CN101029183A - Method for separating and purifying high-tone jasmine flavine from jasmine - Google Patents
Method for separating and purifying high-tone jasmine flavine from jasmine Download PDFInfo
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Abstract
A method for separating and purifying gardenin from capejasmine is carried out by extracting gardenin from capejasmine by hydrophilic organic solvent, preparing into concrete, enriched purifying by macro-porous adsorptive resin to prepare gardenin crude product, extracting by heated carbethoxy acetate, removing impurities and preparing into gardenin with E4401%1cm>=580, A238/A440<=0.25 and A320/A440<=0.24. It's simple, cheap and efficient, has better purity and easy storage.
Description
Technical field
The present invention relates to a kind of from plant the Green Chemistry preparation method of separation and purification of natural pigment, more specifically relate to a kind of from cape jasmine the method for separation and purification high luminance relay valency Gardenia Yellow.
Background technology
Cape jasmine is the fruit of madder wort cape jasmine (Gardenia jasminoides Ellis), have effects such as mattress courage, flat liver, heat-clearing, hemostasis, step-down, antidiarrheal, be the large traditional Chinese medicine material of China, it is one of first batch of integration of drinking and medicinal herbs material of Ministry of Health's promulgation, it is the choice drug of tcm clinical practice treatment icterohepatitis, also be the raw material that extracts the natural gardenia pigment, abound with in Fujian, province mountain areas such as Zhejiang, Jiangxi, emblem, Hunan.
Up to now, the compound that isolation identification goes out from cape jasmine mainly contains water-soluble carotenoid, iridoid glycoside compounds, chlorogenic acid, flavonoid, alcohol compound, cape jasmine polysaccharide etc.Wherein, Gardenia Yellow is the water-soluble carotenoid class natural pigment of the unique existence of nature of extracting from cape jasmine fruit, have that strong coloring force, lovely luster, tone are soft naturally, good stability, solvability are strong, free from extraneous odour, have no side effect, the safety performance advantages of higher, be widely used in food, fruit wine, beverage, medicine, daily-use chemical industry, makeup etc., being popular natural additive for foodstuff in the world at present, is herbal industry, beverage/food industry, cosmetic industry, the indispensable natural pigment raw material of pharmaceutical industries.
Gardenia Yellow is rather well received in developed countries such as America and Europe, Japan, and the international demand amount is increasing with average annual 10% speed, ranking the 4th in Japanese natural pigment market.Japanese high luminance relay valency Gardenia Yellow (E in 2005
440 1% 1cm〉=220, A
238/ A
440≤ 0.40) demand is 400 tons, and price is 360,000 yuan/ton of Renminbi.Gardenia Yellow (the E of China's production in 2005
440 1% 1cm≤ 90, A
238/ A
440〉=1.5) ultimate production is 180 tons, and 80% outlet Japan specializes in the secondary deep processing.The A of the Gardenia Yellow that China produces
238/ A
440Chang Gaoda 2.0～3.0, and wherein jasminoidin content is higher reaches 7～8%.The Gardenia Yellow that Japan produces can be accomplished A
238/ A
4400.25 and A
320/ A
440≤ 0.25.
At present, the Gardenia Yellow of Shi Yonging is still a kind of mixture in the world, be that crocin (Crocin) and crocetin (Crocetin) with the water-soluble carotenoid class is main component, also contain part chlorogenic acid and iridoid glycoside compounds impurity such as (being mainly jasminoidin).Therefore, the Gardenia Yellow aqueous solution has three absorption peak: 238nm, 320nm, 440nm in the ultraviolet-visible light district, is respectively the charateristic avsorption band of jasminoidin, chlorogenic acid, Crocin and trans-crocetin.Usually adopt A in the world
238/ A
440And A
320/ A
440As weighing the index that green change of Gardenia Yellow and ash become possibility, A
238/ A
440≤ 0.40 can avoid the generation of green change, A
320/ A
440≤ 0.36 generation that can avoid ash to become.
Jasminoidin is the principal element that causes the green change of gardenia yellow pigment, it under the effect of proteolytic enzyme or beta-glucosidase easily and the primary amino compound generation gardenia blue pigment that reacts.Chlorogenic acid is oxidized easily in storage and use, is the principal element that causes that gardenia yellow pigment ash becomes.In order to prevent that effectively green change and ash from becoming, obtain high luminance relay valency Gardenia Yellow, must be from extracting and refining setting about, remove impurity such as jasminoidin in the gardenia yellow pigment and chlorogenic acid as much as possible.
Jasminoidin and chlorogenic acid are soluble in water, methyl alcohol, ethanol isopolarity solvent, are insoluble in hydrophobic organic solvents such as ether, chloroform, tetracol phenixin.Jasminoidin and chlorogenic acid be solvable in the ethyl acetate of heat, put and can separate out after cold.In the ultraviolet-visible light zone, the maximum charateristic avsorption band of jasminoidin and chlorogenic acid is respectively 238nm and 320nm.
With crocin and crocetin is soluble in water, the ethanol isopolarity solvent of Gardenia Yellow of main component, is insoluble in non-polar solvents such as ethyl acetate, chloroform, ether, benzene, sherwood oil, normal hexane.Crocin and crocetin have three absorption peaks in the ultraviolet-visible light zone, 400～500nm absorption peak is very strong, 320～340nm absorption peak is medium, 250～260nm absorption peak is very weak, therefore, when adopting 440nm as the maximum charateristic avsorption band of Crocin and trans-crocetin, the ultimate value of the pure product of Gardenia Yellow is A
238/ A
440〉=0.20 and A
320/ A
440〉=0.22.
Summary of the invention
The object of the present invention is to provide a kind of from cape jasmine the method for separation and purification high luminance relay valency Gardenia Yellow, this preparation method adopts the separation and purification integrated technology of hydrophilic organic solvent extraction, macroporous adsorbent resin enrichment and ethyl acetate extraction removal of impurities, preparation high luminance relay valency Gardenia Yellow from cape jasmine, not only preparation technology is simple, separation and purification efficient height, suitability for industrialized production, and the look valency of the Gardenia Yellow of preparation easily and purity height, production cost are low.
Of the present invention a kind of from cape jasmine the method steps of separation and purification high luminance relay valency Gardenia Yellow be:
(1) preparation of Gardenia Yellow crude extract medicinal extract: with the cape jasmine is raw material, adopt 30～60% hydrophilic organic solvent aqueous solution of 5～20 times of cape jasmine dry weights (W/W), under 50～80 ℃ of conditions, extract 1～3 time, each 1～3 hour, united extraction liquid, filter, filtrate-0.06～-0.095MPa, 50～80 ℃ of conditions under, become Gardenia Yellow crude extract medicinal extract through decompression and solvent recovery, vacuum concentration;
(2) resin concentration of Gardenia Yellow crude product: medicinal extract is extremely saturated through the absorption with macroporous adsorbent resin Gardenia Yellow, debris and the more weak water-soluble impurity of adsorptive power that elder generation is not adsorbed with water (V/V) flush away that is no less than 2 times of amount of resin, again with 15～30% aqueous ethanolic solution (V/V) the flush away middle polarity impurity that is no less than 3 times of amount of resin, use 40～70% hydrophilic organic solvent aqueous solution (V/V) wash-out Gardenia Yellows of 3～9 times of amount of resin at last, elutriant-0.05～-0.09MPa, under 50～65 ℃ of conditions, through decompression and solvent recovery, vacuum concentration becomes the Gardenia Yellow crude product;
(3) purifying of high luminance relay valency Gardenia Yellow: under 50～70 ℃ of conditions, ethyl acetate with 3～10 times of amounts (W/W) fully extracts jasminoidin and the chlorogenic acid of removing in the Gardenia Yellow crude product, raffinate-0.05～-0.09MPa, 50～65 ℃ of conditions under, become high luminance relay valency Gardenia Yellow through decompression and solvent recovery, vacuum concentration.
Remarkable advantage of the present invention is:
One: the present invention adopts one or more mixed solvents in methyl alcohol, ethanol, acetone, propyl alcohol or the Virahol to extract Gardenia Yellow as hydrophilic organic solvent from cape jasmine, advantage 1: the solubility property of hydrophilic organic solvents such as methyl alcohol, ethanol is good, penetrativity to the cape jasmine cell is strong, easier being penetrated in the cape jasmine internal organizational structure improved the dissolution rate and the extraction efficiency of Gardenia Yellow in the cape jasmine greatly; Advantage 2: hydrophilic organic solvents such as the methyl alcohol of heat, ethanol are very big to the solubleness of Gardenia Yellow in the cape jasmine, and less to the solubleness of impurity such as protein, polysaccharide, essential oil, inorganic salt, be more conducive to follow-up further separation and purification and obtain look valency and the higher Gardenia Yellow of purity.
Two: the present invention preferentially selects for use methyl alcohol or acetone as the advantage of hydrophilic solvent to be: though the extraction effect of hydrophilic organic solvents such as methyl alcohol, ethanol, acetone, propyl alcohol or Virahol is suitable, but for other hydrophilic organic solvent, the boiling point of methyl alcohol or acetone is lower, energy consumption is littler during solvent recuperation, the rate of recovery is higher, can significantly reduce the preparation cost of product.
Three: the present invention makes full use of macroporous adsorbent resin to different with to the adsorptive power of impurity such as jasminoidin, chlorogenic acid, protein, polysaccharide, inorganic salt of the adsorptive power of Gardenia Yellow, and in the hydrophilic organic solvent aqueous solution, with crocin and crocetin is the dissolubility difference of impurity such as the Gardenia Yellow of main component and jasminoidin, chlorogenic acid, really reaches the high efficiency separation of Gardenia Yellow and impurity.
Four: adopt purification by silica gel column chromatography to adopt technology such as polyamide column chromatography separates to compare with ZL 200310111453.3 with existing patent documentation CN 1807441A, the present invention makes full use of crocin and crocetin is insoluble in ethyl acetate, and jasminoidin and chlorogenic acid are solvable in the ethyl acetate of heat, put the characteristics that to separate out after cold, do not adopt column chromatography technology, and directly adopt the ethyl acetate extraction mode to remove impurity such as jasminoidin in the gardenia yellow pigment and chlorogenic acid, obtain high luminance relay valency Gardenia Yellow, the green change and the ash that can reduce Gardenia Yellow significantly become possibility, a green change and the difficult problem that ash becomes take place in Gardenia Yellow that energy solves Chinese domestic production for a long time easily in storage and use, have bigger generalization.
Five: the present invention makes up the integrated technology that adopts hydrophilic organic solvent extraction, macroporous adsorbent resin enrichment and ethyl acetate extraction removal of impurities, can suitability for industrialized production high luminance relay valency Gardenia Yellow, have that theoretical novelty, reasonable in technology, operational safety, technology are easy, an economically feasible, advantages of environment protection.
Embodiment
Implement separation and purification high luminance relay valency Gardenia Yellow from cape jasmine according to the described method steps of content of the present invention.
Wherein, the middle polarity impurity described in the step (2) is iridoid glycoside compounds, chlorogenic acid or flavones.
Used hydrophilic organic solvent can be one or more mixed solvents in methyl alcohol, ethanol, acetone, propyl alcohol or the Virahol, preferentially selects methyl alcohol or acetone for use.
The chemical constitution of the skeleton of used macroporous adsorbent resin can be one or both in polystyrene and the polyacrylic acid.
The index of the Gardenia Yellow that final separation and purification obtains is E
440 1% 1cm〉=580, A
238/ A
440≤ 0.25, A
320/ A
440≤ 0.24.
The Fructus Gardeniae iridoid glycoside compounds is one or more compounds in jasminoidin, different jasminoidin, genipin gentiobiose glycosides or the Geniposidic acid.
Gardenia Yellow is one or more compounds in crocetin, crocin 1, crocin 2 or the crocin 3.
The physical and chemical parameter measuring method of each prepared product of the present invention is as follows:
The high performance liquid chromatograph that the content of Gardenia Yellow, chlorogenic acid and Fructus Gardeniae iridoid glycoside compounds adopts the ultraviolet-visible three-wavelength to detect is simultaneously measured.Condition determination: Agilent 1100 type high performance liquid chromatographs (DAD diode-array detector), Waters Nova-Pak C18 chromatographic column (Ф 3.9 * 150mm, 5 μ m), methyl alcohol-0.2% phosphate aqueous solution is that moving phase is carried out gradient elution, the methyl alcohol ratio rises to 100% from 15% linear gradient in 60min, keeps 2min then.Flow velocity 1.0mL/min, 34 ℃ of column temperatures, sample size 20 μ L.The detection wavelength of Gardenia Yellow, chlorogenic acid and Fructus Gardeniae iridoid glycoside compounds is respectively 440nm, 320nm and 238nm.
Standard substance: jasminoidin, different jasminoidin, Geniposidic acid, genipin gentiobiose glycosides are purchased in Yoneyama company (Japan), and crocetin is purchased the company in Sigma, and chlorogenic acid, crocin are purchased in Nat'l Pharmaceutical ﹠ Biological Products Control Institute.
After measured, the content of testing compositions such as Fructus Gardeniae iridoid glycoside compounds, Gardenia Yellow and chlorogenic acid in used Zherong, the Fujian product cape jasmine (water content 3.8%) is respectively 70.5g/kg, 4.2g/kg and 12.8g/kg, and the index of the various high luminance relay valency Gardenia Yellows that separation and purification obtains is E
440 1% 1cm〉=580, A
238/ A
4400.25, A
320/ A
440≤ 0.24.
Preparation method's of the present invention embodiment is presented below:
Embodiment 1
Producing cape jasmine with the Zherong, Fujian is raw material, with the washing of bright cape jasmine, dry (air-dry, all can dry or dry), pulverize, cross 10～30 mesh sieves, get Cape Jasmine Fruit, the 3.3kg Cape Jasmine Fruit is put into extractor, with 60% methanol aqueous solution of 5 times of powder dry weights (W/W), refluxing extraction is 2 hours under 80 ℃ of conditions, filters, filtrate-0.06～-0.095MPa, 50～80 ℃ of conditions under, become Gardenia Yellow crude extract medicinal extract through decompression and solvent recovery, vacuum concentration.
Adding distil water is adjusted medicinal extract concentration and is reached 3.6 degree Beaume, adopt the HZ816 macroporous adsorbent resin, with 1.16 times of amount of resin/hour last column flow rate (V/V), the dynamic adsorption Gardenia Yellow is to saturated, debris and the more weak water-soluble impurity of adsorptive power that elder generation is not adsorbed with distilled water (V/V) flush away that is no less than 2 times of amount of resin, use 19% aqueous ethanolic solution (V/V) of 8 times of amount of resin to be divided into again 2 times, under the mixing speed condition of 68r/min, flush away iridoid glycoside compounds, middle polarity such as chlorogenic acid and flavones impurity, 40% methanol aqueous solution (V/V) of using 9 times of amount of resin at last with 0.56 times of amount of resin/hour flow velocity (V/V) wash-out Gardenia Yellow, elutriant-0.05～-0.09MPa, under 50～65 ℃ of conditions, through decompression and solvent recovery, vacuum concentration becomes the Gardenia Yellow crude product.
Under 50 ℃ of conditions, ethyl acetate with 4 times of amounts (W/W) fully extracts jasminoidin and the chlorogenic acid of removing in the Gardenia Yellow crude product, raffinate-0.05～-0.09MPa, 50～65 ℃ of conditions under, become high luminance relay valency Gardenia Yellow through decompression and solvent recovery, vacuum concentration.After measured, the index of Gardenia Yellow is E
440 1% 1cm=615, A
238/ A
440=0.20, A
320/ A
440=0.22.
Embodiment 2
The Cape Jasmine Fruit 2.6kg of 10～30 orders degreasing is put into extractor, 30% methanol aqueous solution with 20 times of Cape Jasmine Fruit dry weights (W/W), under 50 ℃ of conditions, extract 2 times, each 3 hours, united extraction liquid filters, filtrate-0.06～-0.095MPa, 50～80 ℃ of conditions under, become Gardenia Yellow crude extract medicinal extract through decompression and solvent recovery, vacuum concentration, medicinal extract concentration reaches 8 degree Beaume.
Under the mixing speed condition of 75r/min, directly adopt the HZ801 macroporous adsorbent resin that medicinal extract is carried out enrichment absorption Gardenia Yellow to saturated, debris and the more weak water-soluble impurity of adsorptive power that elder generation is not adsorbed with distilled water (V/V) flush away that is no less than 2 times of amount of resin, 24% the aqueous ethanolic solution (V/V) of using 6 times of amount of resin again with 1.0 times of amount of resin/hour flow velocity (V/V) flush away iridoid glycoside compounds, middle polarity such as chlorogenic acid and flavones impurity, 49% methanol aqueous solution (V/V) of using 6 times of amount of resin at last is under the mixing speed condition of 100r/min, the wash-out Gardenia Yellow, elutriant-0.05～-0.09MPa, under 50～65 ℃ of conditions, through decompression and solvent recovery, vacuum concentration becomes the Gardenia Yellow crude product.
Under 70 ℃ of conditions, ethyl acetate with 3 times of amounts (W/W) fully extracts jasminoidin and the chlorogenic acid of removing in the Gardenia Yellow crude product, raffinate-0.05～-0.09MPa, 50～65 ℃ of conditions under, become high luminance relay valency Gardenia Yellow through decompression and solvent recovery, vacuum concentration.After measured, the index of Gardenia Yellow is E
440 1% 1cm=583, A
238/ A
440=0.24, A
320/ A
440=0.24.
Embodiment 3
10～30 mesh sieves are washed, pulverize, crossed to bright cape jasmine, with the 2.6kg cape jasmine (with dry weight basis, W/W) drop in the extractor, add methyl alcohol-acetone (1: 1) solution of 10 times of cape jasmine dry weights (W/W), make the final concentration of methyl alcohol-acetone in the system (1: 1) aqueous solution reach 52%, refluxing extraction is 3 hours under 78 ℃ of conditions, filters, filtrate-0.06～-0.095MPa, 50～80 ℃ of conditions under, become Gardenia Yellow crude extract medicinal extract through decompression and solvent recovery, vacuum concentration.
Adding distil water is adjusted medicinal extract concentration and is reached 3 degree Beaume, adopt the HZ806 macroporous adsorbent resin, with 0.75 times of amount of resin/hour last column flow rate (V/V), the dynamic adsorption Gardenia Yellow is to saturated, debris and the more weak water-soluble impurity of adsorptive power that elder generation is not adsorbed with distilled water (V/V) flush away that is no less than 2 times of amount of resin, 30% the aqueous ethanolic solution (V/V) of using 3 times of amount of resin again with 0.5 times of amount of resin/hour flow velocity (V/V) flush away iridoid glycoside compounds, middle polarity such as chlorogenic acid and flavones impurity, 70% methyl alcohol-acetone (1: 1) of using 9 times of amount of resin at last (V/V) with 1.05 times of amount of resin/hour flow velocity (V/V) wash-out Gardenia Yellow, elutriant-0.05～-0.09MPa, under 50～65 ℃ of conditions, through decompression and solvent recovery, vacuum concentration becomes the Gardenia Yellow crude product.
Under 62 ℃ of conditions, ethyl acetate with 5 times of amounts (W/W) fully extracts jasminoidin and the chlorogenic acid of removing in the Gardenia Yellow crude product, raffinate-0.05～-0.09MPa, 50～65 ℃ of conditions under, become high luminance relay valency Gardenia Yellow through decompression and solvent recovery, vacuum concentration.After measured, the index of Gardenia Yellow is E
440 1% 1cm=603, A
238/ A
440=0.21, A
320/ A
440=0.23.
Embodiment 4
10～30 order Cape Jasmine Fruit 2.9kg are put into extractor, 60% aqueous ethanolic solution with 5 times of Cape Jasmine Fruit dry weights (W/W), lixiviate is 3 times under 80 ℃ of conditions, each 2 hours, united extraction liquid, filter, filtrate-0.06～-0.095MPa, 50～80 ℃ of conditions under, become Gardenia Yellow crude extract medicinal extract through decompression and solvent recovery, vacuum concentration.
Adding distil water is adjusted medicinal extract concentration and is reached 3 degree Beaume, adopt the D101 macroporous adsorbent resin, under the mixing speed condition of 78r/min, the absorption Gardenia Yellow is to saturated, earlier with debris and the adsorptive power more weak water-soluble impurity of distilled water (V/V) flush away aqueous ethanolic solution (V/V) not that is no less than 2 times of amount of resin to be adsorbed, use again 27%1.03 times of amount of resin of 4 times of amount of resin/hour flow velocity (V/V) flush away iridoid glycoside compounds, middle polarity such as chlorogenic acid and flavones impurity, 62% aqueous ethanolic solution (V/V) of using 3 times of amount of resin at last is under the mixing speed condition of 89r/min, the wash-out Gardenia Yellow, elutriant-0.05～-0.09MPa, under 50～65 ℃ of conditions, through decompression and solvent recovery, vacuum concentration becomes the Gardenia Yellow crude product.
Under 65 ℃ of conditions, ethyl acetate with 4 times of amounts (W/W) fully extracts jasminoidin and the chlorogenic acid of removing in the Gardenia Yellow crude product, raffinate-0.05～-0.09MPa, 50～65 ℃ of conditions under, become high luminance relay valency Gardenia Yellow through decompression and solvent recovery, vacuum concentration.After measured, the index of Gardenia Yellow is E
440 1% 1cm=592, A
238/ A
440=0.23, A
320/ A
440=0.24.
Embodiment 5
10～30 order Cape Jasmine Fruit 2.6kg are put into extractor, 55% methyl alcohol-Virahol (1: 1) aqueous solution with 12 times of Cape Jasmine Fruit dry weights (W/W), under 73 ℃ of conditions, extract 2 times, each 2 hours, united extraction liquid, filter, filtrate-0.06～-0.095MPa, 50～80 ℃ of conditions under, become Gardenia Yellow crude extract medicinal extract through decompression and solvent recovery, vacuum concentration.
Adding distil water is adjusted medicinal extract concentration and is reached 4.5 degree Beaume, adopt the DK110 macroporous adsorbent resin, with 1.0 times of amount of resin/hour flow velocity (V/V), the dynamic adsorption Gardenia Yellow is to saturated, debris and the more weak water-soluble impurity of adsorptive power that elder generation is not adsorbed with distilled water (V/V) flush away that is no less than 2 times of amount of resin, use 15% aqueous ethanolic solution (V/V) of 12 times of amount of resin to be divided into again 4 times, under the mixing speed condition of 60r/min, flush away iridoid glycoside compounds, middle polarity such as chlorogenic acid and flavones impurity, 50% methyl alcohol-Virahol (1: 1) aqueous solution (V/V) of using 8 times of amount of resin at last is under the mixing speed condition of 90r/min, the wash-out Gardenia Yellow, elutriant-0.05～-0.09MPa, under 50～65 ℃ of conditions, through decompression and solvent recovery, vacuum concentration becomes the Gardenia Yellow crude product.
Under 58 ℃ of conditions, ethyl acetate with 6 times of amounts (W/W) fully extracts jasminoidin and the chlorogenic acid of removing in the Gardenia Yellow crude product, raffinate-0.05～-0.09MPa, 50～65 ℃ of conditions under, become high luminance relay valency Gardenia Yellow through decompression and solvent recovery, vacuum concentration.After measured, the index of Gardenia Yellow is E
440 1% 1cm=602, A
238/ A
440=0.22, A
320/ A
440=0.23.
Embodiment 6
10～30 order Cape Jasmine Fruit 2.4kg are put into extractor, 30% aqueous ethanolic solution with 20 times of Cape Jasmine Fruit dry weights (W/W), under 50 ℃ of conditions, extract 2 times, each 3 hours, filter, filtrate-0.06～-0.095MPa, 50～80 ℃ of conditions under, become Gardenia Yellow crude extract medicinal extract through decompression and solvent recovery, vacuum concentration, medicinal extract concentration reaches 8 degree Beaume.
Under the mixing speed condition of 50r/min, directly adopt macroporous adsorbent resin HZ801: HZ802 (2: 1) that medicinal extract is carried out enrichment absorption Gardenia Yellow to saturated, the absorption Gardenia Yellow is to saturated, debris and the more weak water-soluble impurity of adsorptive power that elder generation is not adsorbed with distilled water (V/V) flush away that is no less than 2 times of amount of resin, 25% the aqueous ethanolic solution (V/V) of using 5 times of amount of resin again with 0.65 times of amount of resin/hour flow velocity (V/V) flush away iridoid glycoside compounds, middle polarity such as chlorogenic acid and flavones impurity, 70% aqueous ethanolic solution (V/V) of using 6 times of amount of resin at last with 1.0 times of amount of resin/hour flow velocity (V/V) wash-out Gardenia Yellow, elutriant-0.05～-0.09MPa, under 50～65 ℃ of conditions, through decompression and solvent recovery, vacuum concentration becomes the Gardenia Yellow crude product.
Under 50 ℃ of conditions, ethyl acetate with 10 times of amounts (W/W) fully extracts jasminoidin and the chlorogenic acid of removing in the Gardenia Yellow crude product, raffinate-0.05～-0.09MPa, 50～65 ℃ of conditions under, become high luminance relay valency Gardenia Yellow through decompression and solvent recovery, vacuum concentration.After measured, the index of Gardenia Yellow is E
440 1% 1cm=584, A
238/ A
440=0.25, A
320/ A
440=0.24.
Embodiment 7
10～30 order Cape Jasmine Fruit 2.9kg are put into extractor, with 20 times of cape jasmines (with dry weight basis, W/W) 30% aqueous acetone solution, under 50 ℃ of conditions, extract 3 times, each 3 hours, united extraction liquid filtered, filtrate-0.06～-0.095MPa, 50～80 ℃ of conditions under, become Gardenia Yellow crude extract medicinal extract through decompression and solvent recovery, vacuum concentration.
Adding distil water is adjusted medicinal extract concentration and is reached 4 degree Beaume, adopt Amberlite XAD-4 macroporous adsorbent resin, with 0.75 times of amount of resin/hour flow velocity (V/V), the dynamic adsorption Gardenia Yellow is to saturated, debris and the more weak water-soluble impurity of adsorptive power that elder generation is not adsorbed with distilled water (V/V) flush away that is no less than 2 times of amount of resin, use 15% aqueous ethanolic solution (V/V) of 12 times of amount of resin to be divided into again 5 times, under the mixing speed condition of 60r/min, flush away iridoid glycoside compounds, middle polarity such as chlorogenic acid and flavones impurity, 48% aqueous acetone solution (V/V) of using 3 times of amount of resin at last is under the mixing speed condition of 85r/min, the wash-out Gardenia Yellow, elutriant-0.05～-0.09MPa, under 50～65 ℃ of conditions, through decompression and solvent recovery, vacuum concentration becomes the Gardenia Yellow crude product.
Under 65 ℃ of conditions, ethyl acetate with 5 times of amounts (W/W) fully extracts jasminoidin and the chlorogenic acid of removing in the Gardenia Yellow crude product, raffinate-0.05～-0.09MPa, 50～65 ℃ of conditions under, become high luminance relay valency Gardenia Yellow through decompression and solvent recovery, vacuum concentration.After measured, the index of Gardenia Yellow is E
440 1% 1cm=580, A
238/ A
440=0.25, A
320/ A
440=0.24.
Embodiment 8
10～30 order Cape Jasmine Fruit 2.5kg are put into extractor, 60% aqueous acetone solution with 5 times of Cape Jasmine Fruit dry weights (W/W), refluxing extraction is 2 hours under 80 ℃ of conditions, filter, filtrate-0.06～-0.095MPa, 50～80 ℃ of conditions under, become Gardenia Yellow crude extract medicinal extract through decompression and solvent recovery, vacuum concentration, medicinal extract concentration reaches 7.5 degree Beaume.
Under the mixing speed condition of 60r/min, directly adopt the HZ802 macroporous adsorbent resin that medicinal extract is carried out enrichment absorption Gardenia Yellow to saturated, debris and the more weak water-soluble impurity of adsorptive power that elder generation is not adsorbed with distilled water (V/V) flush away that is no less than 2 times of amount of resin, 30% the aqueous ethanolic solution (V/V) of using 3 times of amount of resin again is under the mixing speed condition of 75r/min, flush away iridoid glycoside compounds, middle polarity such as chlorogenic acid and flavones impurity, 70% aqueous acetone solution (V/V) of using 3 times of amount of resin at last is under the mixing speed condition of 90r/min, the wash-out Gardenia Yellow, elutriant-0.05～-0.09MPa, under 50～65 ℃ of conditions, through decompression and solvent recovery, vacuum concentration becomes the Gardenia Yellow crude product.
Under 70 ℃ of conditions, ethyl acetate with 3 times of amounts (W/W) fully extracts jasminoidin and the chlorogenic acid of removing in the Gardenia Yellow crude product, raffinate-0.05～-0.09MPa, 50～65 ℃ of conditions under, become high luminance relay valency Gardenia Yellow through decompression and solvent recovery, vacuum concentration.After measured, the index of Gardenia Yellow is E
440 1% 1cm=598, A
238/ A
440=0.22, A
320/ A
440=0.23.
Embodiment 9
10～30 order Cape Jasmine Fruit 2.3kg are put into extractor, 60% methyl alcohol-ethanol (2: 5) aqueous solution with 13 times of Cape Jasmine Fruit dry weights (W/W), refluxing extraction is 2 hours under 75 ℃ of conditions, filter, filtrate-0.06～-0.095MPa, 65～80 ℃ of conditions under, become Gardenia Yellow crude extract medicinal extract through decompression and solvent recovery, vacuum concentration.
Adding distil water is adjusted medicinal extract concentration and is reached 5 degree Beaume, adopt the HZ803 macroporous adsorbent resin, with 0.85 times of amount of resin/hour flow velocity (V/V), the dynamic adsorption Gardenia Yellow is to saturated, debris and the more weak water-soluble impurity of adsorptive power that elder generation is not adsorbed with distilled water (V/V) flush away that is no less than 2 times of amount of resin, 24% the aqueous ethanolic solution (V/V) of using 6 times of amount of resin again with 1.0 times of amount of resin/hour flow velocity (V/V) flush away iridoid glycoside compounds, middle polarity such as chlorogenic acid and flavones impurity, 40% methyl alcohol-ethanol (2: 5) aqueous solution (V/V) of using 9 times of amount of resin at last with 0.75 times of amount of resin/hour flow velocity (V/V), the dynamic desorption Gardenia Yellow, elutriant-0.05～-0.09MPa, under 50～65 ℃ of conditions, through decompression and solvent recovery, vacuum concentration becomes the Gardenia Yellow crude product.
Under 50 ℃ of conditions, ethyl acetate with 10 times of amounts (W/W) fully extracts jasminoidin and the chlorogenic acid of removing in the Gardenia Yellow crude product, raffinate-0.05～-0.09MPa, 50～65 ℃ of conditions under, become high luminance relay valency Gardenia Yellow through decompression and solvent recovery, vacuum concentration.After measured, the index of Gardenia Yellow is E
440 1% 1cm=608, A
238/ A
440=0.21, A
320/ A
440=0.23.
Above embodiment is intended to further describe for example the present invention, rather than limits the present invention by any way.
Of the present invention a kind of from cape jasmine the method for separation and purification high luminance relay valency Gardenia Yellow, technology is simple, separation and purification is effective, product yield is high, production cost is low, to the reasonable utilization of China's cape jasmine plant resources, the guarantee of food safety and the extension of traditional Chinese medicine industrial chain, solve the agriculture, rural areas and farmers problem, all have important social value and realistic meaning.
Claims (8)
1. the method for a separation and purification high luminance relay valency Gardenia Yellow from cape jasmine, it is characterized in that: the step of described method is:
(1) preparation of Gardenia Yellow crude extract medicinal extract: with the cape jasmine is raw material, adopt 30～60% hydrophilic organic solvent aqueous solution of 5～20 times of cape jasmine dry weights (W/W), under 50～80 ℃ of conditions, extract 1～3 time, each 1～3 hour, united extraction liquid, filter, filtrate-0.06～-0.095MPa, 50～80 ℃ of conditions under, become Gardenia Yellow crude extract medicinal extract through decompression and solvent recovery, vacuum concentration;
(2) resin concentration of Gardenia Yellow crude product: medicinal extract is extremely saturated through the absorption with macroporous adsorbent resin Gardenia Yellow, debris and the more weak water-soluble impurity of adsorptive power that elder generation is not adsorbed with water (V/V) flush away that is no less than 2 times of amount of resin, again with 15～30% aqueous ethanolic solution (V/V) the flush away middle polarity impurity that is no less than 3 times of amount of resin, use 40～70% hydrophilic organic solvent aqueous solution (V/V) wash-out Gardenia Yellows of 3～9 times of amount of resin at last, elutriant-0.05～-0.09MPa, under 50～65 ℃ of conditions, through decompression and solvent recovery, vacuum concentration becomes the Gardenia Yellow crude product;
(3) purifying of high luminance relay valency Gardenia Yellow: under 50～70 ℃ of conditions, ethyl acetate with 3～10 times of amounts (W/W) fully extracts jasminoidin and the chlorogenic acid of removing in the Gardenia Yellow crude product, raffinate-0.05～-0.09MPa, 50～65 ℃ of conditions under, become high luminance relay valency Gardenia Yellow through decompression and solvent recovery, vacuum concentration.
2. according to claim 1 a kind of from cape jasmine the method for separation and purification high luminance relay valency Gardenia Yellow, it is characterized in that: described hydrophilic organic solvent is one or more mixed solvents in methyl alcohol, acetone, ethanol, propyl alcohol or the Virahol.
3. according to claim 2 a kind of from cape jasmine the method for separation and purification high luminance relay valency Gardenia Yellow, it is characterized in that: described hydrophilic organic solvent is preferentially selected methyl alcohol or acetone for use.
4. according to claim 1 a kind of from cape jasmine the method for separation and purification high luminance relay valency Gardenia Yellow, it is characterized in that: the middle polarity impurity described in the step (2) is iridoid glycoside compounds, chlorogenic acid or flavones.
According to claim 1 or 4 described a kind of from cape jasmine the method for separation and purification high luminance relay valency Gardenia Yellow, it is characterized in that: described iridoid glycoside compounds is one or more compounds in jasminoidin, different jasminoidin, genipin gentiobiose glycosides or the Geniposidic acid.
6. according to claim 1 a kind of from cape jasmine the method for separation and purification high luminance relay valency Gardenia Yellow, it is characterized in that: described Gardenia Yellow is one or more compounds in crocetin, crocin 1, crocin 2 or the crocin 3.
7. according to claim 1 a kind of from cape jasmine the method for separation and purification high luminance relay valency Gardenia Yellow, it is characterized in that: the chemical constitution of macroporous adsorbent resin skeleton is one or both in polystyrene and the polyacrylic acid.
8. according to claim 1 from cape jasmine the method for separation and purification high luminance relay valency Gardenia Yellow, it is characterized in that: the index of described high luminance relay valency Gardenia Yellow is E
440 1% 1cm〉=580, A
238/ A
440≤ 0.25, A
320/ A
440≤ 0.24.
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