CN105477026A - Process for extracting ginkgolic acid, flavone, terpene lactones and polysaccharose from gingko exotesta in combined mode - Google Patents
Process for extracting ginkgolic acid, flavone, terpene lactones and polysaccharose from gingko exotesta in combined mode Download PDFInfo
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K36/00—Medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicines
- A61K36/16—Ginkgophyta, e.g. Ginkgoaceae (Ginkgo family)
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/60—Salicylic acid; Derivatives thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/70—Carbohydrates; Sugars; Derivatives thereof
- A61K31/715—Polysaccharides, i.e. having more than five saccharide radicals attached to each other by glycosidic linkages; Derivatives thereof, e.g. ethers, esters
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2236/00—Isolation or extraction methods of medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicine
- A61K2236/30—Extraction of the material
- A61K2236/33—Extraction of the material involving extraction with hydrophilic solvents, e.g. lower alcohols, esters or ketones
- A61K2236/331—Extraction of the material involving extraction with hydrophilic solvents, e.g. lower alcohols, esters or ketones using water, e.g. cold water, infusion, tea, steam distillation, decoction
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2236/00—Isolation or extraction methods of medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicine
- A61K2236/30—Extraction of the material
- A61K2236/33—Extraction of the material involving extraction with hydrophilic solvents, e.g. lower alcohols, esters or ketones
- A61K2236/333—Extraction of the material involving extraction with hydrophilic solvents, e.g. lower alcohols, esters or ketones using mixed solvents, e.g. 70% EtOH
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2236/00—Isolation or extraction methods of medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicine
- A61K2236/30—Extraction of the material
- A61K2236/35—Extraction with lipophilic solvents, e.g. Hexane or petrol ether
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2236/00—Isolation or extraction methods of medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicine
- A61K2236/30—Extraction of the material
- A61K2236/39—Complex extraction schemes, e.g. fractionation or repeated extraction steps
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2236/00—Isolation or extraction methods of medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicine
- A61K2236/50—Methods involving additional extraction steps
- A61K2236/53—Liquid-solid separation, e.g. centrifugation, sedimentation or crystallization
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2236/00—Isolation or extraction methods of medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicine
- A61K2236/50—Methods involving additional extraction steps
- A61K2236/55—Liquid-liquid separation; Phase separation
Abstract
The invention belongs to the fields of agriculture, biology and chemical engineering, and particularly relates to a process for extracting ginkgolic acid, flavone, terpene lactones and polysaccharose from gingko exotesta in a combined mode. The process includes the steps that firstly, extraction is conducted on dry gingko exotesta multiple times to obtain crude extract of ginkgolic acid and first-time residues, and the crude extract of ginkgolic acid is further extracted to obtain ginkgolic acid with the purity larger than 97wt%; extraction is conducted on the first-time residues multiple times to obtain crude extract of flavone and terpene lactones and second-time residues, and further purification is conducted on the crude extract of flavone and terpene lactones to obtain extract with flavone larger than or equal to 24wt% and terpene lactones larger than or equal to 6wt%; water extraction is conducted on the second-time residues multiple times to obtain crude extract of polysaccharose and non-toxic residues, and the crude extract of polysaccharose is further purified to obtain ginkgo polysaccharose with the purity larger than 98wt%. By means of the combined extraction process, the resource, namely, gingko exotesta, is fully used, and the process has the advantages of being easy to operate and low in extraction cost.
Description
Technical field
The invention belongs to agricultural, biology, chemical field, be specifically related to a kind of technique of combined extracting ginkgoic acid, flavone and terpene lactones and polysaccharide from gingko episperm.
Background technology
Semen Ginkgo is the important medical and economical seeds of China.Modern medicine study shows, all contains that flavone, terpene lactones, ginkgoic acid, polysaccharide etc. are multiple has bioactive composition in Folium Ginkgo, ginkgo nut, gingko episperm.Wherein, ginkgetin and terpene lactones have the effect of scavenging free radicals and blood vessel dilating, antagonism PF (platelet factor), Semen Ginkgo polysaccharide has the effect reducing blood glucose, slow down aging, raising immunity, and ginkgoic acid has antitumor, antimicrobial effect but simultaneously have again stronger fetal toxicity and cytotoxicity.
Folium Ginkgo is due to flavone and terpene lactones content higher (3.6%), ginkgoic acid content lower (0.25%), its flavone and terpene lactones extract (EGB) have become the medicine of important treatment cardiovascular and cerebrovascular disease at present, but pharmacopoeia of each country all limits the content of ginkgoic acid in EGB.As, the U.S. limits equal < 5ppm with Germany for ginkgoic acid content in EGB, and China limits equal < 10ppm for ginkgoic acid content in EGB.
Gingko episperm is remaining part after ginkgo nut stripping pit, and its flavonoid active component content lower (1.3% ~ 2.7%), the content of ginkgoic acid is higher (5.4%), is never effectively utilized.The annual whole nation is at Semen Ginkgo growing area according to statistics, has the gingko episperm under nearly 100,000 tons of gingkos are peeled off directly to be discarded.Discarded gingko episperm can rot to volatilize the stench abnormal smells from the patient stimulated, and causes environmental pollution, biological death, according to the flavone containing 1300 ~ 2770t in these discarded gingko episperms of preresearch estimates, and the ginkgoic acid of 5900t, the polysaccharide of 6580t.The method for individually extracting of what current research was more is flavone and terpene lactones, ginkgoic acid or polysaccharide, cost is high, efficiency is low, can not realize suitability for industrialized production.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, object is the technique providing a kind of combined extracting ginkgoic acid, flavone and terpene lactones and polysaccharide from gingko episperm.
For achieving the above object, the technical solution used in the present invention is:
From gingko episperm, a technique for combined extracting ginkgoic acid, flavone and terpene lactones and polysaccharide, comprises the steps:
(1) gingko episperm of drying is shattered sieve, then non-polar solven is added, under agitation, non-polar solven is utilized repeatedly to extract the ginkgoic acid removed in gingko episperm, be separated and collect each extraction phase extracted, until terminate extraction in gingko episperm time ginkgoic acid content < 0.01wt% (10mg/kg), merge repeatedly extract collection extraction phase and after evaporate to dryness extractant, obtain ginkgoic acid crude extract, obtain gingko episperm residue simultaneously; Adopt silica column purification ginkgoic acid crude extract, with after after concentrate drying, obtain the solid ginkgoic acid that purity is greater than 97wt%;
(2) after gingko episperm residue drying step (1) obtained, add alcohol-water mixture wherein and carry out extracted many times, be separated and collect the lixiviating solution of each lixiviate, until terminate lixiviate during the content≤0.2wt% of flavone and terpene lactones in gingko episperm residue, the lixiviating solution merging extracted many times collection obtains flavone and terpene lactones crude extract, obtains gingko episperm secondary residual simultaneously; Adopt macroporous resin purification of flavone and terpene lactones crude extract, with after obtain flavone >=24wt%, terpene lactones >=6wt%, the flavone of ginkgoic acid content < 0.01wt% and terpene lactones extract through concentrated;
(3) after gingko episperm secondary residual drying step (2) obtained, add water wherein and carry out repeatedly water extraction, merge repeatedly water extraction to be separated the Aqueous extracts obtained and to obtain Semen Ginkgo polysaccharide crude extract, obtain gingko episperm three residues simultaneously, described gingko episperm three nontoxic odorlesses of residue are pollution-free, can directly discard; Adopt the protein in Sevage method removing Semen Ginkgo polysaccharide crude extract, then obtain by recrystallization purifying the Semen Ginkgo polysaccharide that purity is greater than 98wt%.
In such scheme, step (1) described non-polar solven is petroleum ether, C
5-C
10between alkane, C
5-C
10between alkene, C
5-C
10between cycloalkane and one or more in chloroform.
In such scheme, the mode of step (1) described extraction is stirring and refluxing extraction, sand milling extraction, ball milling wall-breaking abstraction or ultrasound on extracting.
In such scheme, the extraction time of the described each extraction of step (1) is 0.2 ~ 2h, and solid-liquid mass ratio is 1:5 ~ 1:8.
In such scheme, step (2) described alcohol-water mixture is methanol aqueous solution or ethanol water.
In such scheme, the mode of step (2) described lixiviate is stirring and leaching, backflow lixiviate, sand milling lixiviate, ball milling lixiviate or ultrasonic wave added lixiviate.
In such scheme, the extraction time of the described each lixiviate of step (2) is 0.2 ~ 2h, and solid-liquid mass ratio is 1:5 ~ 1:6.
In such scheme, the mode of step (3) described water extraction is for stirring water extraction, backflow water extraction, sand milling water extraction, ball milling water extraction or ultrasonic wave added water extraction.
In such scheme, the water extraction time of each water extraction of step (3) is 0.2 ~ 2h, and solid-liquid mass ratio is 1:5 ~ 1:7.
Beneficial effect of the present invention is as follows: the ginkgoic acid in gingko episperm, flavone and terpene lactones and polysaccharide, by a process route, are extracted acquisition extract, take full advantage of this resource of gingko episperm by the present invention respectively; The present invention is by the technique of combined extracting; with extract separately compared with a certain active component; incorporate remove ginkgoic acid step, simplify the operating procedure extracted separately with these compositions, the cost that reduces extraction, set up basis for utilizing gingko episperm resource, protection of the environment and industrial applications.
Accompanying drawing explanation
Fig. 1 is the flow chart of technique of the present invention.
Detailed description of the invention
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
Embodiment 1
From gingko episperm, a technique for combined extracting ginkgoic acid, flavone and terpene lactones and polysaccharide, comprises the steps:
(1) dry gingko episperm is got, crossing 60 mesh sieves after crushed, take petroleum ether as extractant, and solid-liquid mass ratio is 1:5, ball milling-solvent-extracted mode is adopted to extract 40min, after extracting 5 times, detect that the content of ginkgoic acid in gingko episperm is 0.007wt%, terminate extraction, merge the extraction phase of three extractions, after extractant evaporate to dryness, obtain ginkgoic acid crude extract, remaining as gingko episperm residue, by ginkgoic acid crude extract petroleum ether redissolution (redissolution of 1g ginkgoic acid crude extract 10ml petroleum ether), be splined on processed silicagel column (silica gel 100g, blade diameter length ratio 1:15, internal diameter is 30mm, wet method dress post), ginkgoic acid crude extract is separated through silica gel column chromatography, with petroleum ether (95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%), isopropyl alcohol (4%, 9%, 14%, 19%, 24%, 29%, 34%, 39%), the mixed solution of acetic acid (1%) is that eluant carries out gradient elution, collect three stream parts that ginkgoic acid content is high, concentrated and vacuum drying after three stream parts are merged, obtain the solid Semen Ginkgo acid product of bright yellowish-brown, detect through HPLC, the purity of ginkgoic acid is 97.5wt%.
(2) gingko episperm residue is placed in 70 DEG C of oven drying 24h, with 80Vt% (percent by volume) alcoholic solution for extractant, solid-liquid mass ratio is 1:5, adopt stirring-solvent-extracted mode lixiviate 60min, after lixiviate 2 times, detect flavone and the terpene lactones content≤0.2wt% in gingko episperm, terminate lixiviate, merge the extracting solution of 2 lixiviates, after concentrated 5 times, be flavone and terpene lactones crude extract, remaining as gingko episperm secondary residual; Filter after flavone and terpene lactones crude extract are left standstill 6h, regulate filtrate pH to 6, filtrate rotary evaporation is dry to paste final vacuum, again with ethanol redissolution (concentration is 2mg/mL), upper AB-8 macroporous resin column, first with 4BV water wash, the alcoholic solution changing 20Vt% again rinses, finally use 70Vt% ethanol elution flavone and terpene lactones, be flavone and terpene lactones extract after eluent evaporation and concentration 3 times, after measured, wherein the content of flavone is 25.2wt%, the content of terpene lactones is 6.3wt%, and ginkgoic acid content is 5.2ppm.
(3) gingko episperm secondary residual is placed in 70 DEG C, vacuum drying oven and dries 24h, with 90 DEG C of water for Extraction solvent, solid-liquid mass ratio is 1:5, with-mode solvent extraction extraction the 120min that refluxes, merges the filtrate of twice water extraction, after measured, the thick extraction ratio of Semen Ginkgo polysaccharide is 72.7wt%, filtrate is concentrated to 1/5 of original volume, then the ethanol adding 4 times of volumes leaves standstill 24h at 5 DEG C, sucking filtration, by washing with alcohol; Reclaim solid and vacuum drying, obtain the thick product of Semen Ginkgo polysaccharide, after measured, its purity is 34wt%; Thick for above-mentioned gained Semen Ginkgo polysaccharide product water is redissolved, adopt the n-butyl alcohol of 1/4 liquor capacity: chloroform=1:3 mixed solvent (Sevage method) extracts 3 times except deproteinize, again with the ethyl alcohol recrystallization adding 4 times of volumes, obtain that purity is 98.2wt%, ginkgoic acid content is the Semen Ginkgo polysaccharide of 1.8ppm.
Embodiment 2
From gingko episperm, a technique for combined extracting ginkgoic acid, flavone and terpene lactones and polysaccharide, comprises the steps:
(1) dry gingko episperm is got, crossing 60 mesh sieves after crushed, take normal hexane as extractant, and solid-liquid mass ratio is 1:5, sand milling-solvent-extracted mode is adopted to extract 100min, after extracting 5 times, detect that the content of ginkgoic acid in gingko episperm is 0.006wt%, terminate extraction, merge the extraction phase of three extractions, after extractant evaporate to dryness, obtain ginkgoic acid crude extract, remaining as gingko episperm residue, by ginkgoic acid crude extract petroleum ether redissolution (redissolution of 1g ginkgoic acid crude extract 10ml petroleum ether), be splined on processed silicagel column (silica gel 100g, blade diameter length ratio 1:15, internal diameter is 30mm, wet method dress post), ginkgoic acid crude extract is separated through silica gel column chromatography, with petroleum ether (95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%), isopropyl alcohol (4%, 9%, 14%, 19%, 24%, 29%, 34%, 39%), the mixed solution of acetic acid (1%) is that eluant carries out gradient elution, collect three stream parts that ginkgoic acid content is high, concentrated and vacuum drying after three stream parts are merged, obtain the solid gingkolic acid purified product of bright yellowish-brown, detect through HPLC, the purity of ginkgoic acid is 98.2wt%.
(2) gingko episperm residue is placed in 70 DEG C of oven drying 24h, with 80Vt% (percent by volume) methanol solution for extractant, solid-liquid mass ratio is 1:6, adopt ball milling-solvent-extracted mode lixiviate 40min, after lixiviate 2 times, detect flavone and the terpene lactones content≤0.2wt% in gingko episperm, terminate lixiviate, merge the extracting solution of 2 lixiviates, after concentrated 5 times, be flavone and terpene lactones crude extract, remaining as gingko episperm secondary residual; Filter after flavone and terpene lactones crude extract water precipitating 6h, regulate filtrate pH to 6, filtrate rotary evaporation is dry to paste final vacuum, again with ethanol redissolution (concentration is 2mg/mL), upper AB-8 macroporous resin column, first with 4BV water wash, the alcoholic solution changing 20Vt% again rinses, finally use 70Vt% ethanol elution flavone and terpene lactones, be flavone and terpene lactones extract after eluent evaporation and concentration 3 times, after measured, wherein the content of flavone is 26.4wt%, the content of terpene lactones is 6.1wt%, and ginkgoic acid content is 4.3ppm.
(3) gingko episperm secondary residual is placed in 70 DEG C, vacuum drying oven and dries 24h, with 90 DEG C of water for Extraction solvent, solid-liquid mass ratio is 1:6, and backflow water extraction 2h, merges the filtrate of twice water extraction, after measured, the thick extraction ratio of Semen Ginkgo polysaccharide is 73.5wt%, filtrate is concentrated to 1/5 of original volume, then the ethanol adding 4 times of volumes leaves standstill 24h at 5 DEG C, sucking filtration, by washing with alcohol; Reclaim solid and vacuum drying, obtain the thick product of Semen Ginkgo polysaccharide, after measured, its purity is 34wt%; Thick for above-mentioned gained Semen Ginkgo polysaccharide product water is redissolved, adopt the n-butyl alcohol of 1/4 liquor capacity: chloroform=1:3 mixed solvent (Sevage method) extracts 3 times except deproteinize, again with the ethyl alcohol recrystallization adding 4 times of volumes, obtain that purity is 98.8wt%, ginkgoic acid content is the Semen Ginkgo polysaccharide of 2.1ppm.
Embodiment 3
From gingko episperm, a technique for combined extracting ginkgoic acid, flavone and terpene lactones and polysaccharide, comprises the steps:
(1) dry gingko episperm is got, crossing 60 mesh sieves after crushed, take normal octane as extractant, and solid-liquid mass ratio is 1:8, ultrasonic-solvent-extracted mode is adopted to extract 120min, after extracting 6 times, detect that the content of ginkgoic acid in gingko episperm is 0.008wt%, terminate extraction, merge the extraction phase of three extractions, after extractant evaporate to dryness, obtain ginkgoic acid crude extract, remaining as gingko episperm residue, by ginkgoic acid crude extract petroleum ether redissolution (redissolution of 1g ginkgoic acid crude extract 10ml petroleum ether), be splined on processed silicagel column (silica gel 100g, blade diameter length ratio 1:15, internal diameter is 30mm, wet method dress post), ginkgoic acid crude extract is separated through silica gel column chromatography, with petroleum ether (95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%), isopropyl alcohol (4%, 9%, 14%, 19%, 24%, 29%, 34%, 39%), the mixed solution of acetic acid (1%) is that eluant carries out gradient elution, collect three stream parts that ginkgoic acid content is high, concentrated and vacuum drying after three stream parts are merged, obtain the solid gingkolic acid purified product of bright yellowish-brown, detect through HPLC, the purity of ginkgoic acid is 98.6wt%.
(2) gingko episperm residue is placed in 70 DEG C of oven drying 24h, with 80Vt% (percent by volume) alcoholic solution for extractant, solid-liquid mass ratio is 1:6, adopt ball milling-solvent-extracted mode lixiviate 40min, after lixiviate 2 times, detect flavone and the terpene lactones content≤0.2wt% in gingko episperm, terminate lixiviate, merge the extracting solution of 2 lixiviates, after concentrated 5 times, be flavone and terpene lactones crude extract, remaining as gingko episperm secondary residual; Filter after flavone and terpene lactones crude extract water precipitating 6h, regulate filtrate pH to 6, filtrate rotary evaporation is dry to paste final vacuum, again with ethanol redissolution (concentration is 2mg/mL), upper AB-8 macroporous resin column, first with 4BV water wash, the alcoholic solution changing 20Vt% again rinses, finally use 70Vt% ethanol elution flavone and terpene lactones, be flavone and terpene lactones extract after eluent evaporation and concentration 3 times, after measured, wherein the content of flavone is 27.5wt%, the content of terpene lactones is 6.8wt%, and ginkgoic acid content is 4.3ppm.
(3) gingko episperm secondary residual is placed in 70 DEG C, vacuum drying oven and dries 24h, with 90 DEG C of water for Extraction solvent, solid-liquid mass ratio is 1:7, and backflow-solvent extraction 2h merges the filtrate of twice water extraction, after measured, the thick extraction ratio of Semen Ginkgo polysaccharide is 76.8wt%, runic thing is concentrated to 1/5 of original volume, then the ethanol adding 4 times of volumes leaves standstill 24h at 5 DEG C, sucking filtration, by washing with alcohol; Reclaim solid and vacuum drying, obtain the thick product of Semen Ginkgo polysaccharide, its purity is 34wt%; Thick for above-mentioned gained Semen Ginkgo polysaccharide product water is redissolved, adopt the n-butyl alcohol of 1/4 liquor capacity: chloroform=1:3 mixed solvent (Sevage method) extracts 3 times except deproteinize, again with the ethyl alcohol recrystallization adding 4 times of volumes, obtain that purity is 98.8wt%, ginkgoic acid content is the Semen Ginkgo polysaccharide of 3.5ppm.
Embodiment 4
From gingko episperm, a technique for combined extracting ginkgoic acid, flavone and terpene lactones and polysaccharide, comprises the steps:
(1) dry gingko episperm is got, crossing 60 mesh sieves after crushed, take cyclohexane extraction as extractant, and solid-liquid mass ratio is 1:5, ball milling-solvent-extracted mode is adopted to extract 40min, after extracting 5 times, detect that the content of ginkgoic acid in gingko episperm is 0.007wt%, terminate extraction, merge the extraction phase of three extractions, after extractant evaporate to dryness, obtain ginkgoic acid crude extract, remaining as gingko episperm residue, by ginkgoic acid crude extract petroleum ether redissolution (redissolution of 1g ginkgoic acid crude extract 10ml petroleum ether), be splined on processed silicagel column (silica gel 100g, blade diameter length ratio 1:15, internal diameter is 30mm, wet method dress post), ginkgoic acid crude extract is separated through silica gel column chromatography, with petroleum ether (95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%), isopropyl alcohol (4%, 9%, 14%, 19%, 24%, 29%, 34%, 39%), the mixed solution of acetic acid (1%) is that eluant carries out gradient elution, collect three stream parts that ginkgoic acid content is high, concentrated and vacuum drying after three stream parts are merged, obtain the solid Semen Ginkgo acid product of bright yellowish-brown, detect through HPLC, the purity of ginkgoic acid is 97.5wt%.
(2) gingko episperm residue is placed in 70 DEG C of oven drying 24h, with 80Vt% (percent by volume) alcoholic solution for extractant, solid-liquid mass ratio is 1:5, adopt stirring-solvent-extracted mode lixiviate 60min, after lixiviate 2 times, detect flavone and the terpene lactones content≤0.2wt% in gingko episperm, terminate lixiviate, merge the extracting solution of 2 lixiviates, after concentrated 5 times, be flavone and terpene lactones crude extract, remaining as gingko episperm secondary residual; Filter after flavone and terpene lactones crude extract are left standstill 6h, regulate filtrate pH to 6, filtrate rotary evaporation is dry to paste final vacuum, again with ethanol redissolution (concentration is 2mg/mL), upper AB-8 macroporous resin column, first with 4BV water wash, the alcoholic solution changing 20Vt% again rinses, finally use 70Vt% ethanol elution flavone and terpene lactones, be flavone and terpene lactones extract after eluent evaporation and concentration 3 times, after measured, wherein the content of flavone is 25.2wt%, the content of terpene lactones is 6.3wt%, and ginkgoic acid content is 5.2ppm.
(3) gingko episperm secondary residual is placed in 70 DEG C, vacuum drying oven and dries 24h, with 90 DEG C of water for Extraction solvent, solid-liquid mass ratio is 1:5, with-mode solvent extraction extraction the 120min that refluxes, merges the filtrate of twice water extraction, after measured, the thick extraction ratio of Semen Ginkgo polysaccharide is 72.7wt%, filtrate is concentrated to 1/5 of original volume, then the ethanol adding 4 times of volumes leaves standstill 24h at 5 DEG C, sucking filtration, by washing with alcohol; Reclaim solid and vacuum drying, obtain the thick product of Semen Ginkgo polysaccharide, after measured, its purity is 34wt%; Thick for above-mentioned gained Semen Ginkgo polysaccharide product water is redissolved, adopt the n-butyl alcohol of 1/4 liquor capacity: chloroform=1:3 mixed solvent (Sevage method) extracts 3 times except deproteinize, again with the ethyl alcohol recrystallization adding 4 times of volumes, obtain that purity is 98.2wt%, ginkgoic acid content is the Semen Ginkgo polysaccharide of 1.8ppm.
Embodiment 5
From gingko episperm, a technique for combined extracting ginkgoic acid, flavone and terpene lactones and polysaccharide, comprises the steps:
(1) dry gingko episperm is got, crossing 60 mesh sieves after crushed, take n-hexylene as extractant, and solid-liquid mass ratio is 1:5, ultrasonic-solvent-extracted mode is adopted to extract 100min, after extracting 5 times, detect that the content of ginkgoic acid in gingko episperm is 0.007wt%, terminate extraction, merge the extraction phase of three extractions, after extractant evaporate to dryness, obtain ginkgoic acid crude extract, remaining as gingko episperm residue, by ginkgoic acid crude extract petroleum ether redissolution (redissolution of 1g ginkgoic acid crude extract 10ml petroleum ether), be splined on processed silicagel column (silica gel 100g, blade diameter length ratio 1:15, internal diameter is 30mm, wet method dress post), ginkgoic acid crude extract is separated through silica gel column chromatography, with petroleum ether (95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%), isopropyl alcohol (4%, 9%, 14%, 19%, 24%, 29%, 34%, 39%), the mixed solution of acetic acid (1%) is that eluant carries out gradient elution, collect three stream parts that ginkgoic acid content is high, concentrated and vacuum drying after three stream parts are merged, obtain the solid Semen Ginkgo acid product of bright yellowish-brown, detect through HPLC, the purity of ginkgoic acid is 98.1wt%.
(2) gingko episperm residue is placed in 70 DEG C of oven drying 24h, with 80Vt% (percent by volume) alcoholic solution for extractant, solid-liquid mass ratio is 1:5, adopt stirring-solvent-extracted mode lixiviate 60min, after lixiviate 2 times, detect flavone and the terpene lactones content≤0.2wt% in gingko episperm, terminate lixiviate, merge the extracting solution of 2 lixiviates, after concentrated 5 times, be flavone and terpene lactones crude extract, remaining as gingko episperm secondary residual; Filter after flavone and terpene lactones crude extract are left standstill 6h, regulate filtrate pH to 6, filtrate rotary evaporation is dry to paste final vacuum, again with ethanol redissolution (concentration is 2mg/mL), upper AB-8 macroporous resin column, first with 4BV water wash, the alcoholic solution changing 20Vt% again rinses, finally use 70Vt% ethanol elution flavone and terpene lactones, be flavone and terpene lactones extract after eluent evaporation and concentration 3 times, after measured, wherein the content of flavone is 27.2wt%, the content of terpene lactones is 6.1wt%, and ginkgoic acid content is 5.7ppm.
(3) gingko episperm secondary residual is placed in 70 DEG C, vacuum drying oven and dries 24h, with 90 DEG C of water for Extraction solvent, solid-liquid mass ratio is 1:5, with-mode solvent extraction extraction the 120min that refluxes, merges the filtrate of twice water extraction, after measured, the thick extraction ratio of Semen Ginkgo polysaccharide is 72.7wt%, filtrate is concentrated to 1/5 of original volume, then the ethanol adding 4 times of volumes leaves standstill 24h at 5 DEG C, sucking filtration, by washing with alcohol; Reclaim solid and vacuum drying, obtain the thick product of Semen Ginkgo polysaccharide, after measured, its purity is 34wt%; Thick for above-mentioned gained Semen Ginkgo polysaccharide product water is redissolved, adopt the n-butyl alcohol of 1/4 liquor capacity: chloroform=1:3 mixed solvent (Sevage method) extracts 3 times except deproteinize, again with the ethyl alcohol recrystallization adding 4 times of volumes, obtain that purity is 98.2wt%, ginkgoic acid content is the Semen Ginkgo polysaccharide of 2.5ppm.
Embodiment 6
From gingko episperm, a technique for combined extracting ginkgoic acid, flavone and terpene lactones and polysaccharide, comprises the steps:
(1) dry gingko episperm is got, crossing 60 mesh sieves after crushed, take chloroform as extractant, and solid-liquid mass ratio is 1:5, ball milling-solvent-extracted mode is adopted to extract 40min, after extracting 5 times, detect that the content of ginkgoic acid in gingko episperm is 0.007wt%, terminate extraction, merge the extraction phase of three extractions, after extractant evaporate to dryness, obtain ginkgoic acid crude extract, remaining as gingko episperm residue, by ginkgoic acid crude extract petroleum ether redissolution (redissolution of 1g ginkgoic acid crude extract 10ml petroleum ether), be splined on processed silicagel column (silica gel 100g, blade diameter length ratio 1:15, internal diameter is 30mm, wet method dress post), ginkgoic acid crude extract is separated through silica gel column chromatography, with petroleum ether (95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%), isopropyl alcohol (4%, 9%, 14%, 19%, 24%, 29%, 34%, 39%), the mixed solution of acetic acid (1%) is that eluant carries out gradient elution, collect three stream parts that ginkgoic acid content is high, concentrated and vacuum drying after three stream parts are merged, obtain the solid Semen Ginkgo acid product of bright yellowish-brown, detect through HPLC, the purity of ginkgoic acid is 97.5wt%.
(2) gingko episperm residue is placed in 70 DEG C of oven drying 24h, with 80Vt% (percent by volume) alcoholic solution for extractant, solid-liquid mass ratio is 1:5, adopt sand milling-solvent-extracted mode lixiviate 80min, after lixiviate 2 times, detect flavone and the terpene lactones content≤0.2wt% in gingko episperm, terminate lixiviate, merge the extracting solution of 2 lixiviates, after concentrated 5 times, be flavone and terpene lactones crude extract, remaining as gingko episperm secondary residual; Filter after flavone and terpene lactones crude extract are left standstill 6h, regulate filtrate pH to 6, filtrate rotary evaporation is dry to paste final vacuum, again with ethanol redissolution (concentration is 2mg/mL), upper AB-8 macroporous resin column, first with 4BV water wash, the alcoholic solution changing 20Vt% again rinses, finally use 70Vt% ethanol elution flavone and terpene lactones, be flavone and terpene lactones extract after eluent evaporation and concentration 3 times, after measured, wherein the content of flavone is 26.6wt%, the content of terpene lactones is 6.3wt%, and ginkgoic acid content is 5.8ppm.
(3) gingko episperm secondary residual is placed in 70 DEG C, vacuum drying oven and dries 24h, with 90 DEG C of water for Extraction solvent, solid-liquid mass ratio is 1:5, with-mode solvent extraction extraction the 120min that refluxes, merges the filtrate of twice water extraction, after measured, the thick extraction ratio of Semen Ginkgo polysaccharide is 72.7wt%, filtrate is concentrated to 1/5 of original volume, then the ethanol adding 4 times of volumes leaves standstill 24h at 5 DEG C, sucking filtration, by washing with alcohol; Reclaim solid and vacuum drying, obtain the thick product of Semen Ginkgo polysaccharide, after measured, its purity is 34wt%; Thick for above-mentioned gained Semen Ginkgo polysaccharide product water is redissolved, adopt the n-butyl alcohol of 1/4 liquor capacity: chloroform=1:3 mixed solvent (Sevage method) extracts 3 times except deproteinize, again with the ethyl alcohol recrystallization adding 4 times of volumes, obtain that purity is 98.2wt%, ginkgoic acid content is the Semen Ginkgo polysaccharide of 1.7ppm.
Embodiment 7
From gingko episperm, a technique for combined extracting ginkgoic acid, flavone and terpene lactones and polysaccharide, comprises the steps:
(1) dry gingko episperm is got, crossing 60 mesh sieves after crushed, take ethyl acetate as extractant, and solid-liquid mass ratio is 1:5, ball milling-solvent-extracted mode is adopted to extract 40min, after extracting 5 times, detect that the content of ginkgoic acid in gingko episperm is 0.007wt%, terminate extraction, merge the extraction phase of three extractions, after extractant evaporate to dryness, obtain ginkgoic acid crude extract, remaining as gingko episperm residue, by ginkgoic acid crude extract petroleum ether redissolution (redissolution of 1g ginkgoic acid crude extract 10ml petroleum ether), be splined on processed silicagel column (silica gel 100g, blade diameter length ratio 1:15, internal diameter is 30mm, wet method dress post), ginkgoic acid crude extract is separated through silica gel column chromatography, with petroleum ether (95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%), isopropyl alcohol (4%, 9%, 14%, 19%, 24%, 29%, 34%, 39%), the mixed solution of acetic acid (1%) is that eluant carries out gradient elution, collect three stream parts that ginkgoic acid content is high, concentrated and vacuum drying after three stream parts are merged, obtain the solid Semen Ginkgo acid product of bright yellowish-brown, detect through HPLC, the purity of ginkgoic acid is 97.1wt%.
(2) gingko episperm residue is placed in 70 DEG C of oven drying 24h, with 80Vt% (percent by volume) methanol solution for extractant, solid-liquid mass ratio is 1:5, adopt backflow-solvent-extracted mode lixiviate 60min, after lixiviate 2 times, detect flavone and the terpene lactones content≤0.2wt% in gingko episperm, terminate lixiviate, merge the extracting solution of 2 lixiviates, after concentrated 5 times, be flavone and terpene lactones crude extract, remaining as gingko episperm secondary residual; Filter after flavone and terpene lactones crude extract are left standstill 6h, regulate filtrate pH to 6, filtrate rotary evaporation is dry to paste final vacuum, again with ethanol redissolution (concentration is 2mg/mL), upper AB-8 macroporous resin column, first with 4BV water wash, the alcoholic solution changing 20Vt% again rinses, finally use 70Vt% ethanol elution flavone and terpene lactones, be flavone and terpene lactones extract after eluent evaporation and concentration 3 times, after measured, wherein the content of flavone is 24.2wt%, the content of terpene lactones is 6.1wt%, and ginkgoic acid content is 5.8ppm.
(3) gingko episperm secondary residual is placed in 70 DEG C, vacuum drying oven and dries 24h, with 90 DEG C of water for Extraction solvent, solid-liquid mass ratio is 1:5, with ball milling-mode solvent extraction extraction 120min, merges the filtrate of twice water extraction, after measured, the thick extraction ratio of Semen Ginkgo polysaccharide is 72.7wt%, filtrate is concentrated to 1/5 of original volume, then the ethanol adding 4 times of volumes leaves standstill 24h at 5 DEG C, sucking filtration, by washing with alcohol; Reclaim solid and vacuum drying, obtain the thick product of Semen Ginkgo polysaccharide, after measured, its purity is 34wt%; Thick for above-mentioned gained Semen Ginkgo polysaccharide product water is redissolved, adopt the n-butyl alcohol of 1/4 liquor capacity: chloroform=1:3 mixed solvent (Sevage method) extracts 3 times except deproteinize, again with the ethyl alcohol recrystallization adding 4 times of volumes, obtain that purity is 98.2wt%, ginkgoic acid content is the Semen Ginkgo polysaccharide of 1.6ppm.
Obviously, above-described embodiment is only for the example done clearly is described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And therefore amplified apparent change or variation are still within the protection domain of the invention.
Claims (9)
1. the technique of combined extracting ginkgoic acid, flavone and terpene lactones and polysaccharide from gingko episperm, is characterized in that, comprise the steps:
(1) gingko episperm of drying is shattered sieve, then non-polar solven is added, under agitation, non-polar solven is utilized repeatedly to extract the ginkgoic acid removed in gingko episperm, be separated and collect the extraction phase of each extraction, until terminate extraction in gingko episperm during ginkgoic acid content < 0.01wt%, merging the extraction phase that repeatedly extracts collection and after evaporate to dryness extractant, obtain ginkgoic acid crude extract, obtain gingko episperm residue simultaneously; Adopt silica column purification ginkgoic acid crude extract, with after after concentrate drying, obtain the solid ginkgoic acid that purity is greater than 97wt%;
(2) after gingko episperm residue drying step (1) obtained, add alcohol-water mixture wherein and carry out extracted many times, be separated and collect the lixiviating solution of each lixiviate, until terminate lixiviate during the content≤0.2wt% of flavone and terpene lactones in gingko episperm residue, the lixiviating solution merging extracted many times collection obtains flavone and terpene lactones crude extract, obtains gingko episperm secondary residual simultaneously; Adopt macroporous resin purification of flavone and terpene lactones crude extract, with after obtain flavone >=24wt%, terpene lactones >=6wt%, the flavone of ginkgoic acid content < 0.01wt% and terpene lactones extract through concentrated;
(3) after gingko episperm secondary residual drying step (2) obtained, add water wherein and carry out repeatedly water extraction, merge repeatedly water extraction to be separated the Aqueous extracts obtained and to obtain Semen Ginkgo polysaccharide crude extract, obtain gingko episperm three residues simultaneously, described gingko episperm three nontoxic odorlesses of residue are pollution-free, can directly discard; Adopt the protein in Sevage method removing Semen Ginkgo polysaccharide crude extract, then obtain by recrystallization purifying the Semen Ginkgo polysaccharide that purity is greater than 98wt%.
2. technique according to claim 1, is characterized in that, step (1) described non-polar solven is petroleum ether, C
5-C
9between alkane, C
5-C
9between alkene, C
5-C
9between cycloalkane, ethyl acetate and chloroform in one or more.
3. technique according to claim 1, is characterized in that, the mode of step (1) described extraction is sand milling-solvent extraction, ball milling-solvent extraction or ultrasonic wave added-solvent extraction.
4. technique according to claim 1, is characterized in that, the solid-liquid mass ratio of the described each extraction of step (1) is 1:5 ~ 1:8, and the time of each extraction is 0.2 ~ 2h.
5. technique according to claim 1, is characterized in that, step (2) described alcohol-water mixture is methanol aqueous solution or ethanol water.
6. technique according to claim 1, is characterized in that, the mode of step (2) described lixiviate is stirring-solvent extraction, backflow-solvent extraction, sand milling-solvent extraction, ball milling-solvent extraction or ultrasonic wave added-solvent extraction.
7. technique according to claim 1, is characterized in that, the solid-liquid mass ratio of the described each lixiviate of step (2) is 1:5 ~ 1:6, and the time of each lixiviate is 0.2 ~ 2h.
8. technique according to claim 1, is characterized in that, the mode of step (3) described water extraction is stirring-solvent extraction, backflow-solvent extraction, sand milling-solvent extraction, ball milling-solvent extraction or ultrasonic wave added-solvent extraction.
9. technique according to claim 1, is characterized in that, the water extraction time of each water extraction of step (3) is 0.2 ~ 2h, and solid-liquid mass ratio is 1:5 ~ 1:7.
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