with the concentration and the raising of the compound that forms stable product (for example, stabilizing agent or cause stop other free radicals) or reduce multiple other reaction conditions of the reaction rate of described oxidation reaction.Molecular oxygen is to keep from UFAs to produce one of required most important species of peroxide, and factor mentioned above has complicated relation.

Generally speaking, the concentration of the prooxidant of initiation free radical species formation depends on the concrete prooxidant and the initiation reaction of generation with the stability relationship of height unsaturated oils.When consuming molecular oxygen in the growth steps of whole oxidation reaction flow process, it is linear that the relation between molecule keto concentration and the UFA oxidation rate is approximately.Yet molecular oxygen can participate in the other types reaction in the whole oxidation reaction flow process.For example, the triggering mechanism of proposition is to capture hydrogen by trace metal ion from UFA.In addition, have been found that UV light and temperature can improve the directtissima rate of oxygen to UFAs.Think that in addition UFAs passes through from the hydrogen peroxide that water decomposition generated of metal catalytic or by oxidized with the reaction of trace singlet oxygen.All these react all plausibilities, and can cause described processing factors, stability and the oil quality hereinafter discussed between complex relationship.

Though the relation of stabilizer concentration and UFA oxidation rate depends on concrete stabilizing agent, should concern can be because complicated more than a kind of existence of stabilizing agent.The adding of multiple stabilizing agent can be used for stable each other, and when this situation occurred, the combination of two or more stabilizing agents is compared with the single stable agent can more effective termination free radical.For example, this combination of stabilizing agent can have add with effect or be used from generation with use same amount arbitrary stabilizing agent reached compares better effect.

Although the described complexity of UFA oxidation can be determined to comprise the stability of the composition of UFAs by the compound of measuring some type that is produced by different oxidation reactions.For example, peroxide value (PV) is to weigh peroxide concentrations in the described oil with meq/kg.Peroxide generates between the heat of oxidation at UFA, thereby the PV value is high more, and then many more UFA oxidations take place.In addition, the formation by reducing peroxide or by removing/decompose the PV that the peroxide that is present in the oil or hydroperoxides can reduce described oil to greatest extent.Can reduce PV to greatest extent by multiple technologies, include, but are not limited to process formula (processing protocols).

Be used to estimate the suffered rear oxidation of oil stress another kind of criterion be known as the anisidine value (AV) of oil.AV represents described oil elapsed amount of oxidation before measuring, and is the criterion of the concentration of secondary oxidative product.The AV of oil is a standard of weighing non-volatile aldehyde in the described oil and/or ketone amount.Because the AV of oil weighs non-volatile aldehyde and/or ketone concentration (not having unit usually) in the described oil, so it is a kind of criterion of the oxidation history of oil.Aldehyde and ketone are produced by the decomposition of peroxide or hydroperoxides species, and described species are main oxidation products of olefinic degree of functionality on the aliphatic acid.Measuring the PV of oil or the method for AV is known in affiliated field, and comprises AOCS Cd 8-53 and AOCS Cd 18-90 respectively.

When estimating oil oxidation stability, reducing the amount of oxidation of measuring by PV and AV to greatest extent can have great importance.For example, peroxide and hydroperoxides can easily decompose to form peculiar smell and aldehyde and ketone, and they can serve as the catalyst that is used for the described oil of further oxidation Decomposition.

Another criterion of fatty acid oxidation is total oxidation or totox value.The totox value is in conjunction with calculating to the measurement of main oxidation product (PV) and secondary oxidative product (AV) and by equation 2PV+AV.

A kind of method of determining oxidation stability is oxidative stability index (OSI); A kind of method of measuring OSI is AOCS Cd 12b-92.The value of OSI is the time (usually in hour) of (build phase that generally is called oxidation reaction) before the maximum rate of oxidation changes; So-called induction period of this time.Though the factor of the OSI value of many influence oil is arranged, this value is predicted together with the sxemiquantitative that other criterions can be used for making about oil-proofness.

The another kind of method of determining oil oxidation stability is to adopt the standardization sensory evaluation.Generally speaking, smell, taste, tactile characteristics and the local flavor of this standardization sensory evaluation evaluation oil and by fried food in described oil or oil is introduced the characteristic of the food that comprises described oil in the food.For example, can estimate described oil and the food made from this oil or have the numerous characteristics of this oil as the food of composition.In addition, trained respondent can select from different value classes to evaluate the acceptable grade of the oil that experimentizes in sensory evaluation.The those skilled in the art can design suitable sensory evaluation.This sensory evaluation result is identified for oil acceptable of special-purpose and is an important criterion of oil-proofness therefore.

Specific scent relevant with oil and taste indication comprise the bacon flavor, beans flavors (beany), bitter taste, flat taste, the smell of burning (burnt), cardboard flavor (cardboardy), the paddy flavor, the deep-fried flavor, fishiness, fruity, the grass local flavor, underdone (green), the hay flavor, deep fat, shell flavor (hully), hydrogenated oil and fat, lard, light struck oil, the melon flavor, metallic taste, musty, the nut flavor, cross deep fat, (oxidized) of oxidation, excitant (pointy), paraffin oil, peanut oil, nut oil, oil, phenol, pine tar, oil, phenol, pine tar, plastics, fishy smell (pondy), the pumpkin flavor, putrefactive odor, original flavor, restore oil, the rubber flavor, the soap flavor, tart flavour, sulfur smoke, sunflower seed shell, watermelon, the wax flavor, weedy character and woody flavour.Usually, the oil meter that contains more than 4 two keys reveals fishiness or fishy smell feature.A kind of embodiment of the present invention is to prepare the oil that contains more than 4 two keys, and its taste and smell when producing is a flat taste.Another embodiment of the present invention is the organoleptic properties who makes that when storing the several months these oil keep its flat taste.

B. the fluid composition that has the aliphatic acid that has 4 or more pairs of keys

Having two main polyunsaturated fatty acid families, particularly is omega-fatty acid and ω-6 aliphatic acid.The mankind can pass through Δ from so-called basic aliphatic acid, linoleic acid (LA, C18:2 ω 6) and alpha-linolenic acid (ALA, C18:3 ω 3) ⁶-desaturation approach synthesizes ω-6 and omega-3 polyunsaturated fatty acids.LA passes through Δ ¹²-desaturase produces from oleic acid (C18:1 ω 9).LA passes through Δ again respectively ⁶-desaturase or prolongation enzyme (elongase) change into gamma-Linolenic acid (GLA, C18:3 ω 6) or ω 6-eicosadienoic acid (EDA).GLA and EDA are then separately respectively by prolonging enzyme or Δ ⁸Desaturase change into dihomo-gamma-linolenic acid (DGLA, C20:3).DGLA passes through Δ ⁵Desaturase catalysis forms arachidonic acid (AA, C20:4 ω 6).As selection, LA can change into alpha-linolenic acid (ALA, C18:3 ω 3).ALA changes into parinaric acid (SDA, C18:4 ω 3) or eicosatrienoic acid (EtrA, C20:3 ω 3) again.SDA and EtrA change into eicosatetraenoic acid then, and (ETA, C20:4), it changes into EPA.EPA becomes clupanodonic acid by the prolongation enzymatic conversion then, and (DPA, C22:5), it then passes through Δ ⁴-desaturase change into DHA (DPA, C22:6).Yet these approach efficient are very low, and think that it is necessary directly obtaining these polyunsaturated fatty acids from diet.

In a kind of exemplary embodiment of the present invention, based on the gross weight of aliphatic acid or derivatives thereof in the described composition, fluid composition comprises at least about 0.4,1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43,44 or 45wt% or bigger at least a polyunsaturated fatty acid or derivatives thereof with 4 or more carbon-to-carbon double bonds.In one embodiment, described composition further comprise at least about 400,450,500,600,700,800,805,810,820,830,840,850,860,870,880,890,900,1000,1100,1200,1300,1400,1500,1600,1700,1800,1900, the tocopherol of 2000ppm or more.In another embodiment, described composition has at least about 0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9 or the peroxide value of 1.0meq/kg, and is derived from the source except marine oil (for example except fish oil, marine alga wet goods).In another embodiment, described composition has less than about anisidine value of 0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1.0,1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2.0,2.1,2.2,2.3,2.4,2.5,2.6,2.7,2.8,2.9 or 3.0, and comprises at least a other polyunsaturated fatty acid or derivatives thereof with 4 or more carbon-to-carbon double bonds.In another embodiment, described composition further comprises the trans-fatty acid less than 1wt%.

In addition, the present invention relates to fluid composition, gross weight based on aliphatic acid or derivatives thereof in the described composition, it comprises at least about 0.4,1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43,44 or 45wt% or bigger at least a polyunsaturated fatty acid or derivatives thereof with 4 or more carbon-to-carbon double bonds, described source is from arabidopsis (Arabidopsis), rape, carrot, coconut, cereal, cotton, flax, flaxseed, corn, palm kernel, peanut, potato, rapeseed, safflower, soybean, the transgenic seed of sunflower and/or tobacco.In one embodiment, described composition has 0,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1.0,1.5,2.0,2.5,3.0,3.5,4.0,4.5,5.0,5.5,6.0,6.5,7.0,7.5,8.0,8.5,9.0,9.5 or the peroxide value of 10.0meq/kg.In another embodiment, described composition has 0,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1.0,1.5,2.0,2.5,3.0,3.5,4.0,4.5,5.0,5.5,6.0,6.5,7.0,7.5,8.0,8.5,9.0,9.5,10,11,12,13,14,15,16,17,18,19 or 20 anisidine value.In another embodiment, described composition has 0,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1.0,1.5,2.0,2.5,3.0,3.5,4.0,4.5,5.0,5.5,6.0,6.5,7.0,7.5,8.0,8.5,9.0,9.5,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25 or 26 totox value.In another embodiment, described composition further comprises at the most 100,200,300,400,500,600,700,800,900,1000,1100,1200,1300,1400,1500,1600,1700,1800,1900,2000,2100,2200,2300,2400,2500,2600,2700,2800,2900,3000,3100,3200,3300,3400,3500,3600,3700,3800,3900,4000,4100,4200,4300,4400,4500,4600,4700,4800,4900 or the tocopherol of 5000ppm or bigger.Tocopherol is naturally occurring stabilizing agent and comprises alpha-tocopherol, betatocopherol, Gamma-Tocopherol and Delta-Tocopherol.In another embodiment, described composition further comprises and is not more than 0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1.0,1.5,2.0,2.5,3.0,3.5,4.0,4.5,5.0,5.5,6.0,6.5,7.0,7.5,8.0,8.5,9.0,9.5 or the 10.0wt% trans-fatty acid.In another embodiment, described composition further comprises at least about 0.4,0.5,0.6,0.7,0.8,0.9,1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43,44,45,46,47,48,49 or gamma-Linolenic acid (GLA, C18:3) or derivatives thereof of 50wt%.

Exemplary polyunsaturated fatty acid or derivatives thereof with 3 or more pairs of keys is parinaric acid (SDA, C18:4), eicosatetraenoic acid (ETA), eicosapentaenoic acid (EPA, C20:5), clupanodonic acid (DPA, C22:5), DHA (DHA) and arachidonic acid (AA, C20:4).Preferably, the polyunsaturated fatty acid or derivatives thereof of above-mentioned fluid composition comprises at least a ω-3 or ω-6 aliphatic acid, and preferably comprise ω-3 parinaric acid (SDA, C18:4), ω-3 eicosatetraenoic acid (ETA), ω-3 eicosapentaenoic acid (EPA, C20:5), ω-3 clupanodonic acid (DPA, C22:5), ω-3 DHA (DHA; C22:6) or ω-6 arachidonic acid (AA, C20:4).

The present invention also can be used for containing the genetically modified plants oil that the above content of polyunsaturated fatty acid of 3 carbon-to-carbon double bonds improves.Example comprises the vegetable seeds that is derived from arabidopsis (Arabidopsis), rape, carrot, coconut, corn, cotton, flax, flaxseed, maize, palm kernel, peanut, potato, rapeseed, safflower, soybean, sunflower and/or tobacco.Exemplary polyunsaturated fatty acid or derivatives thereof with 3 or more pairs of keys is parinaric acid (SDA, C18:4), eicosatrienoic acid (EtrA, C20:3), eicosatetraenoic acid (ETA, C20:4), eicosapentaenoic acid (EPA, C20:5), clupanodonic acid (DPA, C22:5), DHA (DHA, C22:6), gamma-Linolenic acid (GLA, C18:3), dihomo-gamma-linolenic acid (DGLA, C20:3) and arachidonic acid (AA, C20:4).Preferably, the polyunsaturated fatty acid or derivatives thereof of above-mentioned fluid composition comprises at least a ω-3 or ω-6 aliphatic acid, and preferably comprise ω-3 parinaric acid (SDA, C18:4), ω-3 eicosatrienoic acid (EtrA, C20:3), ω-3 eicosatetraenoic acid (ETA, C20:4), ω-3 eicosapentaenoic acid (EPA, C20:5), ω-3 clupanodonic acid (DPA, C22:5), ω-3 DHA (DHA, C22:6), ω-6 gamma-Linolenic acid (GLA, C18:3), ω-6 dihomo-gamma-linolenic acid (DGLA, C20:3) or ω-6 arachidonic acid (AA, C20:4).

More than can further comprise gamma-Linolenic acid or derivatives thereof (C-γ 18:3) or DH-gamma-Linolenic acid (C-DH-γ 20:3) or its derivative at the composition described in this section.

As indicated above, the higher relatively oil of omega-fatty acid unit concentration is favourable food composition.Method of the present invention can be used for from containing at least a polyunsaturated fatty acid or derivatives thereof with 4 or more carbon-to-carbon double bonds, for example in the oily seed of parinaric acid, based on aliphatic acid gross weight in the described composition with greater than about 0.4,1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43,44 or 45wt% or bigger amount extract oil, described composition has less than about 0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1.0,1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2.0,2.1,2.2,2.3,2.4,2.5,2.6,2.7,2.8,2.9 or 3.0 anisidine value.Preferably, the oily seed through extracting is the seed that comprises the ratio of SDA similar to described fluid composition and total fatty acid content.Therefore, the SDA content in the whole seed be its aliphatic acid total concentration at least about 0.4wt%.In addition, the SDA content in the oil is at least about 0.4,0.5,1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30,31,32,33,34,35,36,37,38,39 or 40wt% based on aliphatic acid gross weight in the described composition during the whole processing.

In another embodiment, during the processing or whole afterwards seed or fluid composition have based on aliphatic acid gross weight in the described composition about at the most 18,19,20,21,22,23,24,25,30,35 or 40wt% linoleic acid (LA, C18:2n6) content, and based on aliphatic acid gross weight in the described composition at least about 0.4,5,10,15,20,25,30,35,40 or the SDA content of 45wt%.Attention is in described other SDA compositions arbitrarily of these compositions or this section, and the polyunsaturated fatty acid or derivatives thereof that can make another kind have 4 or more carbon-to-carbon double bonds substitutes SDA.

As selection, fluid composition is during processing or have afterwards based on the SDA content of aliphatic acid gross weight in the described composition at least about 0.4wt%, and during processing or have about at the most AV of 0.5,0.6,0.7,0.8,0.9,1.0,1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9 or 2 afterwards.In specific embodiment, described fluid composition is through refining, bleaching and taste removal (RBD) fluid composition, and it has based on SDA content and at the most about 0.1,0.2,0.3,0.4 or 0.5 the AV of aliphatic acid gross weight in the described composition at least about 0.4wt%.

In another embodiment, described RBD oil have based on aliphatic acid gross weight in the described composition at least about under the SDA content of 0.4wt% and 110 ℃ at least about 0.5,0.6,0.7,0.8,0.9,1,1.1,1.2,1.3,1.4 or 1.5 hour OSI.

In addition, can be derived from vegetable oil except blackcurrant oil, borage oil, blueweed oil, evening primrose oil, gooseberry oil, cannabis oil or red gallons of oil at the fluid composition described in the I.B joint.In addition, described fluid composition can be derived from the oil except fish oil (for example oily Pacific herring, sardine, tuna, cod, mackerel, catfish), algal oil or other marine oil.The algae that generation has 4 oil more than two keys comprises chrysophyceae, crytophyte, diatom (diatoms) and dinoflagellate (Behrens and Kyle, 1996:J.Food Lipids, 3:259-272), comprise the oil that is derived from latent dinoflagellate (Crypthecodiniumcohnii), rhombus algae (Nitzchia sp), Nannochloropsis oculata (Nannochloropsis), boat-shaped algae (Navicula sp.), Phaeodactylum tricornutum (Phaedactylum), purple ball algae (Porphyridium) and splits kettle algae (Schizochytrium).In addition, can be derived from transgenic arabidopsis (Arabidopsis), rape, carrot, coconut, cereal, cotton, flax, flaxseed, corn, palm kernel, peanut, potato, rapeseed, safflower, soybean, sunflower and/or tobacco at the fluid composition described in the I.B joint.At last, above-mentioned fluid composition can be the oil without bleaching.

As mentioned above, the mankind can pass through Δ ⁶-desaturation approach is from linoleic acid and synthetic ω-6 of alpha-linolenic acid and omega-3 polyunsaturated fatty acids, to obtain gamma-Linolenic acid and parinaric acid respectively.Further fatty acid prolonging and desaturation step produce arachidonic acid, eicosapentaenoic acid and DHA.Being used for the biosynthetic alternative approach of AA and EPA carries out at some organisms.Here, LA and ALA at first specifically extend to eicosadienoic acid (EDA, C20:2 ω 6) and eicosatrienoic acid (EtrA, C20:3 ω 3) respectively.Subsequently, the Δ of these products ⁸And Δ ⁵Desaturation produces AA and EPA.

It is synthetic from malonyl-CoA precursor that DHA and EPA also can pass through polyketide synthase (PKS) approach.Yazawa，Lipids(1996)31，S297-S300。

Recent report proof is used for the reconstruct of synthetic these Δs 8-desaturation approach of polyunsaturated fatty acid in arabidopsis (Arabidopsis thaliana), and by shifting and express three kinds of gene codes respectively, from active (the IgASE 1) (Qi etc. of the specific prolongation of the Δ 9-of Isochrysis galbana Isochrysis galbana, FEBS Lett. (2002) 510,159-165), Δ 8-desaturase (Eu Δ 8) (Wallis and Browse from euglena gracilis (Euglena gracilis), Arch.Biochem.Biophys.J. (1999) 365,307-316) and from the Δ of Mortierella alpina (Mortierella alpina) ⁵-desaturase (Mort Δ ⁵) (Michaelson etc., J.Biol.Chem. (1998) 273, and 19055-19059), (Qi etc., Nature Biotechnol. (2004) 22,739-745) in the accumulation of the discernable amount of AA and EPA in genetically modified plants.In addition, (Plant Cell (2004) 16,1-15) reported the ω 3 successful in transgene tobacco (Nicotiana tabacum) and flaxseed (Linum usitatissimum) and the specific generation of seed of ω 6 polyunsaturated fatty acids for Abbadi etc.Pereira etc. (Biochem.J. (2004) 378 (665-671)) have reported the omega-3-aliphatic acid desaturase that relates in the EPA biosynthesis.Method and composition of the present invention can be used for extracting and/or stable polyunsaturated fatty acid from the organism of producing according to the above-mentioned report of enumerating.

In the multiple oil of the present invention some can be extracted from plant tissue, comprise plant seed tissue.The plant that therefrom can isolate polyunsaturated fatty acid comprises the plant of the polyunsaturated fatty acid with natural content and the plant of improving the polyunsaturated fatty acid of content through the genetic engineering design with demonstration.The example of plant with polyunsaturated fatty acid of natural content comprises the oily seed crop, as rape (canola), safflower and flaxseed, and such as the plant of flax, evening primrose (Oenothera biennis), Common Borage (Borago officinalis) and red gallon (Ribes nigrum), Trichodesma calycosum (Trichodesma) and blueweed.Some liver moss, small liwan moss (Physcomitrellapatens) for example, known natural generation can be extracted and the polyunsaturated fatty acid of purifying according to method of the present invention.As another example, method of the present invention can be used for (comprising for example arabidopsis from the plant and/or the recombinant plant of for example making with the composition and the method for following patent and patent application, rape, carrot, coconut, cereal, cotton, flax, flaxseed, corn, palm kernel, peanut, potato, rapeseed, safflower, soybean, sunflower, tobacco and their mixture) in extract and/or stable polyunsaturated fatty acid (comprises for example parinaric acid, DHA, eicosapentaenoic acid, gamma-Linolenic acid, arachidonic acid, dihomo-gamma-linolenic acid, clupanodonic acid and parinaric acid): US 6,677,145; 6,683,232; 6,635,451; 6,566,583; 6,459,018; 6,432,684; 6,355,861; 6,075,183; 5,977,436; 5,972,664; 5,968,809; 5,959,175; 5,689,050; 5,614,393; 5,552,306 and 5,443,974, and WO 02/26946; WO 98/55625; WO 96/21022, and u.s. patent application serial number 20040078845; 20030196217; 20030190733; 20030177508; 20030163845; 20030157144; 20030134400; 20030104596; 20030082754; 20020138874 and 20020108147 (these formerly list of references incorporate this paper by reference into).

Other fluid compositions can extract from fungi.The fungi that therefrom can isolate polyunsaturated fatty acid comprises the fungi of the polyunsaturated fatty acid with natural content and the fungi of improving the polyunsaturated fatty acid of content through the genetic engineering design with demonstration.For example, method of the present invention can be used for (comprising for example saccharomycete (Saccharomyces) (degree of fermentation saccharomyces cerevisiae (S.Cerevisiae) and saccharomyces carlsbergensis (S.Carlsbergensis) comprising) from the fungi and/or the recombinant fungi of for example making with the composition and the method for following patent and patent application, Candida (Candida spp.), little Ke Yinhan mould (Cunninghamella spp.) (comprises cunninghamella elegans (C.Elegans), cunninghamella blakesleana (C.Blakesleegna) and cunninghamella echinulata (C.Echinulate)), saccharomyces oleaginosus (Lipomyces starkey), separate fat Ye Shi yeast (Yarrowia lipolytica), Crewe Vickers yeast (Kluyveromyces spp.), Hansenula yeast (Hansenula spp.), aspergillus (Aspergillus

Spp.), mould (Penicillium spp.), arteries and veins spore mould (Neurospora spp.), filament water mold (Saprolegnia diclina), wood mould (Trichoderma spp.), branch mould (Thamnidiumelegans), Pichia pastoris (Pichia spp.), pythium spp (Pythium spp.) (comprises ultimate corruption mould (P.Ultimum), pythium debaryanum (P.Debaryanum), abnormal female corruption mould (P.Irregulare) and wilting corruption mould (P.Insidiosum), thraustochytriale (Thraustochytrium aureum) and Mortierella (Mortierella spp.) (comprise long spore Mortierella (M.Elongata), small Mortierella (M.Exigua), the wet Mortierella (M.Hygrophila) of happiness, mortierella ramanniana (M.Ramanniana), the mutation of mortierella ramanniana (M.ramanniana var.Angulispora, M.ramanniana var.Nana), Mortierella alpina (M.Alpina), Mortierella isabellina (M.Isabellina) and Portugal's wine and women-sensual pursuits Mortierella (M.vinacea))) in extract and/or stable polyunsaturated fatty acid (comprises parinaric acid, DHA, eicosapentaenoic acid, gamma-Linolenic acid, arachidonic acid, dihomo-gamma-linolenic acid, clupanodonic acid and parinaric acid): US 6,677,145; 6,635,451; 6,566,583; 6,432,684; 6,410,282; 6,355,861; 6,280,982; 6,255,505; 6,136,574; 5,972,664; 5,968,809; 5,658,767; 5,614,393; 5,376,541; 5,246,842; 5,026,644; 4,871,666 and 4,783,408; And WO 02/26946; And u.s. patent application serial number 20040078845; 20030196217; 20030190733; 20030180898; 20030177508; 20030163845; 20030157144; 20030104596; 20030082754; 20020138874; 20020108147 and 20010046691 (this list of references is formerly incorporated this paper by reference into).

Other fluid composition can extract from microorganism.The microorganism that therefrom can isolate polyunsaturated fatty acid comprises the microorganism of the polyunsaturated fatty acid with natural content and the microorganism of improving the polyunsaturated fatty acid of content through the genetic engineering design with demonstration.Described microorganism comprises bacterium and cyanobacteria.For example, method of the present invention can be used for extracting and/or stable polyunsaturated fatty acid (comprising parinaric acid, DHA, eicosapentaenoic acid, gamma-Linolenic acid, arachidonic acid, dihomo-gamma-linolenic acid, clupanodonic acid and parinaric acid) from microorganism of for example making with the composition and the method for following patent and patent application and/or recombinant microorganism (comprising for example Escherichia, cyanobacteria, Bacillus acidi lactici and hay bacillus): US 6,677,145; 6,635,451; 6,566,583; 6,432,684; 5,972,664; 5,614,393 and 5,552,306 and WO 02/26946, and u.s. patent application serial number 20040078845; 20030180898; 20030177508; 20030163845; 20030157144; 20030104596; 20030082754; 20020138874; 20020108147 and 20010046691 (this list of references is formerly incorporated this paper by reference into).

In addition, can from algae, extract fluid composition.The algae that therefrom can isolate polyunsaturated fatty acid comprises the algae of the polyunsaturated fatty acid with natural content and the algae of improving the polyunsaturated fatty acid of content through the genetic engineering design with demonstration.The example of algae with polyunsaturated fatty acid of natural content comprises Phaeodactylum tricornutum (Phaeodactylum tricornutum), latent dinoflagellate (Crypthecodinium cohnii), Ba Fuzao (Pavlova), Isochrysis galbana (lsochrysisgalbana) and thraustochytriale (Thraustochytrium).For example, method of the present invention can be used for extracting and/or stable polyunsaturated fatty acid (comprising parinaric acid, DHA, eicosapentaenoic acid, gamma-Linolenic acid, arachidonic acid, dihomo-gamma-linolenic acid, clupanodonic acid and parinaric acid) from algae of for example making with the composition and the method for following patent and patent application and/or recombinant algae: US 6,727,373; 6,566,583; 6,255,505; 6,136,574; 5,972,664; 5,968,809; 5,547,699 and 5,407,957, and u.s. patent application serial number 20040168648; 20030180898; 20030177508; 20030163845; 20030134400 and 20010046691 (this list of references is formerly incorporated this paper by reference into).

The stabilisation of C. high PUFA seed oil

In the oxidation stability that strengthens the fluid composition that does not add stable compound, fluid composition also can comprise stabilizing agent.Usually in fluid composition, add stabilizing agent to prolong initiating stage and to postpone the beginning of build phase.Compare with the propagation of the oil that does not add stabilizing agent, stabilizing agent can make propagation delay about 15 times or higher mutually.The characteristic that depends on specified stabiliser, these compounds can have different binding modes.Some stabilizing agent chelated minerals or interact with the triglyceride of oil and improve other catalytic specie of the oxidation rate of oil.Other stabilizing agent work as antioxidant molecule and with the radical reaction that the fatty acid oxidation of triglyceride can be become peroxide (conversely, other aliphatic acid of its oxidation, described in detail) as top I.A. part.

Exemplary stabilizing agent can comprise 2,4,5-trihydroxy butyrophenone, 2, the 6-DI-tert-butylphenol compounds, 3, the 4-dihydroxy-benzoic acid, 3-t-Butyl-4-hydroxyanisole, 4-methylol-2, the 6-DI-tert-butylphenol compounds, 6-ethyoxyl-1,2-dihydro-2,2, the 4-trimethylquinoline, anoxomer antioxidant (anoxomer), ascorbic acid, ascorbyl palmitate, ascorbyl stearate, β-A Piao-8 '-carotenic acid, beta carotene (β-Caraotent), butylated hydroxyanisol (BHA), Yoshinox BHT (BHT), caffeic acid, Calcium Ascorbate, calcium disodium edathamil, canthaxanthin, carnosol, carvacrol, catalase, the gallic acid cetyl, chlorogenic acid, citric acid, Flos Caryophylli extract, coffee bean extract, acetic acid D-alpha-tocopherol, dilauryl thiodipropionate, disodium citrate, the EDTA disodium, the DL-alpha-tocopherol, acetic acid DL-alpha-tocopherol, lauryl gallate, lauryl gallate, the D-alpha-tocopherol, ethylenediamine tetra-acetic acid, arabo-ascorbic acid, aesculetin (Esculetin), aesculin (Esculin), ethoxyquinoline, progallin A, ethyl maltol (ethylmatol), eucalyptus extracts, forulic acid, flavonoids (is characterized as: carbon backbone chain such as C6-C3-C6, two aromatic rings generally connect by three carbon aliphatic chains, and its common condensation forms pyrans or less insight seldom forms furan nucleus), flavones is (as apiolin, Chrysin, cyanidenon), flavonols (datiscetin for example, Nyricetin, Daemfero), flavanones, chalcone, fraxetin, fumaric acid, Radix Gentianae extract, gluconic acid, glucose oxidase, P-hydroxybenzoic acid heptyl ester (heptylparaben), hesperetin, hydroxycinnamic acid (Hydroxycinammic acid), the hydroxyl glutaric acid, hydroxyl tyrosol (Hydroxytryrosol), the citric acid isopropyl ester, lecithin, the lemon juice solid, lemon juice, L-tartaric acid, lutein, lycopene, malic acid, maltol, gallicin, methyl p-hydroxybenzoate (methylparaben), morin, the N-hydroxy succinic acid, NDGA, octyl gallate, the p-coumaric acid, phosphatid ylcholine, phosphoric acid, the p-hydroxybenzoic acid, phytic acid (inositol hexaphosphate), allspice is got thing, potassium bisulfite, potassium lactate, potassium metabisulfite, anhydrous sodium potassium tartrate tetrahydrate, n-propyl gallate, pyrophosphate (ester), Quercetin, the rice bran extract, Rosmarinus officinalis extract (RE), Rosmarinic acid, the sagebruss extract, sesamol, sinapic acid, sodium ascorbate, sodium ascorbate, sodium isoascorbate, sodium isoascorbate, sodium hypohosphate, sodium hypohosphate, sodium pyrosulfite, sodium sulfite, the sodium thiosulfate pentahydrate, sodium phosphate trimer (sodium tryphophate), bean powder, butanedioic acid, sucrose, syringic acid, tartaric acid, tertiary butylated hydroquinone (TBHQ), thymol, tocopherol, D-, tocotrienols, trans-resveratrol, tyrosol, vanillic acid, wheat germ oil, zeaxanthin, α-terpineol and its combination.

A series of researchs (referring to embodiment 1-3) have been finished to be identified for the primary stabilizing agent and the combination of stabilizers of fluid composition of the present invention.These stabilizing agents can be selected from citric acid (CA), ascorbyl palmitate (AP), tertiary butylated hydroquinone (TBHQ), n-propyl gallate (PG) and combination thereof.In multiple embodiments, the stabilizing agent in the oil is CA, TBHQ and combination thereof.In a plurality of alternative embodiment, the stabilizing agent in the oil is AP, PG and combination thereof.In other embodiment preferred, the stabilizing agent in the oil is

Citric acid with about 1ppm to about 100ppm, preferably approximately 20ppm is to about 80ppm, more preferably approximately 40ppm joins in the fluid composition to the about concentration of 60ppm.Ascorbyl palmitate with about 50ppm to about 1000ppm, preferably approximately 100ppm is to about 750ppm, more preferably approximately 400ppm joins in the fluid composition to the about concentration of 600ppm.TBHQ with about 10ppm to about 500ppm, preferably approximately 50ppm is to about 200ppm, more preferably approximately 100ppm joins in the fluid composition to the about concentration of 140ppm.N-propyl gallate with about 10ppm to about 120ppm, preferably approximately 50ppm is to about 120ppm, more preferably approximately 100ppm joins in the fluid composition to the about concentration of 120ppm.The combination of two or more these stabilizing agents will have as above each stabilizing agent of scope.

Study in some of seeds at these, used the accelerated ageing method that adopts a kind of novel thin film IR method.This method of determining the oxidability of oil is included in preparation fluid composition under the inert environments; Described fluid composition layer is placed on the infrared ray plate to form treated infrared ray plate; Treated infrared ray plate is placed on reaches time enough in the inert environments so that this layer has homogeneous thickness in fact; The infrared ray plate that will have the uniform in fact layer of thickness is exposed in the air; And the infrared spectrum of regularly gathering described fluid composition.The particular aspects of this method is described among the embodiment 3 in further detail.In the multiple embodiments of this method, between the collection infrared spectrum, will have the uniform in fact infrared ray plate of thick layer and be stored in about 25 ℃ to about 80 ℃, preferred about 50 ℃ to about 70 ℃ even more preferably from about 55 ℃ to about 65 ℃.Aspect this method other, about 12 hours to about 36 hours at interval, preferred about 24 hours collection infrared spectrums.

Another aspect of the present invention is the method that reduces oils anisidine value (AV).Anisidine value is to be used for successfully the easy oxygenated oil that the synthetic food product has high unsaturated content to make the maximized important parameter of its oil-proofness.Reduce AV greater than the new method of the AV of 1 refining, bleaching, taste removal oil (RBD oil) open and be described in down in further detail and embodiment 4 in.Usually, method comprises with the AV depressant handling oil composition that can combine with aldehyde in the fluid composition and/or ketone, and physical separation AV depressant and fluid composition are to remove aldehyde and/or ketone and the reduction AV that combines with the AV depressant from fluid composition.The AV depressant comprise attached to can with the amine on the holder of described fluid composition physical separation.

This method that reduces AV in the RBD oil has adopted when peroxide and hydroperoxides decomposition the unique function of non-volatile aldehyde and ketone in the RBD oil.Particularly, non-volatile aldehyde and ketone form substituted imine (substituted imine is called schiff bases sometimes) by condensation reaction and amine reaction.By amine is connected can with the holder of fluid composition physical separation on aldehyde and ketone can be removed from fluid composition.In multiple embodiments, this holder is insoluble holder or macroscopical holder (macroscopicsupport).In a single day reaction is finished, non-volatile aldehyde and ketone (this moment is with the form of substituted imine) can be by filtering physical separation from oil, because they are connected on the insoluble holder.

Said method can be used for from multiple oil, as removing aldehyde and ketone in vegetable oil, fish oil, oil, edible oil, frying oils, coating oil and the combination thereof.

This method is except being applicable to multiple oil, and various kinds of amine and support material also suit to use.For example, amine can be fatty amine or aromatic amine, and preferably, described amine is aromatic amine.Holder can be selected from multiple particulate matter, comprises polystyrene, styrene diethylene benzene copoly mer, polyethylene glycol-styrene-grafted polymer, polyethylene glycol, polyacrylamide, polyacrylamide-PEG copolymer, silica, polysaccharide and its combination.In multiple preferred embodiment, holder comprises polystyrene, particularly the polystyrene resin pearl.

This processing method can any step in the oil refining process adopt.Resin renewable or use after abandon.Preferably, resin is reproduced; This can be by realizing with the outstanding imines of hot acid water hydrolysis.This kind regeneration allows resin drying and can be used for removing how non-volatile aldehyde and ketone.The formation of substituted imine and regeneration of resin can be carried out in packed column or stirred-tank reactor.The organoleptic attribute of D. high PUFA seed oil

Usually, the SDA of containing oil of the present invention has low overall experience.Therefore, another aspect of the present invention be comprise at least about 0.4,1,2,4,6,8,10,12,14,15,16,17,18,19, the fluid composition of 20wt% (based on aliphatic acid or derivatives thereof gross weight in the composition) or higher at least a polyunsaturated fatty acid (having 4 or more a plurality of carbon-to-carbon double bond) or derivatives thereof, composition has and reaches as high as about 2.5 fragrance and always influence branch, and wherein total influence is determined by standard sense organ Evaluation Method.

Another aspect be comprise at least about 0.4,1,2,4,6,8,10,12,14,15,16,17,18,19, the fluid composition of 20wt% (based on aliphatic acid or derivatives thereof gross weight in the composition) or higher at least a polyunsaturated fatty acid (having 4 or more a plurality of carbon-to-carbon double bond) or derivatives thereof, composition has and reaches as high as fragrance/fragrance of about 2.5 and always influence branch, and wherein total influence is determined by standard sense organ Evaluation Method.

Oil of the present invention also has low fish raw meat and/or pond/marine alga smell except having low total influence.Therefore, further the aspect be comprise at least about 0.4,1,2,4,6,8,10,12,14,15,16,17,18,19, the fluid composition of 20wt% (based on aliphatic acid or derivatives thereof gross weight in the composition) or higher polyunsaturated fatty acid (have 4 or more a plurality of carbon-to-carbon double bond and 18 and still less carbon atom) or derivatives thereof, described composition has and reaches as high as about 0.5,1,1.5,2,2.5,3,3.5,4 or 4.5 flavor branch with sweet and sour flavor (fishy aroma score), and flavor wherein with sweet and sour flavor is determined by standard sense organ Evaluation Method.

Another aspect of the present invention be comprise at least about 0.4,1,2,4,6,8,10,12,14,15,16,17,18,19, the fluid composition of 20wt% (based on aliphatic acid or derivatives thereof gross weight in the composition) or higher polyunsaturated fatty acid (have 4 or more a plurality of carbon-to-carbon double bond and 18 and still less carbon atom) or derivatives thereof, composition has the fishiness/fishy smell branch that reaches as high as about mixing of 0.5,1,1.5,2,2.5, and wherein fishiness/the fishy smell of Hun Heing is determined by standard sense organ Evaluation Method.

Another aspect of the present invention is the fluid composition that comprises polyunsaturated fatty acid (having 6 carbon-to-carbon double bonds and 22 carbon atoms) or derivatives thereof that is less than about 1,5,10,12,14,16,18,20,22,24,26,28,30,32,34wt% (based on aliphatic acid or derivatives thereof gross weight in the composition), described composition has and reaches as high as 0.5,1,1.5,2,2.5 fishy smell branch, and wherein fishy smell is determined by standard sense organ Evaluation Method.

In addition, along with the prolongation of time, the quality of fluid composition of the present invention is not significant to be changed.For example, the fluid composition that comprises about at least 0.4,1,2,4,6,8,10,12,14,15,16,17,18,19,20wt% (based on aliphatic acid or derivatives thereof gross weight in the composition) or higher polyunsaturated fatty acid (having 4 or more a plurality of carbon-to-carbon double bond) or derivatives thereof, the oil when comparative assessment begins with store reach about 1,2 or during more a plurality of months same oil fragrance always influence branch difference less than about 0.5 or 1.0.

Another aspect be comprise at least about 0.4,1,2,4,6,8,10,12,14,15,16,17,18,19, the fluid composition of 20wt% (based on aliphatic acid or derivatives thereof gross weight in the composition) or higher at least a polyunsaturated fatty acid (having 4 or more a plurality of carbon-to-carbon double bond) or derivatives thereof, the oil when comparative assessment begins with store reach about 1,2 or during more a plurality of months same oil smell/local flavor always influence branch difference less than about 0.5 or 1.0.

For in the above-mentioned many aspects each, fluid composition can be stabilized or not be added stabilisation.Above the fluid composition of stabilisation is described in more.II. method for compositions produces oil

Generally speaking, the following step is used to process seed oil: prepare, break and shell, regulate, grind, in flakes or squeeze, extract, come unstuck, make with extra care, bleaching and taste removal.Each will narrate these steps in more detail following.The process in used each step in present commercial the application has been described in this discussion in detail.The described step that will appreciate that those of ordinary skill can make up, use or carry out conversion with different order.

Usually, preliminary step comprises initial cleaning course, other chips that it is removed stone, earth, branch, larva, insect, metal fragment and gathers in the crops and assemble between the storage life at seed.Above-mentioned foreign substance can influence the quality of final seed oil by the compound that comprises its chemical stability of negative effect.Preferably, use chlorophyll content reduces and free fatty acid content reduces maturation, seed does not break.

After preliminary step, seed is broken and shell.Breaking and shell can be with accomplished in many ways known in the affiliated field.For example, can seed be broken and shell with seed disruptor (seed cracker), it mechanically makes seed break and sloughs shell and directly the seed meat of the inside is exposed in the air.After breaking, can shell and seed meat be separated by hulling machine.On the one hand, because the density variation between shell and the seed, hulling machine can make shell separate with seed meat; Shell is so fine and close unlike seed meat.For example, suction can make shell and the seed meat that breaks separate.Shelling can reduce crude fiber content, increases the protein concentration of the seed meat that is extracted simultaneously.Randomly, after shelling, can be with the shell screening to reclaim the fines that generates during seed breaks.After the recovery, this fines can be added back in the seed meat before regulating.

In case make seed break, the oxygen exposure of seed meat is minimized, this will reduce oily oxidation and improve oil quality.In addition, it will be understood by those skilled in the art that minimizing of oxygen exposure can generation independently in each described subsequently oily seed procedure of processing.

In case seed broken and shell, they are regulated so that seed meat limbers up in further first being processed.In addition, described adjusting makes oil body split.By obtain in this in stage soft seed meat make with regard in flakes, grind or other grinding techniques with regard to further processing easier.Usually, make seed meat remove or add wet the branch to reach the 6-10wt% moisture content.If remove the branch that dries, this process is called baking, if add wet the branch, then this process is called boiling (cooking).Usually, with steam seed meat is heated to 40-90 ℃, this steam is drying or moistening according to the adjusting direction of the moisture content of this seed meat.In some cases, make under the minimized condition of oxygen exposure or for the high seed of PUFA content, carrying out regulating step at a lower temperature.

In case make seed meat through overregulating, they can be ground to form required granularity or in blocks to required surface area.In some cases, in flakes or grind making under the minimized condition of oxygen exposure and carry out.Carry out in flakes or grind increasing the surface area of seed meat, and make that equally oil body splits, promote more effective extraction thus.Many grinding techniques be suit and also be well known in the art.Consideration when selecting Ginding process and grinding the granularity of seed decide on the oil content of this seed and required seed meat or the extraction efficiency of seed, still is not limited thereto.When making seed meat in blocks, the about 0.5mm of the about usually 0.1-of lamellar body is thick; About 0.1-is about, and 0.35mm is thick; About 0.3-is about, and 0.5mm is thick; The about 0.4mm of perhaps about 0.2-is thick.

Randomly, after grinding seed meat, they can be squeezed.Usually, when the oil content of seed meat during greater than about 30wt% of this seed, squeezing seed meat.Yet, can squeeze seed with higher or lower oil content.Can for example in hydraulic press or mechanical screws, squeeze seed meat.Usually, after the working substance input, seed meat is heated to less than about 55 ℃.When squeezing, make the oil in the seed meat be pressed through screen cloth, collect and filter.Oil through collecting is oil expression just.To be called oil cake from the seed meat after the squeezing; This oil cake oil-containing and can carry out solvent extraction.

Grind, after the in blocks or optional squeezing, can be fuel-displaced by seed meat or oil cake being contacted with solvent therefrom extract.Preferably, in extraction step, n-hexane or isohexane are used as solvent.Usually, make solvent with the degassing before oil contacts.Can extract with several different methods as known in the art.For example, extraction can be intermittence or continuous technology, is continuous counter-current process ideally.In continuous counter-current process, solvent contacts with seed meat, and oily leaching is gone in this solvent, and more and more denseer miscella (being solvent-oil) is provided, and marc (marc) (being solvent-solid) is contacted with the miscella that reduces concentration.After extraction, remove from miscella with methods known in the art and to desolvate.For example, distillation, rotary evaporation or climbing film evaporator and steam stripper can be used for except that desolvating.After solvent is removed,, it can be heated under about 95 ℃ and about 60mmHg if raw oil still contains residual solvent.

But above-mentioned raw oil through processing comprises phosphatide hydration and can not hydration.Therefore, by adding water and be heated to about 40～about 75 ℃ of about 5-60 minutes, but this raw oil is come unstuck to remove the phosphatide of hydration according to phospholipid concentration.Randomly, but can add phosphoric acid and/or citric acid so that phosphatide that can not hydration changes into the phosphatide of hydration.Phosphoric acid and citric acid form metal complex, and this can reduce and the concentration of the metal ion of phospholipids incorporate (phosphatide of metal complex be can not hydration), but thereby phosphatide that can not hydration change into the phosphatide of hydration.Randomly, after water heats, can make this raw oil and aqueous mixtures centrifugation so that oil and water are separated, but then remove the water layer that contains hydration phosphatide.Usually, if in the step of coming unstuck, add phosphoric acid and/or citric acid, use the about 5wt% of about 1wt%-, the preferably about 2wt% of about 1wt%-, the about 2wt% of 1.5wt%-more preferably from about.Randomly carry out this procedure of processing by before making water and phosphoric acid and oil contact, outgasing.

In addition, raw oil comprises free fatty (FFAs), and it can be removed by chemistry (as caustic alkali) purification step.When FFAs and alkaline matter (as caustic alkali) reaction, they form can extract the soap class that enters in the aqueous solution.Thereby, raw oil is heated to about 75 ℃ and under agitation add NaOH and reacted about 10-45 minute of about 40-.Then stop to stir, yet continue heating, remove oil that water layer and processing be neutralized to remove the soap class.By washing this oil till water layer has neutral pH, perhaps, described oil is handled by handling the described oil that is neutralized with silica or ion exchange material.Drying should oil under about 95 ℃ and about 10mmHg.In some cases, caustic solution is being outgased to it before contacting with oil.

As selection, can remove FFAs by physics is refining, rather than from oil, remove FFAs by chemical refining.For example, can refining this oil of physics during taste removal.Carry out physics when refining,, from oil, remove FFAs by under low pressure and relative higher temperature, carrying out vacuum distillation.Usually, FFAs has the molecular weight lower than triglyceride, thereby FFAs has lower boiling point usually, and based on this boiling point difference with by means of as azeotropic mixture or nitrogen or the steam stripping of carrier gas to purge out volatile matter from deodorizer, it separated from triglyceride.

Usually, when carrying out the refining rather than chemical refining of physics, change oily processing conditions to reach similar trimmed size.For example, when using acidic aqueous solution in the step of coming unstuck and since higher concentration can not hydration phosphatide (itself otherwise can in the chemical refining step, remove), the acid that may need higher concentration is (for example, until the concentration that exceeds about 100%, preferably exceed the concentration of about 50%-about 100%).In addition, use more substantial bleaching material (for example,, preferably exceeding the amount of about 50-about 100%) until the amount that exceeds about 100%.

Before bleaching, citric acid (50wt% solution) can be joined through come unstuck oily and/or in the oil of chemical refining with the concentration of the about 5wt% of about 0.01wt%-.Can under about 35 ℃-Yue 65 ℃ temperature and the pressure of the about 760mmHg of about 1mmHg-, heat the about 5-of this mixture about 60 minutes then.

Carry out the residual soap class of adsorption treatment (as bleaching) to oil and/or through the oil of chemical refining to remove peroxide, oxidation product, phosphatide, keratinoid, chlorphyloid, coloured object (color body), metal and in alkali refining step or other procedure of processings, to form through coming unstuck.Bleaching is handled and to be comprised with the oil through coming unstuck or through the oil of chemical refining and heat under the vacuum of about 0.1mmHg～about 200mmHg and add bleaching material (for example neutral soil (so-called natural clay or bleaching earth), acid activation soil, activated clay and silicate) and the filter aid that is suitable for removing the above-mentioned species of mentioning, this mixture is heated to thereupon about 75-125 ℃ and with bleaching material with contact about 5-50 minute through come unstuck oily and/or through the oil of chemical refining.Bleaching material before contacting the refining oil of described warp, it is outgased.The amount of used bleaching material is the about 3wt% of about 0.25wt%-, the about 1.5wt% of preferably about 0.25wt%-, and the about 1wt% of 0.5wt%-more preferably from about.After the heating, to bleach oil or refining, bleach oil filters and taste removal.

Bleach oil or refining, bleach oil are carried out taste removal to remove compound and the residual free fatty with overpowering odor and local flavor.Can further alleviate the color of oil by thermal bleaching at elevated temperatures.Can carry out taste removal by multiple technologies, comprise intermittently and continuous taste removal unit such as intermittence stirred-tank reactor, falling film evaporator, luwa evaporator, packed column odor eliminator, column plate type odor eliminator and loop reactor.Usually, preferred continuous taste removal technology.Usually, taste removal condition is carried out under about 160-about 270 ℃ and the about 1.4kPa of about 0.002-.For continuous processing, particularly has the continuous odor eliminator that is used for the continuous column plate that oil crosses, preferably time of staying of 2 hours at the most under about 170 ℃-Yue 265 ℃ temperature; About at the most 30 minutes time of staying under about 240 ℃-Yue 250 ℃ temperature.The taste removal condition can use carrier gas to remove volatile compound (for example steam, nitrogen, argon gas or can not reduce any other gas of the stability or the quality of described oil).

In addition, when adopting the refining rather than chemical refining of physics, in the taste removal step, remove more substantial FFAs, and change the odor eliminator condition to promote removing of free fatty.For example, temperature is improved about 25 ℃; Can be to oily taste removal under about 165 ℃-Yue 300 ℃ temperature.Especially, can be to oily taste removal under the about 250 ℃-temperature of Yue 280 ℃ or about 175 ℃-Yue 250 ℃.In addition, the retention time of described oil in odor eliminator increases until about 100%.For example, retention time can be less than about 1,5,10,30,60,90,100,110,120,130,150,180,210 or 240 minute.In addition, odor eliminator pressure can be reduced to less than about 3 * 10 ^-4, 1 * 10 ^-3, 5 * 10 ^-3, 0.01,0.02,0.03,0.04,0.05,0.06,0.07,0.08,0.09 or 0.1kPa.The taste removal step produces (RBD) oil through refining, bleaching and taste removal.

Randomly, by partial hydrogenation and/or by adding removing or degrading of stabilizing agent or the microcomponent by reducing to help to keep oil-proofness and quality to greatest extent, can stablize RBD oil.Thereby partial hydrogenation is by the double key number order in the aliphatic acid that reduces described oil and comprise and reduce this oily chemical reactivity and make oil stable.Yet partial hydrogenation can increase the concentration of undesirable trans-fatty acid.

Stabilizing agent generally is used for intercepting the free radical that oxidizing process forms.The intercepting that free radical is stabilized agent slows down the oxidation of oil, and this free radical becomes more stable free radical or rearrangement becomes stable molecule, and the reason that oxidation slows down is that the concentration of the reactive free radical of height of oxidable more fattiness acid unit reduces.

For each above-mentioned steps in the part ii, randomly in each step, the exposure to oxygen is minimized, exposure to heat is minimized, exposure to UV light is minimized and randomly first being processed, during or in seed meat or seed oil, add stabilizing agent afterwards.Be used for preparing the U.S. Patent application No.____ that is entitled as " preparation method of fluid composition " that these and other process modification of oil of the present invention submit in attorney docket MTC 6921.201 (38-21 (53354C)), on November 4th, 2005 and obtain describing and illustrating, it all incorporates this paper by reference into.

III. the processing of fluid composition and storage

Usually, when the oil in reserve composition, the further oxidation that reduces aliphatic acid to greatest extent is favourable.A kind of oxidant is a singlet oxygen, and it produces by light and sensitising agent.Singlet oxygen is with the speed response greater than the order of magnitude of triplet oxygen.Therefore, a kind of method that reduces further oxidation to greatest extent is that described oil is stored in dark place or the opaque in fact container, holds them under the moderate moisture and preferably maintenance in the presence of inert gas.Preferably, described oil has stability features, itself and condition of storage and/or stabilizing agent coupling, and will suppress the reverse of oily local flavor, smell, color etc.

More than have favourable storage stability feature usually at the fluid composition described in the part i.For example, in one embodiment, kept the method for the storage stability of oil to be included under the about 45 ℃ temperature of about 4-between transportation or storage life the oil described in the part i is stored in the container at least 1 month, wherein said oil has the anisidine value less than 3 after storage.In another embodiment, kept the method for the storage stability of oil to be included under the about 45 ℃ temperature of about 4-between transportation or storage life oil of the present invention is stored in the container at least 1 month, wherein the absolute change of the anisidine value of described oil is not more than about 0.05,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1.0,2.0,3.0,4.0,5.0,6.0,7.0,8.0,9.0,10,11,12,13,14,15,16,17,18,19 or 20 between the storage life.In addition, oil can be stored in the atmosphere of anaerobic or oxygen minimizing.Preferably, described oil approximately can stored under the room temperature; Preferably, described oil can be stored about 2,3,4,5,6,7,8,9,10,11 or 12 months or longer under about room temperature.Alternatively, described oil can be stored at least 1 month under refrigeration; In addition, described oil can be stored about 2,3,4,5,6,7,8,9,10,11 or 12 months or longer under refrigeration.In another embodiment, described oil sources is from the source except marine oil, for example fish, algae or krill.In another embodiment of this section method, described oil sources is from the vegetable oil except blackcurrant oil, borage oil, blueweed oil, evening primrose oil, gooseberry oil, cannabis oil or red gallons of oil.

More than the method described in the III part may further include storing before or during in described oil, add stabilizing agent.Described stabilizing agent can comprise at least a complexing agent or at least a antioxidant.In a kind of exemplary, described stabilizing agent comprises citric acid, TBHQ, ascorbyl palmitate, n-propyl gallate or its derivative or combination.

IV. food

Can prepare the food that comprises the described any fluid composition of top first.Especially, food compositions can comprise and comprise following food or food analog: contain spray-drying or freeze-dried food particle, extruded food, meat products, meat analog, cereal product, snacks, baked goods, healthy food, fried food, dairy products, cheese analogue, dairy products analog, pet food, animal feed or agriculture feed.In another embodiment, described food is beverage; This beverage can be adult nutrient prescription, infant nutrition type prescription, fruit juice, milk beverage, soymilk, sour milk beverage, contain newborn fruit drink (smoothie) or recoverable dried powder such as vegetable fat powder.In addition, this food can be nutritional supplement, coating, margarine, salad flavoring, edible oil, refrigeration Flour product, microwave popcorn, dairy products (as sour milk, cheese, cream cheese, sour cream or mayonnaise), baked goods (as bread, roll, cake, cake, cookies, muffin or biscuit), entree, garnishes, soup, flavoring, oatmeal, cereal, snacks rod, nutrition bar or dessert.

Contain four or be that greater than the advantage of the oil of four two keys their aroma and flavor is gentle with the inventive method preparation.They can also at room temperature store a period of time, and keep taste and organoleptic properties.In addition, they also have the advantage that can refrigerate and still keep gentleness.These oil can also be with the stable method of fish oil as known in the art encapsulation or freezing.After describing the present invention in detail, obviously the modifications and variations in the scope that does not exceed accessory claim definition of the present invention is passable.And, be appreciated that the determinate embodiment of embodiment right and wrong that the present invention openly provides.

Embodiment

Embodiment 1: the accelerated ageing of oil

Every kind of stabiliser solution of preparation in propane diols.This solution high-eddy 5 minutes.In the glove-type sack that nitrogen purifies, respectively every kind of an amount of solution is joined in 2.5g (2.77ml) experimental oil in the amber vial with cover of 60cc, form mixture.Then with these mixture high-eddies 1 minute.Part with these mixtures shifts out with plastic suction pipe then, puts into amber vial.

The not spiked sample of pure oil is also as above-mentioned preparation (not adding stabilizing agent).Every kind of stabilizing agent adds with following concentration: citric acid (CA) 50ppm, ascorbyl palmitate (AP) 400ppm, TBHQ (TBHQ) 120ppm.

In then that bottle (containing pure oil and the oil of mixing stabilizing agent) is the unlimited air, fully exchange until the bottle headroom.Bottle is covered again, in water-bath, be heated to 55 ℃ then.Take sample away, measure peroxide value with the different time intervals.Usually, sample is deposited 10 days wearing out at the aging sample of depositing under 55 ℃ a day that is equivalent under room temperature (～22-25 ℃).Have 20 weight %SDA and be entitled as " preparation method of fluid composition " who submitted on November 4th, 2005, the experimental oil of acting on behalf of the process conditions preparation of describing among the embodiment 45 and 46 of U.S. Patent application series No.____ of mark no.MTC6921.201 (38-21 (53354C)) wears out with above-mentioned agreement.The result of this ageing research shows in the chart of Fig. 1.Evaluation has three kinds of oil (CA, AP and TBHQ) of independent additive and has two kinds of oil (CA+AP and CA+TBHQ) of binary additive.Two days later, the SDA oil with citric acid changes to propagation stage from initiating stage (IP).Fig. 1 shows the figure of AV to the time.The figure illustrates with respect to the oil that has added CA, the oil that has added ascorbyl palmitate has long IP (about 8 days), add TBHQ oil have long IP (10 days).The oil that has added TBHQ is the best Dan Pin that adds this specific oil of stabilizing agent.

Fig. 1 has also shown the oxidation that adds AP and CA and add the oil of TBHQ and CA.The IP ratio that adds the oil demonstration of AP and CA only adds the oil weak point of AP.The IP that adds the oil of TBHQ and CA is the longest in the multiple oil in this test.

Embodiment 2: the ageing research under 55 ℃ and 25 ℃

The oil that this research comprises is: 20%SDA laboratory sample (TA), under laboratory scale and pilot scale, produce, blank (null) is isopleth (isoline), therefore, be SDA negative (on November 4th, 2005 disclosed being entitled as " preparation method of fluid composition ", act on behalf of the process conditions preparation described among the embodiment 45 and 46 of U.S. Patent application series No.____ of mark no.MTC6921.201 (38-21 (53354C))) and contrast soya-bean oil 1.In addition, 20%SDA oil is mixed with contrast soya-bean oil 1 or blank oil, obtain 4%SDA oil and mix.Based on the PV that under 55 ℃, begins and AV be to the relative grade of the stability of these oil of time with minimum stabilize oil: TA-Lab＜TA-(PS)＜TA-PS and CA＜TA-Lab and CA＜＜mix 4% (TA-PS blank) and CA＜mixed for 4% (TA-PS adds contrast soya-bean oil 1) and CA＜blank＜contrast soya-bean oil 1 (referring to Fig. 2).The relative grade of stability is by relatively PV or AV value and 10 times of intersecting are measured.Usually, this is from beginning to the beginning of propagation stage.Under 25 ℃ (referring to Fig. 3), these five kinds of oil have the transformation (passing through AV) from the initiating stage to the propagation stage, with respect to the relative position of the data that under 55 ℃, obtain, and the similitude on their demonstrations are significantly qualitative and quantitative.

The research of another accelerated ageing under 55 ℃ uses 20%SDA to add the laboratory sample of citric acid (50ppm), ascorbyl palmitate (400ppm) and TBHQ (120ppm).The mixture that contains all three kinds of stabilizing agents of this tittle in sample.In addition, also comprise commercial fish oil product such as fish oil 3 (TBHQ and vitamin E are arranged) and fish oil 4 (ascorbyl palmitate and microorganism E are arranged) as adjusting control agent.In order further to estimate these commercial fish oil products, they are mixed with contrast soya-bean oil 1, produce the EPA+DHA bioequivalence of relative SDA oil.Three SDA molecules of every consumption produce an EPA molecule.Therefore, if the biological effect of supposition EPA, DPA and DHA is identical,, must consume SDA greater than three times of EPA in order to obtain the EPA of equivalent.Since every kind of fish oil and every kind of oil have been diluted to 6.67 weight % with soya-bean oil solution with the SDA oil of 20 weight % directly relatively, thereby measure the total amount of Ω tri-fatty.Fig. 4 has shown that the AV of three kinds of oil is to time relation.Initial AV result shows 20%SDA oil ratio fish oil 3 and the fish oil 4 with the stabilized with mixture of AP, TBHQ and AP, TBHQ and CA, comprises their bioequivalence dilution, has longer initiating stage.

Relative %	Contrast soya-bean oil 1	Fish oil 3	Fish oil 4
Relative %	Contrast soya-bean oil 1	Fish oil 3	Fish oil 4	C12:0
C14:0		9.03	7.29	C12:0
C14:0		9.03	7.29	C16:0	11.01	20.47	17.73
C16:1	0	12.38	6.97	C16:0	11.01	20.47	17.73
C16:1	0	12.38	6.97	C18:0	3.72	3.93	3.33
C18:1n9	21.04	8.94	10.52	C18:0	3.72	3.93	3.33
C18:1n9	21.04	8.94	10.52	C18:1n7		3.63	2.48
C18:2	55.32	1.64	1.42	C18:1n7		3.63	2.48
C18:2	55.32	1.64	1.42	C18:3n6
C18:3n3	6.43	1.76	1.2	C18:3n6

Relative %	Contrast soya-bean oil 1	Fish oil 3	Fish oil 4
Relative %	Contrast soya-bean oil 1	Fish oil 3	Fish oil 4	C18:4n3		3.05	3.43
C20:0	0.32			C18:4n3		3.05	3.43
C20:0	0.32			C20:1	0.2	1.57
C20:5n3		12.54	13.04	C20:1	0.2	1.57
C20:5n3		12.54	13.04	C22:0	0.36		1.58
C22:5n3		2.57	16.76	C22:0	0.36		1.58
C22:5n3		2.57	16.76	C22:6n3		12.55
C24:0				C22:6n3		12.55

The research of embodiment 3:IR film oxidation

The method of oil accelerated ageing and the assessment of oxidation stability are to adopt at McGill university (J.Am.Oil.Chem.Soc., 2003,80,635-41; J.Am.Oil.Chem.Soc., 2004,81,111-6) disclosed method.Use this method during preparation in air, to protect oil and to guarantee consistent film thickness.Oil film is in that (polytetrafluoroethylene (PTFE) is as Teflon by PTEE film on rectangular cardboard

) upward preparation (being convenient to be installed on the IR spectrometer).Cardboard can be from International Crystal Laboratories, Garfield, and NJ, part number 0006-7363 buys.

The oil formulation that is used for testing prepares under the glove box argon gas.Usually, 0.2-0.5g is placed bottle, sealing is removed from drying box then.Each sample is marked on two infrared ray plates at least, launches on thin paper to avoid pollution.With staple fibre brush (not being camel hair) thick-layer is covered with paint or varnish on marking plate then.Because the Teflon supporting film has the crack, so some oil infiltrate on the support thin paper.For fear of too much air exposure, plate is lain in then on the new thin paper in the chest at once.Chest is moved in the vacuum chamber, find time immediately and fill argon gas.In the dark, this plate case keeps a whole night in vacuum chamber.In the meantime, all too much oil penetrate into the oil film that obtains thickness in the thin paper.

Second day, change infrared spectrometer obtains each plate under 4.1 editions software kit controls of the Omnic of Nicolet infrared spectrum with Nicolet Model 550 Fouriers.Then these plates are vertically placed in 60 ℃ baking box, noted not allowing oil film contact with pollution sources.Can use other temperature, but owing to be rich in PUFA in the oil, the oxygenation efficiency that 60 ℃ temperature causes can make the oxidation curve record under the abundant accuracy of spectrum every day.Usually, measure the infrared spectrum of oil film every day; Carry out 32 scanning, spectral region 400-4000cm ^-1This spectral region than want with use regional wide, using it is to provide a wideer baseline because of it.According to the spectrum that obtains, carry out baseline correction with " baseline correction automatically " function of Omnic software.When oily oxidation, at 3400cm ^-1Produce broad peak; This is to be caused by the absorptance that O-H in the peroxidating base stretches.Also observe the 3011cm relevant with the cis carbon-to-carbon double bond ^-1The decay of the absorptance that stretches of C-H, this is for being confirmed to be useful, but the quantitative extent of oxidation obtains by integration peroxidating peak.

For the amount at peroxidating peak, the thickness of film and CH ₂Be stretching in 2900cm ^-1The peak proportional.Spend the night by plate level is placed on the thin paper, obtain two CH of the oil film between 0.2 and 0.6 usually ₂The absorptance peak of the highest energy at stretching peak.For comparative spectrum on consistent basis, make after the baseline correction and before integration, make the spectrum standardization, be 1.0 thereby make the absorptance at this peak.In case highest energy CH ₂The standardization of stretching peak is to peroxidating peak integration.Be the compensation baseline curvature, whole peak is integration not.The best total of points parameter of data that are used for occurring here and following calibration is that baseline is at 3222-3583cm ^-1Integration and 3251-3573cm ^-1Limit of integration.

The calibration of said method is as follows.The peroxide value standard series is by the Wesson soya-bean oil and the preparation of Wesson soya-bean oil of mixed oxidization in new bottle.The oil of oxidation adds 44mg ferric stearate (II) preparation again by adding 126gWesson soya-bean oil to the 250mL round-bottomed flask.This oil sprays spend the night (16 hours) at 90 ℃ of oil bath air.Oil becomes Huang-brown.The last weight of oil is 128g.Some ferric stearates do not dissolve but adhere to flask, when oil shifts it are removed.Titration test shows that the PV of the oil of oxidation is 680meq/kg, and fresh Wesson soya-bean oil is less than 0.1meq/kg.The mixture of two kinds of oil is used to prepare the calibration criterion of above-mentioned analysis.

This method only is used for definite variation from first sample peroxide value.In this context, find,

Δ PV (meq/kg)=Δ area * 228.4

Wherein Δ PV is the variation of peroxide value, and the Δ area is the variation of peak area, by the Omnic software records.

Said method is used for determining the relative stability of the oil of adding stabilizing agent of the present invention for oxidation, and described stabilizing agent is selected from ascorbyl palmitate (AP), propyl gallate (PG), TBHQ (TBHQ) and composition thereof.In these trials, find that the effect of the oxidation of other stabilizing agents postponement experimental oils does not have the aforementioned stable agent good, perhaps other do not allow to be used for food.Effect that these are relatively poor and the non-stabilizing agent that can be used for food are Carotino

, from Carotino, SDN, BDH (mixture of tocotrienols and carrotene), phenanthrolene, five ethene hexamines (PEH), diethanol amine (DEA), Yoshinox BHT (BHT) and composition thereof.

Studies show that with above-mentioned film IR method the effectiveness of stabilizing agent or combination of stabilizers is in proper order for (AP+PG)＞AP＞PG＞TBHQ～oil is untreated.Some is different for accelerated ageing data in this order and embodiment 1 and 2, is because find that in the ageing research of routine TBHQ is a kind of very effective stabilizing agent.But because the exposure condition of oily film, determining that oxidation that the oxidation of film is compared with bulk oil is compared experiences different mechanism probably.For example, the oxidation of the oil of film oil under 60 ℃ of high temperature is similar, therefore should provide and relevant result like those OSI data class.In order to verify these hypothesis, these oil that add stabilizing agent are carried out OSI research.The OSI method as detailed above, and a method of definite OSI value is AOCS Cd 12b-92.

The OSI value of 20%SDA soya-bean oil that contains stabilizing agent shown in the adding is as shown in the table, wherein most of sample is done two kinds of evaluations.

Seeing from the OSI data, is the same to the OSI data with effectiveness to film IR data in proper order.Added PG and AP the 20%SDA fluid composition film IR data example as shown in Figure 5.

Embodiment 4

AV-reduces resin

Can reduce the viewpoint of AV value in the oil with SDA rapeseed oil (canola oil) the sample checking special resin of AV=5.41.In trace " Wheaton-type " RBF, add 10 gram oil, and with its be connected at device with vacuum ability.Test at every turn and in oil, add 1 gram resin.Resin #1 is the silica gel of 2-(4-tosyl diamine)-ethyl-functionalization, 200-400 order (Aldrich 552593-25g.Resin #2 be 3-aminopropyl-functionalization silica gel (Aldrich36,425-8).Then mixture is outgased in system under vacuum.Then oil is reduced in 110 ℃ of oil baths, mixed 1 hour with stirring rod.With the mixture cooling, filter sent for analysis with 0.2um acrodisc.Therefore repeated test 1 obtains two groups of AV values.

EXP#	RESIN#	AV
EXP#	RESIN#	AV	RBD is in the same old way	Do not have	5.41
1	1	0.69，0.75	RBD is in the same old way	Do not have	5.41
1	1	0.69，0.75	2	2	0.65

[0136]Embodiment 5

The purpose of fragrance research (sense organ research 1) is the fragrance of the soya-bean oil of the qualitative SDA of being rich in.As the reference framework, the soya-bean oil that processing contrast soya-bean oil (no seed oil) and several commerce can get and the fragrance of fish oil that contains Ω-3 and algal oil also all will be tested.

The purpose of fragrance/taste/mouthfeel research (sense organ research 2) is fragrance, taste and the mouthfeel of the soya-bean oil of the qualitative SDA of being rich in.As the reference scheme, the soya-bean oil that processing contrast soya-bean oil (no seed oil) and several commerce can get and fragrance, taste, the mouthfeel of fish oil that contains Ω-3 and algal oil also all will be tested.

Use Spctrum

The standard feeling evaluation is estimated following experimental oil, contrast oil and comparison oil.Experimental oil 1 is 15% to be rich in the RBD soya-bean oil (LGNBP739406615BJ9) of SDA; Experimental oil 2 is 15% to be rich in the RBD soya-bean oil (LLNBP739406915CK1) of SDA; Experimental oil 3 is 20% to be rich in the RBD soya-bean oil (LMNBP739406920AQ6) of SDA; Experimental oil 4 is 20% to be rich in the RBD soya-bean oil (LHNBP739406920BJ7) of SDA; Experimental oil 5 is 20% to be rich in the RBD soya-bean oil (LEGLP050115725SN5) of SDA; Experimental oil 6 is 20% to be rich in the RBD soya-bean oil (LTAGT050115759SN3) of SDA; Experimental oil 7 is an isopleth contrast RBD soya-bean oil (LMAGT050115757SU0); Experimental oil 8 is 15% to be rich in the RBD soya-bean oil (LC739046615BX1) of SDA; Experimental oil 9 is 21% to be rich in the RBD soya-bean oil (LZAGT050115759SJ9) of SDA; Experimental oil 10 is to contain the RBD soya-bean oil (LHAGT050716475SO3) that 17% of citric acid is rich in SDA; Experimental oil 11 is to contain the RBD soya-bean oil (LLAGT050716477SY1) that 17% of citric acid is rich in SDA; Experimental oil 12 is to contain the RBD soya-bean oil (LEAGT050716481SU5) that 17% of citric acid is rich in SDA.Contrast oil 1 is from storing blank RBD soya-bean oil (LGAGT050115757SU9); Contrast oil 2 is from storing the blank RBD soya-bean oil (LNAGT050716474SW4) that contains citric acid; Contrast oil 3 is from storing the blank RBD soya-bean oil (LMAGT050816495SL7) that contains citric acid.

For sense organ research 1, the fluid composition that is used for comparison is as described in the following table.Soya-bean oil 1 is the soya-bean oil of commodity production; Soya-bean oil 2 is the soya-bean oil of another kind of commodity production; Soya-bean oil 3 is the soya-bean oil of another kind of commodity production; Fish oil 1 is the fish oil of commodity production; Linseed oil 1 is the linseed oil of commodity production; Algal oil 1 is the algal oil of commodity production; Algal oil 2 is algal oils of another kind of commodity production.

Relative %	Fish oil	1	Linseed oil 1	Algal oil 1	Algal oil 2	Soya-bean oil 3	Soya-bean oil 2	Soya-bean oil 1
Relative %	Fish oil	1	Linseed oil 1	Algal oil 1	Algal oil 2	Soya-bean oil 3	Soya-bean oil 2	Soya-bean oil 1	C12:0	0	0	0.58	6.38	0	0
C14:0	7.43	0	12.62	17.74	0.09	0	0.08		C12:0	0	0	0.58	6.38	0	0
C14:0	7.43	0	12.62	17.74	0.09	0	0.08	C16:0	17.41	0	24.21	13.69	10.48	10.68	10.41
C16:1	9.18	5.03	0.83	2.55	0.09	0	0.09	C16:0	17.41	0	24.21	13.69	10.48	10.68	10.41
C16:1	9.18	5.03	0.83	2.55	0.09	0	0.09	C18:0	3.30	3.77	0.72	0.53	4.43	3.67	4.17
C18:1n9	10.24	21.72	0.51	17.18	23.58	22.48	22.95	C18:0	3.30	3.77	0.72	0.53	4.43	3.67	4.17

Relative %	Fish oil	1	Linseed oil 1	Algal oil 1	Algal oil 2	Soya-bean oil 3	Soya-bean oil 2	Soya-bean oil 1
Relative %	Fish oil	1	Linseed oil 1	Algal oil 1	Algal oil 2	Soya-bean oil 3	Soya-bean oil 2	Soya-bean oil 1	C18:1n7	3.10	0	0	0	0	0	1.15
C18:2	1.79	17.07	0.85	0.88	51.61	53.99	52.30		C18:1n7	3.10	0	0	0	0	0	1.15
C18:2	1.79	17.07	0.85	0.88	51.61	53.99	52.30	C18:3n6	0.43	0	0	0	0	0	0.00
C18:3n3	1.06	51.31	0.18	0	5.07	8.68	7.39	C18:3n6	0.43	0	0	0	0	0	0.00
C18:3n3	1.06	51.31	0.18	0	5.07	8.68	7.39	C18:4n3	3.36	0	0.34	0	0	0	0.00
C20:0	0.00	0.15	0.17	0.11	0.4	0.26	0.31	C18:4n3	3.36	0	0.34	0	0	0	0.00
C20:0	0.00	0.15	0.17	0.11	0.4	0.26	0.31	C20:1	2.56	0.22	0	0	0.14	0	0.17

PCT

C20:5n3	17.38	1.3	0
C20:5n3	17.38	1.3	0		C22:0	0.00	0.13	0.17	0.13	0.29	0.25	0.33
C22:5n3	2.03	0.26	0.31		C22:0	0.00	0.13	0.17	0.13	0.29	0.25	0.33
C22:5n3	2.03	0.26	0.31		C22:6n3	10.05	0	36.0	40.15	0	0
C24:0	0.00	0	0	0.09	C22:6n3	10.05	0	36.0	40.15	0	0

For sense organ research 2, every kind more oily as shown in the table.Relatively oil 1 is the RBD soya-bean oil of commodity production; Relatively oil 2 is the RBD soya-bean oil of commodity production; Relatively oil 3 is the fish oil of commodity production; Relatively oil 5 is the catfish fish oil of commodity production; Relatively oil 6 is the fish oil of commodity production; Relatively oil 7 is algal oils of commodity production; Relatively oil 8 is algal oils of commodity production.

Relative %	Compare oil 1	Compare oil 2	Compare oil 3	Compare oil 5	Compare oil 6	Compare oil 7	Compare oil 8
Relative %	Compare oil 1	Compare oil 2	Compare oil 3	Compare oil 5	Compare oil 6	Compare oil 7	Compare oil 8	C12:0
C14:0			6.21	9.03	6.12	10.04	3.85	C12:0
C14:0			6.21	9.03	6.12	10.04	3.85	C16:0	10.62	11.17	13.09	20.47	12.24	23.27	35.83
C16:1			5.50	12.38	5.01			C16:0	10.62	11.17	13.09	20.47	12.24	23.27	35.83
C16:1			5.50	12.38	5.01			C18:0	4.35	4.06	3.59	3.93	3.31		1.20
C18:1n9	21.51	20.82	6.11	8.94	5.4			C18:0	4.35	4.06	3.59	3.93	3.31		1.20
C18:1n9	21.51	20.82	6.11	8.94	5.4			C18:1n7	1.20	1.18	1.98	3.63	2.02
C18:2	53.91	55.79		1.64	0.83			C18:1n7	1.20	1.18	1.98	3.63	2.02
C18:2	53.91	55.79		1.64	0.83			C18:3n6					4.13
C18:3n3	8.41	6.98		1.76				C18:3n6					4.13
C18:3n3	8.41	6.98		1.76				C18:4n3			4.52	3.05
C20:0								C18:4n3			4.52	3.05
C20:0								C20:1				1.57	1.53
C20:5n3			27.45	12.54	25.61	1.66		C20:1				1.57	1.53
C20:5n3			27.45	12.54	25.61	1.66		C22:0
C22:5n3				2.57	3.95			C22:0
C22:5n3				2.57	3.95			C22:6n3			24.38	12.55	16.66	43.15	46.47

All experimental oils and contrast oil all place the vial amber with cover of 200mL to 1000mL.The nitrogen covering immediately and freezing after preparation of experimental oil and contrast oil.Experimental oil and contrast oil are not opened when storage.Relatively oil obtains from commodity production, stores down or under-20 ℃ of original packagings 5 ℃ of manufacturer's guidance.

Estimate described oil (list of references: Sensory Evaluation Techniques, the third edition with SpectrumTM Descriptive Analysis Method; Meilgaard, Morten; Civille, GailVance.; Carr, B.Thomas; CRC Press LLC, New York, 1999; ISBN 0-8493-0276-5).Test group is by 6-8 the member composition through oil plant evaluation training.Each experiment meeting will be gathered all group members simultaneously.After room temperature raises, estimate with 1/2 to 1 ounce sample.

Each product has all members to estimate simultaneously.The evaluation personnel estimate and discuss total effect and each organoleptic properties of discovering with the prevailing view score of 0 (observation) to 15 (extreme values).The evaluation of total effect and each descriptor is imported Sensory Ballot with Study Director.The fragrance performance comprises but does not limit: the fish raw meat/fishy smell of mixing, fishlike smell, fishy smell, protein/feed, coating flavor, beans flavor fishy smell, fermented flavour, flowery odour, nut flavor, cardboard flavor, new delicate flavour, careless flavor, weedy character, vegetable oil, cereal core and phenol/plastics.Flavor properties comprises but is not limited with: fish raw meat/raw meat mixing flavor, fishlike smell, fishy smell, protein/feed, coating flavor, big beany flavor, fermentation, flowery odour, nut flavor, cardboard flavor, new delicate flavour, careless flavor, weedy character, vegetable oil, cereal flavor, albumin, seed/nut/pumpkin and phenol/plastics.Primary taste carries out performance evaluation in 0 to 15 scope: sweet taste, tart flavour, saline taste and bitter taste.The chemical sensation factor is carried out performance evaluation in 0 to 15 scope: astringent taste, the smell of burning, chemical sensation.Mouthfeel is carried out performance evaluation in 0 to 15 scope: viscosity.Not do not estimate but observe and described pleasant impression.

Experimental oil 10 to 12, and contrast oil 2 and 3 is green oils; The RBD level is processed in their before beginning one's study two months.These oil were tested when first experimental stage of research.As the part of refrigerated stability experiment, experimental oil 8 and 9 is estimated.Before research begins about 1 year, experimental oil 8 is handled, stored down until the research beginning at-80 ℃.This oil was tested when first experimental stage of research.Before research begins about 6 months, experimental oil 9 and contrast oil 1 are handled, stored down at-20 ℃.This oil was tested when first experimental stage of research.There are not other samples to test as the part of the stable experiment of refrigeration.

The stability experiment sample that quickens is kept under 55 ℃ in the incubator of Controllable Temperature (sense organ research 1).The storage stability laboratory sample is kept at (sense organ research 2) in the incubator of Controllable Temperature under 15 ℃.

Following table has shown the data of only fragrance experiment (sense organ research 1).

Following table shows fragrance/taste/mouthfeel experiment (sense organ research 2).

Embodiment 6: the mayonnaise preparation

Soya-bean oil (3720g) and Ω-3 vegetable oil (1800g) are mixed, obtain following fluid composition:

Free fatty, % 0.35

Peroxide value 0.09

Pigment 1.3Y 0.0R

Chlorophyll, ppm 0.00

Anisidine value 0.20

Aliphatic acid is formed, %

C14 (myristic acid) 0.04

C16 (palmitic acid) 11.15

C16:1n7 (palmitoleic acid) 0.11

C18:0 (stearic acid) 4.58

C18:1n9 (oleic acid) 20.24

C18:1 (stearic acid (Ocadecenoic)) 1.36

C18:2n6 (linoleic acid) 45.17

C18:3n6 (gamma linoleic acid) 3.00

C18:3n3 (α linoleic acid) 3.41

C18:4n3 (parinaric acid

(octadecatetrenoic)) 3.21

C20:3n6 (two equal gamma linoleic acids) 0.05

C20:4n6 (arachidonic acid) 0.20

C20:5n3 (eicosapentaenoic acid

(eicosapentaenoic acid) 2.95

C22:6n3 (DHA) 1.96

C20 (arachidic acid) 0.35

C20:1n9 (eicosenoic acid) 0.15

C22 (behenic acid) 0.32

C24 (tetracosanoic acid) 0.12

Other are 1.64 years old

Except the mixing of above-mentioned oil, the composition below also having is used to prepare mayonnaise: vinegar (6300g), egg component (792g), water (3000g) and salt (1300g).The headroom of all mixers covers with nitrogen.By being dispersed in, egg prepares emulsification dressing in the 240g water then.Add salt then.After this, oil is joined in the aqueous dispersions of egg lentamente.This process is carried out under stirring fast.Remaining water and vinegar are added, make loose emulsion by colloid mill (as the Fryma mill).The pH value of the mixture that obtains is 4.0.Products obtained therefrom has the performance and the stability of mayonnaise.Products obtained therefrom is used to produce the turkey sandwich, coleslaw and Potato salad.The food made from the mayonnaise made from the oil that does not contain any aliphatic acid more than four two keys is difficult to differentiate in experiment.

Claims

1. the fluid composition of refining, bleaching of a process and taste removal, gross weight based on aliphatic acid or derivatives thereof in the described composition, it comprises at least a polyunsaturated fatty acid or derivatives thereof with 4 or more carbon-to-carbon double bonds of 0.4wt% at least and one of following

(a) described source is from source except that marine oil with have peroxide value less than 1meq/kg;

(b) described source is from source except that marine oil with have anisidine value less than 3;

(c) described polyunsaturated fatty acid is the parinaric acid or derivatives thereof, further comprise at least a other polyunsaturated fatty acid or derivatives thereof with 4 or more carbon-to-carbon double bonds with described composition, described composition has the anisidine value less than 3;

(d) described composition has and reaches as high as 2.5 fragrance and always influence branch, and wherein total influence is definite by the standardization sensory evaluation; Or

(e) described composition has and reaches as high as fragrance/fragrance of 2.5 and always influence branch, and wherein total influence is definite by the standardization sensory evaluation.

2. the composition of claim 1, based on the gross weight of aliphatic acid or derivatives thereof in the described composition, it comprises 3wt%-30wt% parinaric acid or derivatives thereof, and described composition has less than 3 anisidine value or less than the peroxide value of 1meq/kg.

3. the composition of claim 2, wherein said composition have the peroxide value of 10meq/kg at the most and less than 3 anisidine value.

4. the composition of claim 2, wherein said composition have less than the peroxide value of 1meq/kg and 20 anisidine value at the most.

5. each composition among the claim 2-4, wherein said composition has 26 totox value at the most.

6. each composition among the claim 2-5, wherein said composition comprise at the most 5, the tocopherol of 000ppm.

7. each composition among the claim 1-6, wherein said composition comprises the trans-fatty acid that is not more than 10wt%.

8. each composition among the claim 1-7, wherein said polyunsaturated fatty acid or derivatives thereof comprises the parinaric acid or derivatives thereof.

9. the food, beverage, nutritional supplement and the edible oil that comprise each described oil among the claim 1-8.

10. each composition, beverage, nutritional supplement or edible oil among the claim 1-9, it further comprises the stabilizing agent that is selected from citric acid, ascorbyl palmitate, tertiary butylated hydroquinone, n-propyl gallate and their combination.