CN101200741A - Synthesis of conjugated linoleic acid glyceride derivatives based on enzyme method - Google Patents
Synthesis of conjugated linoleic acid glyceride derivatives based on enzyme method Download PDFInfo
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- CN101200741A CN101200741A CNA2006101565029A CN200610156502A CN101200741A CN 101200741 A CN101200741 A CN 101200741A CN A2006101565029 A CNA2006101565029 A CN A2006101565029A CN 200610156502 A CN200610156502 A CN 200610156502A CN 101200741 A CN101200741 A CN 101200741A
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- linoleic acid
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Abstract
The invention relates to a conjugated linoleic acid glycerides derivative which mainly includes conjugated linoleic acid signal glyceride, conjugated linoleic acid diglyceride and conjugated linoleic acid polyglycerol ester. The product takes the fat with linoleic acid as raw material. The conjugated linoleic acid with high purity is obtained after the alkali isomerization and the molecular distillation purification. Then, the product is obtained under the normal temperature and the normal pressure after the enzymatic promoted catalytic reaction. Compared with the conjugated linoleic acid, the stability and the taste of the product are greatly improved. The invention can be widely applied to the fields of medicine, nutritional health products, food additives, functional feed additives, etc.
Description
Technical field
The present invention relates to a kind of novel conjugate linoleic acid derivative.Specifically be a kind of based on enzymatic means synthetic conjugated linoleic acid glyceride analog derivative, it belongs to biochemical field.
Background technology
(Conjugated linoleic acids CLA) is a plurality of positions of 18 carbon conjugated diolefine acid and the mixture of geometrical isomer to conjugated linolic acid.Studies show that conjugated linolic acid and ester class thereof, salt derivative have the biological activity of multiple beneficial such as anticancer, hypotensive, reducing blood-fat, atherosclerosis, increase immunizing power, fat-reducing, thereby caused people's attention, competitively develop its product at food, medicine, fodder industry.
Conjugated linolic acid is unstable in air, and it is not good that deterioration by oxidation and mouthfeel take place easily, and shelf-life is low.In order to improve its stability, often it is prepared into salt or ester derivative.But the poorly water-soluble of most salt derivatives, thereby range of application is narrow.If conjugated linolic acid can be converted into ester derivative, then its stability and mouthfeel all can significantly improve, thereby will have purposes more widely.The fatty acid ester analog derivative mainly comprises glyceryl ester and sugar esters derivative.Wherein glycerine monofatty ester and triglyceride all belong to nonionic surface active agent, have the good emulsifying ability, thereby are with a wide range of applications in food, medicine and other fields.But do not appear in the newspapers as yet about the synthetic of conjugated linoleic acid glyceride derivative at present.
Chemical processes such as the synthetic employing homogeneous phase solventless method of traditional saturated fatty acid glyceride, phase-transfer catalysis, the catalyzer that is adopted is soda soap normally.The common feature of these methods is to need exacting terms such as High Temperature High Pressure, and the productive rate of direactive glyceride, triglyceride is also on the low side.Because the conjugated linolic acid instability, thereby these methods all are not suitable for the synthetic of conjugated linoleic acid glyceride.
Patent content
The objective of the invention is problem, prepare the conjugated linoleic acid glyceride analog derivative at normal temperatures and pressures,, improve mouthfeel, increase the kind of conjugated linolic acid product, the broadened application scope to improve the stability of product based on enzymatic synthesis method at present existence.
Conjugated linoleic acid glyceride analog derivative of the present invention mainly comprises conjugated linolic acid direactive glyceride, conjugated linolic acid triglyceride, conjugated linolic acid polyglycerol ester etc.Be to be rich in linoleic grease, after alkali isomerization, molecular distillation are purified, obtain the conjugated linolic acid of higher degree, obtain through enzyme-catalyzed change is synthetic with the glycerols compound then.
The enzymatic of conjugated linoleic acid glyceride analog derivative is synthetic, carries out according to the following step:
(1) isomerization: under protection of inert gas, will be rich in linoleic grease and alkaline catalysts and in high boiling point polyol solvent such as ethylene glycol, glycerine, mix, and, obtain conjugate linoleate 100 ℃～200 ℃ back flow reaction.
(2) acidifying: regulate pH value 1～5, obtain mixed fatty acid.
(3) molecular distillation is purified, and obtains the higher conjugated linolic acid of purity.Mainly contain saturated or monounsaturated fatty acids such as stearic acid, Palmiticacid, oleic acid in the remaining waste material, the raw material that can be used as industries such as soapmaking, synthetic diet, oil and fat chemical uses.Realize the waste material utilization with this, increase economic efficiency, prevent the pollution of the environment.
(4) enzymatic esterification: after glycerols compound and conjugated linolic acid mixed in organic solvent, add enzyme catalyst and molecular sieve, enzyme dosage is 0.2%～8% of a conjugated linolic acid quality.Under the protection of inert gas, 20 ℃～70 ℃ stirring reactions 20～75 hours.Organic solvent is removed in distillation, purifies to obtain the conjugated linoleic acid glyceride analog derivative.
The raw material of preparation conjugated linoleic acid glyceride analog derivative is that Semen Maydis oil, Thistle oil, sunflower seeds wet goods are rich in linoleic grease, or directly are raw material with the conjugated linolic acid.
During enzymatic was synthetic, used glycerols compound was compounds such as anhydrous glycerol, Polyglycerine, polyvalent alcohol.Used enzyme can be the lipase that extracts from microorganisms such as candiyeast, head mold, enterobacteria, aspergillus, pseudomonas, look bacillus, candidiasis, slime-fungi and Penicillium, or business-like lipase.Used organic solvent can be DMSO, DMF, the trimethyl carbinol, tetrahydrofuran (THF), acetonitrile, normal hexane, octane, octane-iso, chloroform, pyridine, benzene, toluene or above-mentioned certain several mixed solvent.
The invention has the advantages that the enzymatic synthetic method of utilizing, promptly prepared the conjugated linoleic acid glyceride analog derivative at normal temperatures and pressures, avoided the deterioration by oxidation of conjugated linolic acid.The stability of this analog derivative has significantly raising than conjugated linolic acid, and mouthfeel is also obviously improved.Increased the kind of conjugated linolic acid product, range of application obtains enlarging, and can be widely used in fields such as medicine, health care nutriment, foodstuff additive, functional feedstuff additive.Because the raw material that adopts comprises Semen Maydis oil, safflower wet goods, the present invention has also opened up a new technological line for the deep processing of corn, safflower etc. simultaneously.
Embodiment
Embodiment 1
Synthesizing of conjugated linolic acid direactive glyceride
(1) isomerization: 50 gram KOH are joined in 600 milliliters of ethylene glycol and dissolve, and this alkaline solution mixes with 100 gram Semen Maydis oils, and under nitrogen gas stream was protected, 3 hours postcooling of 160 ℃ of back flow reaction obtained containing the mixture of conjugate linoleate.
(2) acidifying: adopt 1.0M HCl solution acidifying soap mixture, regulating pH value is 3.Collect upper organic phase after the standing demix, be washed to neutrality, obtain mixed fatty acid 85 grams.Gas chromatographic analysis shows that the linolic acid in the Semen Maydis oil is converted into conjugated linolic acid, and transformation efficiency reaches more than 93%.
(3) molecular distillation: mixed fatty acid is changed in the molecular distillation apparatus, and control condition is vacuum tightness 5-10Pa, and distillation temperature is at 160 ℃.Obtain purity and be about 80% conjugated linolic acid 28 grams, productive rate reaches about 33%.
(4) enzymatic esterification: above-mentioned 28 gram conjugated linolic acids are dissolved in 800 ml n-hexanes, add catalyzer CY-1 and molecular sieve that 90 gram glycerine and 2 grams extract from candiyeast.Mix the back nitrogen-filled seal, stirred 24 hours at 30 ℃.Normal hexane is removed in reaction end back distillation, crosses post and separates purification, obtains esterification products 20 grams, and its proton nmr spectra as shown in Figure 1.(m, 1H), 5.9 (m, 1H), 5.7 (m, 1H), 5.3 (m, signal 1H) are respectively the chemical shifts of four alkene hydrogen of conjugated linolic acid wherein to be positioned at 6.3.(m, signal 2H) are the glyceride structure chemical shifts to be positioned at 4.2.(m, signal 2H) are the chemical shifts of hydroxyl hydrogen to be positioned at 4.4.This shows that this esterification products is the conjugated linolic acid direactive glyceride.Productive rate reaches about 50%.
Embodiment 2
Synthesizing of conjugated linolic acid triglyceride
(1) isomerization: 50 gram KOH are joined in 600 milliliters of ethylene glycol and dissolve, and this alkaline solution mixes with 100 gram Semen Maydis oils, and under nitrogen gas stream was protected, 3 hours postcooling of 160 ℃ of back flow reaction obtained containing the mixture of conjugate linoleate.
(2) acidifying: adopt 1.0M HCl solution acidifying soap mixture, regulating pH value is 3.Collect upper organic phase after the standing demix, be washed to neutrality, obtain mixed fatty acid 85 grams.Gas chromatographic analysis shows that the linolic acid in the Semen Maydis oil is converted into conjugated linolic acid, and transformation efficiency reaches more than 93%.
(3) molecular distillation: mixed fatty acid is changed in the molecular distillation apparatus, and control condition is vacuum tightness 5-10Pa, and distillation temperature is below 150 ℃.Obtain purity and be about 80% conjugated linolic acid 28 grams, productive rate reaches about 33%.
(4) enzymatic esterification: above-mentioned 28 gram conjugated linolic acids are dissolved in 800 ml n-hexanes, add catalyzer CY-1 and molecular sieve that 90 gram glycerine and 2 grams extract from candiyeast.Mix the back nitrogen-filled seal, stirred 50 hours at 30 ℃.Normal hexane is removed in reaction end back distillation, crosses to obtain esterification products 19 grams after post separates purification, and its proton nmr spectra as shown in Figure 2.(m, 1H), 5.9 (m, 1H), 5.7 (m, 1H), 5.3 (m, signal 1H) are respectively the chemical shifts of four alkene hydrogen of conjugated linolic acid wherein to be positioned at 6.3.(m, signal 4H) are the chemical shifts of glyceride structure to be positioned at 4.2.(m, signal 1H) are the chemical shifts of hydroxyl hydrogen to be positioned at 4.4.This shows that this esterification products is the conjugated linolic acid triglyceride.Productive rate reaches 45%.
Embodiment 3
Synthesizing of conjugated linolic acid five polyglycerol esters
(1) isomerization: 50 gram KOH are joined in 600 milliliters of ethylene glycol and dissolve, and this alkaline solution mixes with 100 gram sunflower seed oils, and under nitrogen gas stream was protected, 3 hours postcooling of 160 ℃ of back flow reaction obtained containing the mixture of conjugate linoleate.
(2) acidifying: adopt 1.0M HCl solution acidifying soap mixture, regulating pH value is 3.Collect upper organic phase after the standing demix, be washed to neutrality, obtain mixed fatty acid 88 grams.Gas chromatographic analysis shows that the linolic acid in the sunflower seed oil is converted into conjugated linolic acid, and transformation efficiency reaches more than 93%.
(3) molecular distillation: mixed fatty acid is changed in the molecular distillation apparatus, and control condition is vacuum tightness 5-10Pa, and distillation temperature is at 160 ℃.Obtain purity and be about 80% conjugated linolic acid 24 grams, productive rate reaches about 30%.
(4) enzymatic esterification: above-mentioned 24 gram conjugated linolic acids are dissolved in 800 milliliters of pyridines, add enzyme catalyst CY-2 and molecular sieve that 100 gram five Polyglycerine and 2 grams extract from head mold.Mix the back nitrogen-filled seal, stirred 48 hours at 42 ℃.Pyridine is removed in reaction end back distillation, crosses to obtain conjugated linolic acid five polyglycerol esters 39 grams after post separates purification, and productive rate reaches more than 40%.
Embodiment 4
Synthesizing of conjugated linolic acid sorbitol ester
(1) isomerization: 50 gram KOH are joined in 600 milliliters of ethylene glycol and dissolve, and this alkaline solution mixes with 100 gram sunflower seed oils, and under nitrogen gas stream was protected, 3 hours postcooling of 160 ℃ of back flow reaction obtained containing the mixture of conjugate linoleate.
(2) acidifying: adopt 1.0M HCl solution acidifying soap mixture, regulating pH value is 3.Collect upper organic phase after the standing demix, be washed to neutrality, obtain mixed fatty acid 88 grams.Gas chromatographic analysis shows that the linolic acid in the sunflower seed oil is converted into conjugated linolic acid, and transformation efficiency reaches more than 93%.
(3) molecular distillation: mixed fatty acid is changed in the molecular distillation apparatus, and control condition is vacuum tightness 5-10Pa, and distillation temperature is at 160 ℃.Obtain purity and be about 80% conjugated linolic acid 24 grams, productive rate reaches about 30%.
(4) enzymatic esterification: above-mentioned 24 gram conjugated linolic acids are dissolved in 800 milliliters of pyridines, add pure and mild 2 gram enzyme catalyst CY-3 and the molecular sieves of 80 Keshan pears.Mix the back nitrogen-filled seal, stirred 48 hours at 40 ℃.Pyridine is removed in reaction end back distillation, crosses to obtain conjugated linolic acid sorbitol ester 21 grams after post separates purification, and productive rate reaches more than 40%.
Claims (8)
1. based on the conjugated linoleic acid glyceride analog derivative of enzymatic synthesis method preparation, mainly comprise conjugated linolic acid direactive glyceride, conjugated linolic acid triglyceride and conjugated linolic acid polyglycerol ester.It is characterized in that: be will be rich in linoleic grease after alkali isomerization, molecular distillation are purified, obtain the conjugated linolic acid of higher degree, then with the glycerols compound through enzymic catalytic reaction, obtain the conjugated linoleic acid glyceride analog derivative.
2. conjugated linoleic acid glyceride analog derivative according to claim 1 is characterized in that according to the following step synthetic:
(1) isomerization: under protection of inert gas, will be rich in linoleic grease and alkaline catalysts and in high boiling point polyol solvent such as ethylene glycol or glycerine, mix, and, obtain conjugate linoleate 100 ℃～200 ℃ back flow reaction.
(2) acidifying: regulate pH value 1～5, obtain mixed fatty acid.
(3) molecular distillation is purified, and obtains the higher conjugated linolic acid of purity.
(4) enzymatic esterification: after glycerols compound and above-mentioned conjugated linolic acid mixed, add enzyme catalyst and molecular sieve in organic solvent, under the protection of inert gas 20 ℃～70 ℃ stirring reactions 20～75 hours.Organic solvent is removed in distillation, purifies to obtain the conjugated linoleic acid glyceride analog derivative.
3. the synthetic method of conjugated linoleic acid glyceride analog derivative according to claim 2 is characterized in that: the raw material for preparing this product is that Semen Maydis oil, Thistle oil, sunflower seeds wet goods are rich in linoleic grease, or directly are raw material with the conjugated linolic acid.
4. the synthetic method of conjugated linoleic acid glyceride analog derivative according to claim 2 is characterized in that: used glycerols compound is anhydrous glycerol, Polyglycerine, polyvalent alcohol etc.
5. the synthetic method of conjugated linoleic acid glyceride analog derivative according to claim 2, it is characterized in that: used enzyme can be the lipase that extracts from microorganisms such as candiyeast, head mold, enterobacteria, aspergillus, pseudomonas, look bacillus, candidiasis, slime-fungi and Penicillium, or directly uses commercialization lipase as catalyzer.
6. the synthetic method of conjugated linoleic acid glyceride analog derivative according to claim 2 is characterized in that: used organic solvent can be DMSO, DMF, the trimethyl carbinol, tetrahydrofuran (THF), acetonitrile, normal hexane, octane, octane-iso, chloroform, pyridine, benzene, toluene or above-mentioned certain several mixed solvent.
7. conjugated linoleic acid glyceride analog derivative according to claim 1 the medicine of antitumor, hyperlipidemia disease, fat-reducing, strengthening immunity etc. or at food, nutritious prod, milk preparation etc. as Application of Additives.
8. conjugated linoleic acid glyceride analog derivative according to claim 1 in animal-feeds such as pig, chicken, fish as Application of Additives.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102901787A (en) * | 2011-07-29 | 2013-01-30 | 内蒙古蒙牛乳业（集团）股份有限公司 | Detection method for content of total monoglyceride in liquid milk |
| WO2016101894A1 (en) * | 2014-12-26 | 2016-06-30 | Wilmar (Shanghai) Biotechnology Research & Development Center Co., Ltd. | Oil/fat composition and preparation method for the same |
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2006
- 2006-12-14 CN CNA2006101565029A patent/CN101200741A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102901787A (en) * | 2011-07-29 | 2013-01-30 | 内蒙古蒙牛乳业（集团）股份有限公司 | Detection method for content of total monoglyceride in liquid milk |
| CN102901787B (en) * | 2011-07-29 | 2014-06-11 | 内蒙古蒙牛乳业（集团）股份有限公司 | Detection method for content of total monoglyceride in liquid milk |
| WO2016101894A1 (en) * | 2014-12-26 | 2016-06-30 | Wilmar (Shanghai) Biotechnology Research & Development Center Co., Ltd. | Oil/fat composition and preparation method for the same |
| CN105767213A (en) * | 2014-12-26 | 2016-07-20 | 丰益(上海)生物技术研发中心有限公司 | Grease composition and preparation method thereof |
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