CN104803901A - Method for preparing zeaxanthin through in situ enrichment - Google Patents
Method for preparing zeaxanthin through in situ enrichment Download PDFInfo
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- CN104803901A CN104803901A CN201410038945.2A CN201410038945A CN104803901A CN 104803901 A CN104803901 A CN 104803901A CN 201410038945 A CN201410038945 A CN 201410038945A CN 104803901 A CN104803901 A CN 104803901A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
- C07C403/24—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by six-membered non-aromatic rings, e.g. beta-carotene
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- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B61/00—Dyes of natural origin prepared from natural sources, e.g. vegetable sources
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- C07—ORGANIC CHEMISTRY
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Abstract
The invention relates to a method for preparing natural zeaxanthin. The method concretely comprises the following steps: extracting a plant, saponifying to prepare natural zeaxanthin, carrying out in situ enrichment on zeaxanthin through using a solid adsorbent, and drying to obtain natural zeaxanthin with high purity. The method for in situ enrichment of zeaxanthin by using the solid adsorbent can greatly reduce the consumption amount of water and organic solvents, so the method has the advantages of simple process, high efficiency and easy industrial amplification, can be applied to the fields of foods, health foods, medicines and cosmetics, and has good industrial application prospects.
Description
Technical field
The present invention relates to the extracting method of natural corn flavine, specifically the method for zeaxanthin is extracted, prepared to in-situ enrichment method from Vegetables and fruits, and zeaxanthin preparation method of the present invention has the advantages that technique is simple, efficiency is high, solvent usage quantity is few, zeaxanthin purity is high.Prepared natural corn flavine can be used for the fields such as food, protective foods, medicine, makeup.
Background technology
Zeaxanthin (Zeaxanthin, 3,3 '-dihydroxyl-β-carotene, C
40h
56o
2), also known as zeaxanthin, be the carotenoid xanthin with hydroxyl.
The molecular structure of formula 1 zeaxanthin, xenthophylls
Maize have two chiral carbon and is positioned at 3 and 3 ', to four isomerss should be had, be respectively (3R, 3 ' S)-, (3S, 3 ' R)-, (3R, 3 ' R)-, (3S, 3 ' S)-zeaxanthin.Because zeaxanthin molecular structure is symmetrical, (3R, 3 ' S)-, the structure of (3S, 3 ' R)-zeaxanthin is identical, is called as meso-zeaxanthin.The zeaxanthin of occurring in nature is with 3R, and the form of 3 ' R-zeaxanthin exists, and is that raw material is meso-zeaxanthin by the maize yellow that chemical method synthesizes with xenthophylls.
Zeaxanthin and xenthophylls are the unique carotenoid in human body amphiblestroid macula lutea position, are the main composition pigments (Clinics in Dermatology (2009) 27,195 – 201) of macular pigment.Zeaxanthin mainly concentrates on amphiblestroid macular area center, and xenthophylls is then throughout retina.Zeaxanthin has the effect of blue light in specific absorption ultraviolet; blue light can be avoided retina injury; zeaxanthin and xenthophylls also have oxidation resistant effect simultaneously; retina, epithelial cell, choroid etc. can be prevented owing to being oxidized the ocular injury that causes, and therefore zeaxanthin and xenthophylls have important effect (Br J Ophthalmol199983:867-877) for the nutrition protection of human body eyesight and eyes.Experiment proves that zeaxanthin is more even more important for the effect of eyes than xenthophylls, and when zeaxanthin is under-supply, xenthophylls is converted into zeaxanthin by people's cognition automatically.
Senile macular degeneration SMD (AMD) is the primary illness in eye of the elderly's visual disorder and blinding, zeaxanthin in the risk of AMD and blood of human body and xenthophylls concentration closely related, large quantity research proves to take in 6mg zeaxanthin every day and xenthophylls can effectively reduce senile macular degeneration SMD risk, slows down senile macular degeneration SMD process.Macular pigment zeaxanthin and xenthophylls also can improve the eye problems (Academy of Ophthalmic Education) such as ocular photophobia, dazzle recovery, mesopic vision, dark reaction.
Human body cannot self synthesis zeaxanthin, can only pass through ingestion of food, zeaxanthin is mainly present in corn, capsicum, yolk and deep green vegetables, but in deep green vegetables zeaxanthin content well below xenthophylls.AMD High risk group is only relied on to from food, obtain zeaxanthin be very limited, need extra supplement to supplement zeaxanthin.U.S. FDA have rated the security of zeaxanthin, and the human body daily upper limit is 160mg, is zeaxanthin 6mg/ days for prevention AMD and asthenopic recommended amounts.The zeaxanthin of occurring in nature is with 3R, and the form of 3 ' R-zeaxanthin exists, and the safety experiment data of zeaxanthin are also based on 3R, and 3 ' R-zeaxanthin draws.But the resource of zeaxanthin is very limited, zeaxanthin is in the market mainly raw material with xenthophylls, obtained by the method for chemosynthesis, the zeaxanthin that chemical method obtains is meso-zeaxanthin, yet there are no the security report of meso-zeaxanthin.Consider the 3R of extracting directly from plant from security standpoint, 3 ' R-zeaxanthin is the most safe and reliable.（Food and Chemical Toxicology49(2011)2841–2848）
Summary of the invention
The object of this invention is to provide a kind of extraction of natural corn flavine, preparation method; The natural corn flavine of extraction, saponification gained is passed through solid adsorbent in-situ enrichment by method of the present invention, the method reduce the step needed for zeaxanthin separation and purification, greatly reduce the use of solvent, water, the natural corn flavine purity obtained is high, can be applicable to the fields such as food, protective foods, medicine, there is good prospects for commercial application.
For achieving the above object, the technical solution used in the present invention is as follows:
In-situ enrichment legal system is for the technology of natural corn flavine, to the raw material of zeaxanthin be rich in after extracting saponification, in saponification liquor, directly add solid adsorbent carry out in-situ enrichment, then use a small amount of solvent by zeaxanthin wash-out, elutriant concentrate drying obtains the higher zeaxanthin of content.
In-situ enrichment legal system for a preparation method for natural corn flavine,
1) will grind as raw material, according to raw materials quality after one or two or more kinds the position drying in plant: the ratio of solvent volume=1g:10 ~ 100ml adds Extraction solvent, 30 ~ 80 DEG C be stirred extraction 1 ~ 10 hour, extract after terminating and staticly settle filtering separation; Obtain extracting solution and filter residue;
2) according to the operating process of step 1), previous step gained filter residue is extracted again, extract and repeat 2-4 time altogether;
3) united extraction liquid is evaporated to solvent and is evaporated, and adding volume is 1/10 ~ 1 times of former single-trial extraction solvent volume, the alcoholic solution of mass concentration 1 ~ 50%KOH or NaOH, and 10 ~ 80 DEG C are stirred saponification 1 ~ 40 hour;
4) saponification adds solid adsorbent after terminating, and slowly stirs 0.5 ~ 10 hour, standing separation, obtains the solid adsorbent of enrichment natural corn flavine; It is neutral for rinsing the solid adsorbent being rich in natural corn flavine to institute pH with the deionized waters of 20 ~ 50 DEG C or alcoholic solution, removing solution;
5) add medium polar solvent in solid adsorbent slowly to shake, standing separation, removing solid adsorbent, the drying of gained solvent concentration obtains natural corn flavine product.
Described step 2) according to the operating process of step 1), previous step gained filter residue is extracted again, extract and repeat 2-4 time altogether;
Again carry out leaching process: to refer to previous step gained filter residue again according to raw materials quality: the ratio of solvent volume=1g:10 ~ 100ml adds above-mentioned solvent and again extracts, 30 ~ 80 DEG C are stirred extraction 1 ~ 10 hour, extract after terminating and staticly settle filtering separation; Obtain extracting solution and filter residue.
Described plant refers to one or two or more kinds in the fruit of plant, place calyx, root, stem, leaf, flower or whole plant; The plant used is matrimony vine, Franchet Groundcherry Calyx and Fruit, corn, capsicum, sea-buckthorn, pumpkin, one or two or more kinds in persimmon.
Described Extraction solvent is: the solvent mixture of one or two or more kinds in methyl alcohol, ethanol, propyl alcohol, butanols, ethyl acetate, methylene dichloride, trichloromethane, ether, acetone, hexanaphthene, normal hexane, sherwood oil;
Described medium polar solvent is: one or two or more kinds in methyl alcohol, ethanol, propyl alcohol, butanols, ethyl acetate, methylene dichloride, trichloromethane, ether, acetone;
Described solid adsorbent is: one or two or more kinds in silicon-dioxide, hydroxypropyl dextrane gel, polystyrene resin.
Step 3) and 4) in alcoholic solution in alcohol be one or two or more kinds in methyl alcohol, ethanol, propylene glycol.
The amount adding solid adsorbent after saponification terminates is, raw materials quality: solid adsorbent quality=1:0.1 ~ 10.
The add-on of medium polar solvent is, solid adsorbent quality: medium polar solvent volume=1g:2 ~ 20ml.
Described preparation method:
1) will grind as raw material, according to raw materials quality after one or two or more kinds drying in plant: the ratio of solvent volume=1g:10 ~ 50ml adds Extraction solvent, 30 ~ 60 DEG C be stirred extraction 1 ~ 10 hour, extract after terminating and staticly settle filtering separation; Obtain extracting solution and filter residue;
2) according to the operating process of step 1), previous step gained filter residue is extracted again, extract and repeat 2-4 time altogether;
3) united extraction liquid is evaporated to solvent and is evaporated, and adding volume is 1/2 ~ 1 times of former extraction volume, the alcoholic solution of mass concentration 5 ~ 30%KOH or NaOH, and 10 ~ 60 DEG C are stirred saponification 1 ~ 40 hour;
4) saponification adds solid adsorbent after terminating, and the add-on of solid adsorbent is, raw materials quality: solid adsorbent quality=1:0.5 ~ 8; Slow stirring 0.5 ~ 10 hour, standing separation, obtains the solid adsorbent of enrichment natural corn flavine; It is neutral for rinsing the solid adsorbent being rich in natural corn flavine to institute pH with the deionized waters of 20 ~ 50 DEG C or alcoholic solution, removing solution;
5) add medium polar solvent in solid adsorbent, the add-on of medium polar solvent is: solid adsorbent quality: medium polar solvent volume=1g:2 ~ 8ml; Slow concussion, standing separation, removing solid adsorbent, the drying of gained solvent concentration obtains natural corn flavine product.
Described preparation method:
1) will grind as raw material, according to raw materials quality after one or two or more kinds drying in plant: the ratio of solvent volume=1g:20ml adds Extraction solvent, 40 DEG C be stirred extraction 2 hours, extract after terminating and staticly settle filtering separation; Obtain extracting solution and filter residue;
2) according to the operating process of step 1), previous step gained filter residue is extracted again, extract and repeat 3 times altogether;
3) united extraction liquid is evaporated to solvent and is evaporated, and adding volume is 1 times of former extraction volume, the alcoholic solution of mass concentration 10%KOH or NaOH, and 40 DEG C are stirred saponification 10 hours;
4) saponification adds solid adsorbent after terminating, and the add-on of solid adsorbent is, raw materials quality: solid adsorbent quality=1:1; Slow stirring 2 hours, standing separation, obtains the solid adsorbent of enrichment natural corn flavine; It is neutral for rinsing the solid adsorbent being rich in natural corn flavine to institute pH with the deionized waters of 40 DEG C or alcoholic solution, removing solution;
5) add medium polar solvent in solid adsorbent, the add-on of medium polar solvent is: solid adsorbent quality: medium polar solvent volume=1g:6ml; Slow concussion, standing separation, removing solid adsorbent, the drying of gained solvent concentration obtains natural corn flavine product.
Feature of the present invention is as follows:
1 environmental protection.In-situ enrichment method decreases the step that traditional method makes to wash with water alkali, decreases the discharge of waste water; Zeaxanthin after enrichment just can wash-out with a small amount of solvent, decreases the usage quantity of organic solvent, has the feature of environmental protection.
In 2 products, zeaxanthin content is high.The zeaxanthin content prepared by preparation technology of the present invention is adopted to can reach more than 90%.
3 have a good application prospect.Zeaxanthin is the main component of human body macular pigment, and supplementary zeaxanthin can prevent the eye disease such as senile macular degeneration SMD, cataract, and has good mitigation for visual fatigue etc.; Zeaxanthin also has sunscreen effect simultaneously, and the zeaxanthin security of natural extract is high, therefore has good application prospect in fields such as food, healthcare products, medicine, makeup.
Accompanying drawing explanation
Fig. 1 is the mass spectrum of the embodiment of the present invention 1 zeaxanthin.
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the embodiment of the present invention 1 zeaxanthin.
Fig. 3 is the liquid chromatogram (in figure, * is zeaxanthin) of the embodiment of the present invention 1 zeaxanthin.
Embodiment
Embodiment 1
Take Chinese wolfberry fruit as raw material, prepare zeaxanthin according to following technique:
Get Chinese wolfberry fruit lyophilize, clay into power, cross 100 mesh sieve, get undersize powder 1000 grams, according to Chinese wolfberry fruit quality: the ratio of solvent volume=1g:10ml adds ethyl acetate 10 liters, 30 DEG C are stirred extraction 2 hours, extract after terminating and staticly settle separation; Obtain extracting solution and filter residue;
Filter residue again adds ethyl acetate 10 liters and carries out second time extraction; 30 DEG C are stirred extraction 2 hours; Separation is staticly settled after extraction terminates; Obtain extracting solution and filter residue;
Extract and repeat 3 times altogether; United extraction liquid, vacuum concentration is evaporated completely to organic solvent, adds 5 mass per liter concentration 10%KOH ethanolic solns, and 30 DEG C are stirred saponification 20 hours;
Solid adsorbent is added after saponification terminates---hydroxypropyl dextrane gel 1000 grams, slowly stir 0.5 hour, standing separation, obtains the solid adsorbent of enrichment natural corn flavine; It is neutral for rinsing the solid adsorbent being rich in natural corn flavine to institute pH with the deionized waters of 20 DEG C, except anhydrating;
Add 8 liters of ethyl acetate in solid adsorbent slowly to shake, standing separation, removing solid adsorbent, the drying of gained solvent concentration obtains natural corn flavine product 23 grams, by mass spectrum (Fig. 1), proton nmr spectra (Fig. 2), liquid chromatography (Fig. 3), in checking product, main component is zeaxanthin, and purity is 78%.
Embodiment 2
With Franchet Groundcherry Calyx and Fruit fruit for raw material, prepare zeaxanthin according to following technique:
Get the lyophilize of Franchet Groundcherry Calyx and Fruit fruit, clay into power, cross 100 mesh sieve, get undersize powder 1000 grams, according to Franchet Groundcherry Calyx and Fruit fruit quality: the ratio of solvent volume=1g:50ml adds 50 liters, acetone, 60 DEG C are stirred extraction 5 hours, extract after terminating and staticly settle separation; Obtain extracting solution and filter residue;
Filter residue again adds 50 liters, acetone and carries out second time extraction; 60 DEG C are stirred extraction 5 hours; Separation is staticly settled after extraction terminates; Obtain extracting solution and filter residue;
Extract and repeat 3 times altogether; United extraction liquid, vacuum concentration is evaporated completely to organic solvent, adds 50 mass per liter concentration 30%NaOH methanol solutions, and 60 DEG C are stirred saponification 10 hours;
Solid adsorbent is added after saponification terminates---polystyrene resin 10 kilograms, slowly stir 5 hours, standing separation, obtains the solid adsorbent of enrichment natural corn flavine; It is neutral for rinsing the solid adsorbent being rich in natural corn flavine to institute pH with the deionized waters of 20 DEG C, except anhydrating;
Ether and ethyl acetate mixed solvent 100 liters slowly concussion is added in solid adsorbent, standing separation, removing solid adsorbent, the drying of gained solvent concentration obtains natural corn flavine product 30 grams, method by identical with embodiment 1: mass spectrum, proton nmr spectra, liquid chromatography etc. prove that products therefrom is zeaxanthin, and purity is 68%.
Embodiment 3
Take capsicum as raw material, prepare zeaxanthin according to following technique:
Get capsicum lyophilize, clay into power, cross 100 mesh sieve, get undersize powder 1000 grams, according to capsicum quality: the ratio of solvent volume=1g:100ml adds sherwood oil and methylene dichloride mixed solvent (volume ratio 1:1) 100 liters, 80 DEG C are stirred extraction 1 hour, extract after terminating and staticly settle separation; Obtain extracting solution and filter residue;
Filter residue again adds sherwood oil and methylene dichloride mixed solvent 100 liters carries out second time extraction; 80 DEG C are stirred extraction 1 hour; Separation is staticly settled after extraction terminates; Obtain extracting solution and filter residue;
Extract and repeat 3 times altogether; United extraction liquid, vacuum concentration is evaporated completely to organic solvent, adds 10 mass per liter concentration 50%KOH ethanolic solns, and 80 DEG C are stirred saponification 1 hour;
Solid adsorbent is added after saponification terminates---silicon-dioxide 5 kilograms, slowly stir 1 hour, standing separation, obtains the solid adsorbent of enrichment natural corn flavine; It is neutral for rinsing the solid adsorbent being rich in natural corn flavine to institute pH with the ethanolic solns of 20 DEG C, removing solution;
Ether 25 liters slowly concussion is added in solid adsorbent, standing separation, removing solid adsorbent, the drying of gained solvent concentration obtains natural corn flavine product 25 grams, method by identical with embodiment 1: mass spectrum, proton nmr spectra, liquid chromatography etc. prove that products therefrom is zeaxanthin, and purity is 60%.
Embodiment 4
Take franchet groundcherry calyx or fruit as raw material, prepare zeaxanthin according to following technique:
Get franchet groundcherry calyx or fruit lyophilize, clay into power, cross 100 mesh sieve, get undersize powder 1000 grams, add the mixed solvent 50 liters of methyl alcohol and ethyl acetate, 50 DEG C are stirred extraction 8 hours, extract after terminating and staticly settle separation; Obtain extracting solution and filter residue;
The mixed solvent 50 liters that filter residue adds methyl alcohol and ethyl acetate again carries out second time extraction; 50 DEG C are stirred extraction 5 hours; Separation is staticly settled after extraction terminates; Obtain extracting solution and filter residue;
Extract and repeat 3 times altogether; United extraction liquid, vacuum concentration is evaporated completely to organic solvent, adds 40 mass per liter concentration 20%NaOH methanol solutions, and 30 DEG C are stirred saponification 20 hours;
2000 grams of solid adsorbent are added after saponification terminates---polystyrene resin, slowly stir 5 hours, standing separation, obtains the solid adsorbent of enrichment natural corn flavine; It is neutral for rinsing the solid adsorbent being rich in natural corn flavine to institute pH with the deionized waters of 30 DEG C, except anhydrating;
Trichloroethane 40 liters slowly concussion is added in solid adsorbent, standing separation, removing solid adsorbent, the drying of gained solvent concentration obtains natural corn flavine product 60 grams, method by identical with embodiment 1: mass spectrum, proton nmr spectra, liquid chromatography etc. prove that products therefrom is zeaxanthin, and purity is 75%.
Embodiment 5
Take corn as raw material, prepare zeaxanthin according to following technique:
Get corn lyophilize, clay into power, cross 100 mesh sieve, get undersize powder 1000 grams, add the mixed solvent 20 liters of sherwood oil and ethyl acetate, 30 DEG C are stirred extraction 5 hours, extract after terminating and staticly settle separation; Obtain extracting solution and filter residue;
The mixed solvent 20 liters that filter residue adds sherwood oil and ethyl acetate again carries out second time extraction; 30 DEG C are stirred extraction 5 hours; Separation is staticly settled after extraction terminates; Obtain extracting solution and filter residue;
Extract and repeat 3 times altogether; United extraction liquid, vacuum concentration is evaporated completely to organic solvent, adds 10 mass per liter concentration 5%KOH methanol solutions, and 10 DEG C are stirred saponification 20 hours;
500 grams of solid adsorbent are added after saponification terminates---silicon-dioxide, slowly stir 2 hours, standing separation, obtains the solid adsorbent of enrichment natural corn flavine; It is neutral for rinsing the solid adsorbent being rich in natural corn flavine to institute pH with the ethanol of 40 DEG C, except desolventizing;
Trichloroethane 1 liter slowly concussion is added in solid adsorbent, standing separation, removing solid adsorbent, the drying of gained solvent concentration obtains natural corn flavine product 36 grams, method by identical with embodiment 1: mass spectrum, proton nmr spectra, liquid chromatography etc. prove that products therefrom is zeaxanthin, and purity is 60%.
Embodiment 6
With Chinese wolfberry fruit and Leaf of Matrimonyvine for raw material, prepare zeaxanthin according to following technique:
Get Chinese wolfberry fruit and Leaf of Matrimonyvine lyophilize, clay into power, cross 100 mesh sieve, get undersize powder 1000 grams, add the mixed solvent 80 liters of normal hexane and ethanol (volume ratio 1:1), 35 DEG C are stirred extraction 4 hours, extract after terminating and staticly settle separation; Obtain extracting solution and filter residue;
The mixed solvent that filter residue adds normal hexane and ethanol (volume ratio 1:1) again carries out second time extraction; 5 DEG C are stirred extraction 4 hours; Separation is staticly settled after extraction terminates; Obtain extracting solution and filter residue;
Extract and repeat 3 times altogether; United extraction liquid, vacuum concentration is evaporated completely to organic solvent, adds 40 mass per liter concentration 15%KOH ethanolic solns, and 25 DEG C are stirred saponification 8 hours;
3000 grams of solid adsorbent are added after saponification terminates---hydroxypropyl dextrane gel, slowly stir 1 hour, standing separation, obtains the solid adsorbent of enrichment natural corn flavine; It is neutral for rinsing the solid adsorbent being rich in natural corn flavine to institute pH with the methanol solutions of 40 DEG C, except desolventizing;
Methylene dichloride 9 liters slowly concussion is added in solid adsorbent, standing separation, removing solid adsorbent, the drying of gained solvent concentration obtains natural corn flavine product 28 grams, by mass spectrum (Fig. 1), proton nmr spectra (Fig. 2), liquid chromatography (Fig. 3), in checking product, main component is zeaxanthin, and purity is 82%.
Embodiment 7
With pumpkin and Flos Cucurbitae for raw material, prepare zeaxanthin according to following technique:
Get lyophilize, clay into power, cross 100 mesh sieve, get undersize powder 1000 grams, add the mixed solvent 60 liters of sherwood oil and normal hexane (volume ratio 1:1), 40 DEG C are stirred extraction 5 hours, extract after terminating and staticly settle separation; Obtain extracting solution and filter residue;
The mixed solvent 60 liters that filter residue adds sherwood oil and normal hexane again carries out second time and extracts; Stir extraction 5 hours; Separation is staticly settled after extraction terminates; Obtain extracting solution and filter residue;
Extract and repeat 3 times altogether; United extraction liquid, vacuum concentration is evaporated completely to organic solvent, adds 10 mass per liter concentration 35%NaOH methyl alcohol and alcohol mixed solutions, and 40 DEG C are stirred saponification 10 hours;
Add 100 grams of solid adsorbent-polystyrene resins after saponification terminates, slowly stir 5 hours, standing separation, obtains the solid adsorbent of enrichment natural corn flavine; It is neutral for rinsing the solid adsorbent being rich in natural corn flavine to institute pH with the deionized waters of 40 DEG C, except anhydrating;
Ethyl acetate 300 milliliters slowly concussion is added in solid adsorbent, standing separation, removing solid adsorbent, the drying of gained solvent concentration obtains natural corn flavine product 26 grams, method by identical with embodiment 1: mass spectrum, proton nmr spectra, liquid chromatography etc. prove that products therefrom is zeaxanthin, and purity is 69%.
Embodiment 8
Take persimmon as raw material, prepare zeaxanthin according to following technique:
Get persimmon lyophilize, clay into power, cross 100 mesh sieve, get undersize powder 1000 grams, add ethyl acetate 50 liters, 35 DEG C are stirred extraction 3 hours, extract after terminating and staticly settle separation; Obtain extracting solution and filter residue;
Filter residue again adds ethyl acetate 50 liters and carries out second time extraction; 35 DEG C are stirred extraction 3 hours; Separation is staticly settled after extraction terminates; Obtain extracting solution and filter residue;
Extract and repeat 3 times altogether; United extraction liquid, vacuum concentration is evaporated completely to organic solvent, adds 10 mass per liter concentration 20%NaOH methyl alcohol and alcohol mixed solutions, and 35 DEG C are stirred saponification 10 hours;
Solid adsorbent is added after saponification terminates---polystyrene 1000 grams, slowly stir 3 hours, standing separation, obtains the solid adsorbent of enrichment natural corn flavine; It is neutral for rinsing the solid adsorbent being rich in natural corn flavine to institute pH with the deionized waters of 35 DEG C, except anhydrating;
Add 20 liters of methyl alcohol in solid adsorbent slowly to shake, standing separation, removing solid adsorbent, the drying of gained solvent concentration obtains natural corn flavine product 21 grams, by mass spectrum (Fig. 1), proton nmr spectra (Fig. 2), liquid chromatography (Fig. 3), in checking product, main component is zeaxanthin, and purity is 75%.
Embodiment 9
Take sea-buckthorn as raw material, prepare zeaxanthin according to following technique:
Get sea-buckthorn lyophilize, clay into power, cross 100 mesh sieve, get undersize powder 1000 grams, add methyl alcohol 20 liters, 40 DEG C are stirred extraction 2 hours, extract after terminating and staticly settle separation; Obtain extracting solution and filter residue;
Filter residue again adds methyl alcohol 20 liters and carries out second time extraction; 40 DEG C are stirred extraction 2 hours; Separation is staticly settled after extraction terminates; Obtain extracting solution and filter residue;
Extract and repeat 3 times altogether; United extraction liquid, vacuum concentration is evaporated completely to organic solvent, adds 20 mass per liter concentration 10%NaOH methyl alcohol and alcohol mixed solutions, and 40 DEG C are stirred saponification 10 hours;
Solid adsorbent is added after saponification terminates---hydroxypropyl dextrane gel 1000 grams, slowly stir 2 hours, standing separation, obtains the solid adsorbent of enrichment natural corn flavine; It is neutral for rinsing the solid adsorbent being rich in natural corn flavine to institute pH with the deionized waters of 40 DEG C, except anhydrating;
Add 6 liters of methyl alcohol in solid adsorbent slowly to shake, standing separation, removing solid adsorbent, the drying of gained solvent concentration obtains natural corn flavine product 32 grams, by mass spectrum (Fig. 1), proton nmr spectra (Fig. 2), liquid chromatography (Fig. 3), in checking product, main component is zeaxanthin, and purity is 95%.
Embodiment 10
With Franchet Groundcherry Calyx and Fruit fruit and place calyx for raw material, prepare zeaxanthin according to following technique:
Get Franchet Groundcherry Calyx and Fruit fruit and place calyx lyophilize, clay into power, cross 100 mesh sieve, get undersize powder 1000 grams, add 2 liters, acetone, 90 DEG C are stirred extraction 5 hours, extract after terminating and staticly settle separation; Obtain extracting solution and filter residue;
Filter residue again adds 2 liters, acetone and carries out second time extraction; 90 DEG C are stirred extraction 5 hours; Separation is staticly settled after extraction terminates; Obtain extracting solution and filter residue;
Extract and repeat 3 times altogether; United extraction liquid, vacuum concentration is evaporated completely to organic solvent, adds 4 mass per liter concentration 60%NaOH methanol solutions, and 90 DEG C are stirred saponification 10 hours;
80 grams of solid adsorbent are added after saponification terminates---polystyrene resin, slowly stir 5 hours, standing separation, obtains the solid adsorbent of enrichment natural corn flavine; It is neutral for rinsing the solid adsorbent being rich in natural corn flavine to institute pH with the deionized waters of 70 DEG C, except anhydrating;
Ethyl acetate 100 milliliters slowly concussion is added in solid adsorbent, standing separation, removing solid adsorbent, the drying of gained solvent concentration obtains natural corn flavine product 5 grams, method by identical with embodiment 1: mass spectrum, proton nmr spectra, liquid chromatography etc. prove that products therefrom is zeaxanthin, and purity is 16%.
Claims (9)
1. in-situ enrichment legal system is for a preparation method for natural corn flavine, it is characterized in that:
1) will grind as raw material, according to raw materials quality after one or two or more kinds the position drying in plant: the ratio of solvent volume=1g:10 ~ 100ml adds Extraction solvent, 30 ~ 80 DEG C be stirred extraction 1 ~ 10 hour, extract after terminating and staticly settle filtering separation; Obtain extracting solution and filter residue;
2) according to the operating process of step 1), previous step gained filter residue is extracted again, extract and repeat 2-4 time altogether;
3) united extraction liquid is evaporated to solvent and is evaporated, and adding volume is 1/10 ~ 1 times of former single-trial extraction solvent volume, the alcoholic solution of mass concentration 1 ~ 50%KOH or NaOH, and 10 ~ 80 DEG C are stirred saponification 1 ~ 40 hour;
4) saponification adds solid adsorbent after terminating, and slowly stirs 0.5 ~ 10 hour, standing separation, obtains the solid adsorbent of enrichment natural corn flavine; It is neutral for rinsing the solid adsorbent being rich in natural corn flavine to institute pH with the deionized waters of 20 ~ 60 DEG C or alcoholic solution, removing solution;
5) add medium polar solvent in solid adsorbent slowly to shake, standing separation, removing solid adsorbent, the drying of gained solvent concentration obtains natural corn flavine product.
2., according to preparation method according to claim 1, it is characterized in that:
Described step 2) according to the operating process of step 1), previous step gained filter residue is extracted again, extract and repeat 2-4 time altogether;
Again carry out leaching process: to refer to previous step gained filter residue again according to raw materials quality: the ratio of solvent volume=1g:10 ~ 100ml adds above-mentioned solvent and again extracts, 30 ~ 80 DEG C are stirred extraction 1 ~ 10 hour, extract after terminating and staticly settle filtering separation; Obtain extracting solution and filter residue.
3. according to preparation method according to claim 1, it is characterized in that: described plant refers to one or two or more kinds in the fruit of plant, place calyx, root, stem, leaf, flower or whole plant; The plant used is matrimony vine, Franchet Groundcherry Calyx and Fruit, corn, capsicum, sea-buckthorn, pumpkin, one or two or more kinds in persimmon.
4., according to preparation method according to claim 1, it is characterized in that:
Described Extraction solvent is: the solvent mixture of one or two or more kinds in methyl alcohol, ethanol, propyl alcohol, butanols, ethyl acetate, methylene dichloride, trichloromethane, ether, acetone, hexanaphthene, normal hexane, sherwood oil;
Described medium polar solvent is: one or two or more kinds in methyl alcohol, ethanol, propyl alcohol, butanols, ethyl acetate, methylene dichloride, trichloromethane, ether, acetone;
Described solid adsorbent is: one or two or more kinds in silicon-dioxide, hydroxypropyl dextrane gel, polystyrene resin.
5., according to preparation method according to claim 1, it is characterized in that:
Step 3) and 4) in alcoholic solution in alcohol be one or two or more kinds in methyl alcohol, ethanol, propylene glycol.
6., according to preparation method according to claim 1, it is characterized in that:
The amount adding solid adsorbent after saponification terminates is, raw materials quality: solid adsorbent quality=1:0.1 ~ 10.
7., according to preparation method according to claim 1, it is characterized in that:
The add-on of medium polar solvent is, solid adsorbent quality: medium polar solvent volume=1g:2 ~ 20ml.
8., according to preparation method according to claim 1, it is characterized in that:
1) will grind as raw material, according to raw materials quality after one or two or more kinds drying in plant: the ratio of solvent volume=1g:10 ~ 50ml adds Extraction solvent, 30 ~ 60 DEG C be stirred extraction 1 ~ 10 hour, extract after terminating and staticly settle filtering separation; Obtain extracting solution and filter residue;
2) according to the operating process of step 1), previous step gained filter residue is extracted again, extract and repeat 2-4 time altogether;
3) united extraction liquid is evaporated to solvent and is evaporated, and adding volume is 1/2 ~ 1 times of former Extraction solvent volume, the alcoholic solution of mass concentration 5 ~ 30%KOH or NaOH, and 10 ~ 60 DEG C are stirred saponification 1 ~ 40 hour;
4) saponification adds solid adsorbent after terminating, and the add-on of solid adsorbent is, raw materials quality: solid adsorbent quality=1:0.5 ~ 8; Slow stirring 0.5 ~ 10 hour, standing separation, obtains the solid adsorbent of enrichment natural corn flavine; It is neutral for rinsing the solid adsorbent being rich in natural corn flavine to institute pH with the deionized waters of 20 ~ 50 DEG C or alcoholic solution, removing solution;
5) add medium polar solvent in solid adsorbent, the add-on of medium polar solvent is: solid adsorbent quality: medium polar solvent volume=1g:2 ~ 8ml; Slow concussion, standing separation, removing solid adsorbent, the drying of gained solvent concentration obtains natural corn flavine product.
9., according to preparation method according to claim 1, it is characterized in that:
1) will grind as raw material, according to raw materials quality after one or two or more kinds drying in plant: the ratio of solvent volume=1g:20ml adds Extraction solvent, 40 DEG C be stirred extraction 2 hours, extract after terminating and staticly settle filtering separation; Obtain extracting solution and filter residue;
2) according to the operating process of step 1), previous step gained filter residue is extracted again, extract and repeat 3 times altogether;
3) united extraction liquid is evaporated to solvent and is evaporated, and adding volume is 1 times of former Extraction solvent volume, the alcoholic solution of mass concentration 10%KOH or NaOH, and 40 DEG C are stirred saponification 10 hours;
4) saponification adds solid adsorbent after terminating, and the add-on of solid adsorbent is, raw materials quality: solid adsorbent quality=1:1; Slow stirring 2 hours, standing separation, obtains the solid adsorbent of enrichment natural corn flavine; It is neutral for rinsing the solid adsorbent being rich in natural corn flavine to institute pH with the deionized waters of 40 DEG C or alcoholic solution, removing solution;
5) add medium polar solvent in solid adsorbent, the add-on of medium polar solvent is: solid adsorbent quality: medium polar solvent volume=1g:6ml; Slow concussion, standing separation, removing solid adsorbent, the drying of gained solvent concentration obtains natural corn flavine product.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410038945.2A CN104803901A (en) | 2014-01-27 | 2014-01-27 | Method for preparing zeaxanthin through in situ enrichment |
| PCT/CN2014/074707 WO2015109657A1 (en) | 2014-01-27 | 2014-04-03 | Method for manufacturing nature zeaxanthin by means of in-situ concentration |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410038945.2A CN104803901A (en) | 2014-01-27 | 2014-01-27 | Method for preparing zeaxanthin through in situ enrichment |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106543769A (en) * | 2016-10-31 | 2017-03-29 | 中国科学院兰州化学物理研究所 | The method that the carotenoidses monomer pigment based on cryptoxanthin is extracted in Fructus Lycii |
| CN106631953A (en) * | 2016-12-29 | 2017-05-10 | 河南中大恒源生物科技股份有限公司 | Preparation method of beta-carotene in paprika |
| CN110563625A (en) * | 2019-09-29 | 2019-12-13 | 山东天音生物科技有限公司 | Method for separating and purifying zeaxanthin from marigold oleoresin |
| CN110835315A (en) * | 2019-10-28 | 2020-02-25 | 百瑞源枸杞股份有限公司 | Preparation method of lycium ruthenicum red pigment |
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| CN103080238A (en) * | 2010-08-25 | 2013-05-01 | 帝斯曼知识产权资产管理有限公司 | Process for the manufacture of a highly enriched extract containing zeaxanthin and/or its esters |
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| AU1271999A (en) * | 1997-10-21 | 1999-05-10 | Office Of Technology Liaison | Process for extraction and purification of lutein, zeaxanthin and rare carotenoids from marigold flowers and plants |
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- 2014-01-27 CN CN201410038945.2A patent/CN104803901A/en active Pending
- 2014-04-03 WO PCT/CN2014/074707 patent/WO2015109657A1/en active Application Filing
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| CN103080238A (en) * | 2010-08-25 | 2013-05-01 | 帝斯曼知识产权资产管理有限公司 | Process for the manufacture of a highly enriched extract containing zeaxanthin and/or its esters |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106543769A (en) * | 2016-10-31 | 2017-03-29 | 中国科学院兰州化学物理研究所 | The method that the carotenoidses monomer pigment based on cryptoxanthin is extracted in Fructus Lycii |
| CN106631953A (en) * | 2016-12-29 | 2017-05-10 | 河南中大恒源生物科技股份有限公司 | Preparation method of beta-carotene in paprika |
| CN106631953B (en) * | 2016-12-29 | 2019-01-22 | 河南中大恒源生物科技股份有限公司 | The preparation method of beta carotene in a kind of capsicum |
| CN110563625A (en) * | 2019-09-29 | 2019-12-13 | 山东天音生物科技有限公司 | Method for separating and purifying zeaxanthin from marigold oleoresin |
| CN110835315A (en) * | 2019-10-28 | 2020-02-25 | 百瑞源枸杞股份有限公司 | Preparation method of lycium ruthenicum red pigment |
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| WO2015109657A1 (en) | 2015-07-30 |
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