A kind of Sn-2 Structure grease and preparation method thereof rich in docosahexaenoic acidTechnical field
The present invention relates to edible oil and fat technical field, the especially a kind of Sn-2 structure oil rich in docosahexaenoic acidRouge and preparation method thereof.
Background technique
Grease is the general designation of oil & fat, and main component is the glycerol of a molecule glycerol and the Esterification formation of three molecular fatsThree esters, wherein the fatty acid for being located at glycerol backbone middle position is known as Sn-2 fatty acid, the fatty acid positioned at end positions claimsFor Sn-1,3 fatty acid.
Structure grease refers to grease on location with special fatty acid.In broad terms, it refers to any processThe grease of artificial modification, also known as Structured Lipids, structured lipids, type is extensive, triglycerides including a variety of special constructions, sweetOily diester, monoglyceride and non-glycerol base aliphatic ester etc..But usually said Structure grease is primarily referred to as structured triglyceride, knotFatty acyl group on the glycerol backbone of structure triglycerides by one it is scheduled form and distribution, thus there is special nutritive valueAnd physiological function.Structure grease is usually to be not present in nature, needs artificial recombination or synthesis.
Docosahexaenoic acid, i.e. DHA belong to n-3 series long-chain polyunsaturated fatty acid, in the product often with 22 carbonThe form of acid triglycerides exists, and human body itself cannot synthesize, it is necessary to obtain from food, be a kind of fat needed by humanAcid.DHA is played a very important role during fetus and infant's brain and development of vision system, to fetal growth, babyInfant intelligence development and immune function all have significant effect.Meanwhile DHA also has anticoagulation, inhibits platelet aggregation, thrombusIt formed, inhibit cancer, effect that is anti-inflammatory and improving immunity.
DHA is a kind of long-chain highly unsaturated fatty acid, and intramolecular contains 6 unsaturated double-bonds, thus to oxygen, light andHot extreme sensitivity, easily aoxidizes, and not only reduces its Biofunctional, also will form the substance being harmful to the human body.Current DHA isIt is distributed across the Sn-1 of glycerol backbone end positions, on 3, the prior art (CN103725721B) provides a kind of rich in 22The Structure grease and preparation method thereof of carbon acid is that docosahexaenoic acid is distributed in Sn-1,3, palmitinic acid is distributedAt Sn-2, docosahexaenoic acid is supplemented while Sn-2 palmitinic acids are provided, is easy to be digested.But it willDHA is distributed across the Sn-1 of glycerol backbone end positions, and on 3, the oxidation stability of DHA is bad, oxidizable, makes DHA'sBioavailability is low, the physiological function that human body cannot be adequately excellent using DHA.
Summary of the invention
The object of the present invention is to provide a kind of Sn-2 be rich in docosahexaenoic acid Structure grease and preparation method thereof,Solve the Sn-1 that existing DHA is distributed across glycerol backbone end positions, on 3, the oxidation stability of DHA is bad, easy oxygenThe technical issues of change, keeps the bioavailability of DHA low, and human body cannot adequately utilize DHA excellent physiological function.
In order to achieve the above object, the invention provides the following technical scheme:
A kind of Sn-2 Structure grease rich in docosahexaenoic acid, the glycerol backbone of Structure grease Sn-2The docosahexaenoic acid of upper 25% or more opposed configuration grease total fatty acid content of connection, Sn-1,3 upper connection fatty acid.
Since edible oil and fat are mostly taken in the form of triglycerides by human body.Triglycerides in human body metabolism, due toThe height Sn-1 of pancreatic lipase, 3 location specifics, Sn-1,3 fatty glycerides are after pancreatic lipase hydrolyzes, with fatThe form of acid is absorbed by intestinal epithelial cell, then enters portal vein via capillary, is finally quickly transferred to liver and is carried out generationIt thanks and releases energy.After Sn-2 fatty glycerides enter cell in the form of Sn-2 fatty acid monoglyceride, in the cell againThree ester of synthetic glycerine, it is further that the combination such as newly synthesized triglycerides and phosphatide, lipoprotein and carrier protein forms chylomicronIt is metabolized, in the required physiological activator of synthesized human or participation physiological activator synthesis process.Therefore, DHA is enriched in sweetOily skeleton Sn-2, DHA has higher bioavailability, the physiological function that human body can more make full use of DHA excellent.
Meanwhile DHA being distributed on the position glycerol backbone Sn-2 and is distributed in Sn-1 than it, 3 upper oxidation stabilities are good, this isBecause of the protective effect of steric hindrance, it is located at glycerol backbone Sn-1, the partition effect of 3 other fatty acid molecules, for example satisfyAnd fatty acid molecule, for intramolecular without unsaturated double-bond, stability is good, reduce DHA touch opportunity on oxygen molecule and the position Sn-2, thisFundamentally improve the oxidation stability of DHA.Meanwhile according to Different Nutrition function needs, middle Long carbon chain fat can chooseAcid, such as palmitinic acid, octanoic acid, capric acid, are connected to glycerol backbone Sn-1, on 3, due to middle Long carbon chain fatty acid energy supply low in caloriesFast feature is conducive to human body and quickly energizes and the reducing blood lipid of fat reducing fat.
A kind of preparation method of the Sn-2 Structure grease rich in docosahexaenoic acid, comprising the following steps:
Docosahexaenoic acid algae oil is hydrolyzed preparation mixing docosahexaenoic acid by step S101；
Step S102 is enriched with the mixing docosahexaenoic acid to obtain the mixing rouge of docosahexaenoic acid high-contentFat acid；
Step S103, by the fatty acid mixed of docosahexaenoic acid high-content and glycerine in lipase-catalyzed lower progressEnzyme process esterification, then lipase is removed, obtain pure docosahexaenoic acid triglycerides；
Step S104, by the pure docosahexaenoic acid triglycerides and fatty acid donors under the catalysis of lipase intoRow acidolysis reaction, then lipase is removed, obtain the thick Sn-2 Structure grease for being rich in docosahexaenoic acid；
The described thick Sn-2 Structure grease rich in docosahexaenoic acid is purified, obtains Sn-2 by step S105Position is rich in the Structure grease of docosahexaenoic acid.
In a preferred embodiment, in the step S101, the hydrolysis preparation of docosahexaenoic acid algae oil is mixedThe preparation method of docosahexaenoic acid is closed using appointing in enzymatic hydrolysis, alkali process hydrolysis, Acid hydrolysis, high temperature and high pressure method hydrolysisMeaning one or more combine.
In a preferred embodiment, it in the step S102, is enriched with mixing docosahexaenoic acid to obtain twoThe method of the fatty acid mixed of dodecahexaene acid high-content is using any one in molecularly distilled, enzyme process, urea adduct methodKind or a variety of combine；And the absolute content of docosahexaenoic acid is 60% or more in obtained fatty acid mixed.
In a preferred embodiment, in the step S103, the mixing-in fat of docosahexaenoic acid high-contentThe mass ratio of acid and glycerine is 5-20:1；The additive amount of lipase is the fatty acid mixed of docosahexaenoic acid high-contentWith the 1-6% of glycerine total weight, reaction temperature is 40-80 DEG C, reaction time 4-24h.
In a preferred embodiment, in the step S103, the mixing-in fat of docosahexaenoic acid high-contentThe mass ratio of acid and glycerine is 10:1；The additive amount of lipase be docosahexaenoic acid high-content fatty acid mixed withThe 4% of glycerine total weight, reaction temperature are 60 DEG C, reaction time 10h.
In a preferred embodiment, in the step S104, pure docosahexaenoic acid triglycerides and fatThe mass ratio of acid donors is 1-10:1；The additive amount of lipase is pure docosahexaenoic acid triglycerides and fatty acid donorsThe 1-6% of total weight, reaction temperature are 40-80 DEG C, reaction time 4-24h.
In step S104, fatty acid donors can be arbitrary fatty acid and its derivative, such as palmitinic acid, n-nonanoic acid or capric acidDeng.
In a preferred embodiment, in the step S105, purification process uses molecularly distilled, solvent extractionMethod, miscella depickling method, in supercritical extraction any one or a variety of combine.
In a preferred embodiment, further include step S106 after the step S105, described Sn-2 is rich inThe quality and physical and chemical index of the Structure grease of docosahexaenoic acid are detected；If quality or physical and chemical index are unqualified,Decoloration and deodorization processing are carried out to the described Sn-2 Structure grease rich in docosahexaenoic acid.
In a preferred embodiment, it in the step S103 and step S104, is all made of centrifugation or filters out excessivelyLipase is removed, and the lipase is recycled, is recycled.
Compared with prior art, the present invention the beneficial effect is that, in Structure grease of the invention, by two dodecahexaenesAcid is enriched on the position glycerol backbone Sn-2, keeps the oxidation stability of Structure grease more preferable, fundamentally improves how unsaturated rougeThe unstable oxidizable problem of fat acid.Meanwhile glycerol backbone Sn-2 are rich in docosahexaenoic acid, 22 carbon of the position Sn-2Acid can preferably carry out metabolism, and substance necessary to synthesized human growth and development greatly improves 22 carbonThe bioavailability of acid, physiological activity is stronger, can give full play to docosahexaenoic acid educate brain intelligence development, educate the strong view of view,Prevent and treat cardiovascular disease, anticancer, anti-inflammatory and the relevant physiological function of preventing and treating artery sclerosis.In addition, with preparation of the inventionThe content of the Structure grease that method obtains, the docosahexaenoic acid on the position Sn-2 can reach 25% or more, more meetHuman body needs, utilization rate are higher.
Meanwhile according to the demand of Different Nutrition and physiological function, different types of fatty acid is selected to be connected to glycerol backboneSn-1,3, such as selection is sad or capric acid, this kind of middle long chain fatty acids have the characteristics that the fast heat of energy supply is low, are conducive to human bodyQuickly energy supply and the reducing blood lipid of fat reducing fat were suitable for fat constitution crowd and energy supply impaired patients.
Specific embodiment
Technical solution of the present invention is clearly and completely described below, it is clear that described embodiment is only thisInvention a part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art existEvery other embodiment obtained under the premise of creative work is not made, shall fall within the protection scope of the present invention.
Embodiment 1
The synthetic method of Structure grease in the present embodiment the following steps are included:
Step S101: by docosahexaenoic acid algae oil using method preparation two dodecahexaenes of mixing of alkali process hydrolysisAcid；
Wherein, ethyl alcohol is added in oil according to the ratio that w/v is 1:1, opens stirring and be condensed back, opensHeating system is simultaneously passed through nitrogen, is warming up to 60 ± 5 DEG C.After oil and ethyl alcohol are in uniform state, the hydroxide that oil weighs 50% is addedSodium solution, concentration of sodium hydroxide solution 7mol/L, hydrolysis time 2 hours；
After the completion of hydrolysis, cooling system is opened, gained hydrolysate is cooled to room temperature, the pH of above-mentioned hydrolysate is adjustedFor 1-2, hydrolysate is washed, dehydration obtains mixing docosahexaenoic acid.
Step S102: means of the docosahexaenoic acid by molecular distillation will be mixed, enables docosahexaenoic acidEnrichment, obtains the fatty acid mixed of docosahexaenoic acid high-content；
Step S103: by the fatty acid mixed of docosahexaenoic acid high-content and glycerine in lipase-catalyzed lower progressEnzyme process esterification；Lipase is removed by centrifugation again, obtains pure docosahexaenoic acid triglycerides；And lipase is returnedIt receives, recycles.
Wherein, the weight adding proportion of the fatty acid mixed of docosahexaenoic acid high-content and glycerine is 10:1；RougeThe additive amount of fat enzyme is the fatty acid mixed and the 4% of glycerine total weight of docosahexaenoic acid high-content, and reaction temperature is60 DEG C, reaction time 10h；
In addition, opening stirring in enzyme process esterification reaction process, makes reaction system in uniform state, increase enzyme and reactantTouch opportunity.And nitrogen should be passed through in reaction vessel, it plays a protective role.
Step S104: pure docosahexaenoic acid triglycerides and fatty acid donors are subjected to acid under the catalysis of lipaseSolution reaction；Lipase is removed by centrifugation again, obtains the thick Sn-2 Structure grease for being rich in docosahexaenoic acid；And by rougeThe recycling of fat enzyme, recycles.
The present embodiment chooses palmitinic acid as fatty acid donors, the weight of pure docosahexaenoic acid triglycerides and palmitinic acidMeasuring adding proportion is 1.5:1；The additive amount of lipase is pure docosahexaenoic acid triglycerides and palmitinic acid total weight4%, reaction temperature is 60 DEG C, reaction time 20h；
In addition, opening stirring during enzymatic acidolysis reaction, make reaction system in uniform state, increase enzyme with reactThe touch opportunity of object.And nitrogen should be passed through in reaction vessel, it plays a protective role.
Step S105: by the thick Sn-2 Structure grease rich in docosahexaenoic acid take the method for miscella depickling intoRow purifying removes the by-product that Structure grease synthesis process generates, and obtains the Sn-2 structure oil rich in docosahexaenoic acidRouge；
Step S106: the quality and physical and chemical index of Structure grease obtained in step S105 are detected；It is taken off againColor and deodorization processing, obtain better Sn-2 of the quality Structure grease for being rich in docosahexaenoic acid.
The Structure grease that the present embodiment 1 synthesizes, on the position glycerol backbone Sn-2, the content of docosahexaenoic acid reaches42%；On glycerol backbone Sn-1,3, it is rich in palmitinic acid, this Structure grease has better oxidation stability, has higherBioavailability.
Embodiment 2
The synthetic method of Structure grease in the present embodiment the following steps are included:
Step S101: by docosahexaenoic acid algae oil using method preparation two dodecahexaenes of mixing of enzymatic hydrolysisAcid；
Wherein, purified water is added to docosahexaenoic acid algae oil, grease weight ratio 5:1 opens stirring, opens heating systemIt unites and is passed through nitrogen, be warming up to 60 ± 5 DEG C, be added the lipase that oil weighs 1 ‰, hydrolysis time 12 hours；Hydrolysis is completedAfterwards, hydrolysate is washed, dehydration obtains mixing docosahexaenoic acid.
Step S102: means of the docosahexaenoic acid by molecular distillation will be mixed, enables docosahexaenoic acidEnrichment, obtains the fatty acid mixed of docosahexaenoic acid high-content；
Step S103: the fatty acid mixed and glycerine for making docosahexaenoic acid high-content are in lipase-catalyzed lower progressEnzyme process esterification；Lipase is removed by centrifugation again, obtains pure docosahexaenoic acid triglycerides；And lipase is returnedIt receives, recycles.
Wherein, the weight adding proportion of the fatty acid mixed of docosahexaenoic acid high-content and glycerine is 10:1；RougeThe additive amount of fat enzyme is the fatty acid mixed and the 3% of glycerine total weight of docosahexaenoic acid high-content, and reaction temperature is60 DEG C, reaction time 15h；
In addition, opening stirring in lipase-catalyzed esterification reaction process, make reaction system in uniform state, increase enzyme with reactThe touch opportunity of object.And nitrogen should be passed through in reaction vessel, it plays a protective role.
Step S104: pure docosahexaenoic acid triglycerides and fatty acid donors are subjected to acid under the catalysis of lipaseSolution reaction；Lipase is removed by centrifugation again, obtains the thick Sn-2 Structure grease for being rich in docosahexaenoic acid；And by rougeThe recycling of fat enzyme, recycles.
The weight of the fatty acid donors of the present embodiment selection n-nonanoic acid conduct, pure docosahexaenoic acid triglycerides and n-nonanoic acid addsAdding ratio is 3:1；The additive amount of lipase is the 3% of pure docosahexaenoic acid triglycerides and n-nonanoic acid total weight, reaction temperatureDegree is 60 DEG C, and the reaction time is for 24 hours；
In addition, opening stirring during enzymatic acidolysis reaction, make reaction system in uniform state, increase enzyme with reactThe touch opportunity of object.And nitrogen should be passed through in reaction vessel, it plays a protective role.
Step S105: by the thick Sn-2 Structure grease rich in docosahexaenoic acid take the method for miscella depickling intoRow purifying removes the by-product that Structure grease synthesis process generates, and obtains the Sn-2 structure oil rich in docosahexaenoic acidRouge；
Step S106: the quality and physical and chemical index of Structure grease obtained in step S105 are detected；It is taken off againColor and deodorization processing, obtain better Sn-2 of the quality Structure grease for being rich in docosahexaenoic acid.
The Structure grease that the present embodiment 2 synthesizes, on the position glycerol backbone Sn-2, the content of docosahexaenoic acid reaches38%；On glycerol backbone Sn-1,3, it is rich in n-nonanoic acid.This Structure grease has higher bioavailability, Sn-1, on 3N-nonanoic acid can be preferably human body power supply, and have the characteristics that energy is low, facilitate weight-reducing and reducing blood lipid.
Embodiment 3
The synthetic method of Structure grease in the present embodiment the following steps are included:
Step S101: by docosahexaenoic acid algae oil using enzymatic hydrolysis preparation mixing docosahexaenoic acid；
Wherein, purified water is added to docosahexaenoic acid algae oil, grease weight ratio 10:1 opens stirring, opens heatingSystem is simultaneously passed through nitrogen, is warming up to 35 ± 5 DEG C, is added the lipase that oil weighs 1 ‰, and hydrolysis time 24 hours；Hydrolysis is completedAfterwards, hydrolysate is washed, dehydration obtains mixing docosahexaenoic acid；
Step S102: mixing docosahexaenoic acid is enable docosahexaenoic acid to be enriched with, is obtained by urea adduct methodTo the fatty acid mixed of docosahexaenoic acid high-content；
Step S103: by the fatty acid mixed of docosahexaenoic acid high-content and glycerine in lipase-catalyzed lower progressEnzyme process esterification；Lipase is removed by filtration again, obtains pure docosahexaenoic acid triglycerides；And lipase is returnedIt receives, recycles.
Wherein, the weight adding proportion of the fatty acid mixed of docosahexaenoic acid high-content and glycerine is 8:1；RougeThe additive amount of fat enzyme is the fatty acid mixed and the 6% of glycerine total weight of docosahexaenoic acid high-content, and reaction temperature is60 DEG C, reaction time 5h；
In addition, opening stirring in enzyme process esterification reaction process, makes reaction system in uniform state, increase enzyme and reactantTouch opportunity.And nitrogen should be passed through in reaction vessel, it plays a protective role.
Step S104: pure docosahexaenoic acid triglycerides and fatty acid donors are subjected to acid under the catalysis of lipaseSolution reaction；Lipase is removed by filtration again, obtains the thick Sn-2 Structure grease for being rich in docosahexaenoic acid；And by rougeThe recycling of fat enzyme, recycles.
The weight of the fatty acid donors of the present embodiment selection capric acid conduct, pure docosahexaenoic acid triglycerides and capric acid addsAdding ratio is 2:1；The additive amount of lipase is the 6% of pure docosahexaenoic acid triglycerides and capric acid total weight, reaction temperatureDegree is 60 DEG C, reaction time 15h；
In addition, opening stirring during enzymatic acidolysis reaction, make reaction system in uniform state, increase enzyme with reactThe touch opportunity of object.And nitrogen should be passed through in reaction vessel, it plays a protective role.
Step S105: the method that the thick Sn-2 Structure grease rich in docosahexaenoic acid takes molecular distillation is carried outPurifying removes the by-product that Structure grease synthesis process generates, and obtains the Sn-2 Structure greases for being rich in docosahexaenoic acid；
Step S106: the quality and physical and chemical index of Structure grease obtained in step S105 are detected；The present embodimentStructure grease quality and physical and chemical index it is up to standard, no longer carry out decoloration and deodorization processing.
The Structure grease that the present embodiment 3 synthesizes, on the position glycerol backbone Sn-2, the content of docosahexaenoic acid reaches40%；On glycerol backbone Sn-1,3, it is rich in capric acid.This Structure grease has higher bioavailability, Sn-1, on 3Capric acid can be preferably human body power supply, and have the characteristics that energy is low, facilitate weight-reducing and reducing blood lipid.
Case study on implementation 4
The synthetic method of Structure grease in the present embodiment the following steps are included:
Step S101: by docosahexaenoic acid algae oil using method preparation two dodecahexaenes of mixing of enzymatic hydrolysisAcid；
Wherein, purified water is added to docosahexaenoic acid algae oil, grease weight ratio 10:1 opens stirring, opens heatingSystem is simultaneously passed through nitrogen, is warming up to 35 ± 5 DEG C, is added the lipase that oil weighs 1 ‰, and hydrolysis time 24 hours；Hydrolysis is completedAfterwards, hydrolysate is washed, dehydration obtains mixing docosahexaenoic acid；
Step S102: means of the docosahexaenoic acid by molecular distillation will be mixed, enables docosahexaenoic acidEnrichment, obtains the fatty acid mixed of docosahexaenoic acid high-content；
Step S103: the fatty acid mixed and glycerine for making docosahexaenoic acid high-content are in lipase-catalyzed lower progressEnzyme process esterification；Lipase is removed by centrifugation again, obtains pure docosahexaenoic acid triglycerides；And lipase is returnedIt receives, recycles.
Wherein, the weight adding proportion of the fatty acid mixed of docosahexaenoic acid high-content and glycerine is 6:1；RougeThe additive amount of fat enzyme is the fatty acid mixed and the 3% of glycerine total weight of docosahexaenoic acid high-content, and reaction temperature is60 DEG C, reaction time 10h；
In addition, opening stirring in lipase-catalyzed esterification reaction process, make reaction system in uniform state, increase enzyme with reactThe touch opportunity of object.And nitrogen should be passed through in reaction vessel, it plays a protective role.
Step S104: pure docosahexaenoic acid triglycerides and fatty acid donors are subjected to acid under the catalysis of lipaseSolution reaction；Lipase is removed by centrifugation again, obtains the thick Sn-2 Structure grease for being rich in docosahexaenoic acid；And by rougeThe recycling of fat enzyme, recycles.
The present embodiment chooses the mixed acid of n-nonanoic acid and capric acid as fatty acid donors, pure docosahexaenoic acid triglyceridesWeight adding proportion with n-nonanoic acid and capric acid mixed acid is 2:1；Wherein, in mixed acid, the ratio of n-nonanoic acid and capric acid is 2:1；It willThe two is uniformly mixed and adds in reaction vessel.The additive amount of lipase be pure docosahexaenoic acid triglycerides and n-nonanoic acid andThe 3% of capric acid mixed acid total weight, reaction temperature are 60 DEG C, reaction time 20h；
In addition, opening stirring during enzymatic acidolysis reaction, make reaction system in uniform state, increase enzyme with reactThe touch opportunity of object.And nitrogen should be passed through in reaction vessel, it plays a protective role.
Step S105: molecularly distilled is taken to carry out the thick Sn-2 Structure grease rich in docosahexaenoic acid pureChange, remove the by-product that Structure grease synthesis process generates, obtains the Sn-2 Structure greases for being rich in docosahexaenoic acid；
Step S106: the quality and physical and chemical index of Structure grease obtained in step S105 are detected；The present embodimentStructure grease quality and physical and chemical index it is up to standard, no longer carry out decoloration and deodorization processing.
The Structure grease that the present embodiment 4 synthesizes, on the position glycerol backbone Sn-2, the content of docosahexaenoic acid reaches35%；On glycerol backbone Sn-1,3, it is rich in n-nonanoic acid and capric acid.This Structure grease have higher bioavailability, Sn-1,N-nonanoic acid and capric acid on 3 can be preferably human body power supply, and have the characteristics that energy is low, facilitate weight-reducing and reducing blood lipid.
Method for washing, dewatering, filter method, the centrifugal method, molecular distillation side of use in above-described embodiment 1-4Existing conventional technical means can be used in method, miscella acid stripping method, decolorization, deodorization processing etc., does not make herein in detailDescription.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, anyThose familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all containLid is within protection scope of the present invention.Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.