CN1880328A

CN1880328A - Preparation method of hyperin and hypericin of Hypericum perforatum

Info

Publication number: CN1880328A
Application number: CN 200610054268
Authority: CN
Inventors: 周小华; 李端华; 高晶
Original assignee: Chongqing University
Current assignee: Chongqing University
Priority date: 2006-04-30
Filing date: 2006-04-30
Publication date: 2006-12-20
Anticipated expiration: 2026-04-30
Also published as: CN100402543C

Abstract

This invention relates to a method for producing Hypericum perforatum hyperoside and hypericin. This invention comprehensively utilizes Hypericum perforatum fruits which are rich in our country to produce both hyperoside and hypericin pharmaceutical active components with high recovery rate, high product purity, and low cost. During the producing process, it achieves the recovery and cycling use of many solvents like ethanol and ethyl ether, and also achieves the regeneration and cycling use of micelle reextracting agent and absorption resin. The plant biological active compounds produced by this invention can be broadly used in heat-clearing and detoxifying, astringing to arrest bleeding and promote diuresis, and antidepressant drug.

Description

The preparation method of Quercetin 3-galactoside and hypericin in the Herba Hyperici perforati

One, technical field

The invention belongs to the preparing technical field of active constituents of medicine, particularly the preparation method of Quercetin 3-galactoside and hypericin active pharmaceutical ingredients.

Two, background technology

Studies show that: being used for the main active ingredient of medicines such as clearing heat and detoxicating, astringing to arrest bleeding, diuresis and depressed treatment, is hypericin and Quercetin 3-galactoside.Facts have proved: Quercetin 3-galactoside has antianaphylaxis, anti-inflammatory, spasmolysis, diuresis, significantly cough-relieving, hypotensive and effects such as cholesterol and tumour, has the function of analgesia and protection heart especially, and the prevent diabetes cataract is had promoter action etc.; Hypericin has functions such as the human body of adjusting diel rhythm, improvement sleep, lax nervus centralis, HIV (human immunodeficiency virus), hsv, parainfluenza virus, vaccinia virus etc. there is restraining effect, anti-inflammatory analgesic action is arranged, also can be used for treating C type hepatitis and amnesia, prevention and treatment dementia etc.Therefore, preparation Quercetin 3-galactoside and hypericin have important effect to prevention and treatment human diseases, guarantee HUMAN HEALTH.

Quercetin 3-galactoside content in the Herba Hyperici perforati is up to 1.257%, and the content of hypericin is 0.03～0.38%, is the main raw material that extracts Quercetin 3-galactoside and hypericin.China's Herba Hyperici perforati mainly originates in ground such as Sichuan, Shaanxi, Hebei, Shandong, Jiangxi, Jiangsu, and widely distributed, aboundresources helps the preparation of Quercetin 3-galactoside and hypericin.

The existing method of Quercetin 3-galactoside for preparing, the publication number of application was the Chinese patent of CN1493578 as on October 29th, 2002, was raw material with exsiccant Sunset Abelmoschus Root pollen, made through technologies such as hydrophilic solvent extraction, column chromatography, vacuum-dryings; And for example the publication number of application on September 3rd, 2003 is the Chinese patent of CN123032, is raw material with the Medcinal Evodia Fruit medicinal material, makes through numerous and diverse technology.Existing prepare the method for Quercetin 3-galactoside, the Herba Hyperici perforati that does not all utilize china natural resources to enrich, the Quercetin 3-galactoside extraction yield is low, and Quercetin 3-galactoside content is lower in the product, and the production cost height has a large amount of discharging of waste liquid aborning, not only not utilize resources synthetically but also contaminate environment.

The existing plant Herba Hyperici perforati that adopts is that the method for feedstock production hypericin has: what adopt as the Chinese patent of the publication number CN1247071 of application on September 9th, 1998 is to add technologies such as alkaline solution boils, filtration, ethanol elution; As the publication number of on June 7th, 2002 application is that the Chinese patent of CN1385412 adopts aqueous slkali soaking, boils, filters, dry, technology such as water alcohol method is made with extra care; Publication number as application on July 18th, 2002 is technologies such as 1392128 Chinese patents adopt that polar organic solvent extraction, two-phase extraction, acid are sunk; As the publication number of on July 16th, 2003 application is that the Chinese patent of CN1473812 adopts technologies such as machinery is squeezed the juice, alkaline solution extraction.The existing method that adopts the plant Herba Hyperici perforati to prepare hypericin just prepares single hypericin, does not prepare Quercetin 3-galactoside simultaneously, fails to make full use of the Herba Hyperici perforati resource of China's abundant, also has a large amount of discharging of waste liquid in process of production, contaminate environment.

Three, summary of the invention

The objective of the invention is weak point, the preparation method of Quercetin 3-galactoside and hypericin in a kind of Herba Hyperici perforati is provided at existing Quercetin 3-galactoside and hypericin preparation method.Characteristics of the present invention are that the fruit with Herba Hyperici perforati is a raw material, prepare Quercetin 3-galactoside and hypericin simultaneously.Therefore; the present invention has the Herba Hyperici perforati resource of the China's abundant of making full use of; in process of production; recycling spe medium, resin and solvent etc., the product purity height can be used as the raw material of deep processing; product recovery rate height; production cost is lower, and discharging of waste liquid greatly reduces, and helps characteristics such as environment protection.

The object of the present invention is achieved like this: the preparation method of Quercetin 3-galactoside and hypericin in a kind of Herba Hyperici perforati is characterized in: with the Herba Hyperici perforati fruit is raw material, prepares Quercetin 3-galactoside and hypericin simultaneously.Its preparation principle is that Quercetin 3-galactoside has another name called Quercetin-3-O-β-D and adjoins the galactoside of muttering, hyperin, and hyperin, Quercetin-3-galactoside is faint yellow needle-like crystal, 227 ℃-230 ℃ of fusing points, molecular formula is C ₂₁H ₂₀O ₁₂, molecular weight is 464.37, its structure is as follows:

Quercetin 3-galactoside is the flavonol glycosides compound, is soluble in the organic solvents such as methyl alcohol, ethanol, ethyl acetate, therefore available these organic solvent extraction; Be dissolved in the Quercetin 3-galactoside in the organic solvent, can be adsorbed resin absorption, realize partly separating, realize the partial purification of Quercetin 3-galactoside with other impurity; Under alkaline condition, Quercetin 3-galactoside is electronegative.Electronegative Quercetin 3-galactoside can form electrostatic interaction with reverse micelle positively charged, that be made of tensio-active agent cetyl trimethylammonium bromide (CTAB) and minor amount of water, thereby be extracted " solubilising " and enter in the reverse micelle, separate with other not charged impurity; Make strippant with the aqueous solution, destroy reverse micelle, make the Quercetin 3-galactoside reextraction of " solubilising " enter water; With anti-stripping agent vacuum concentration and lyophilize, promptly obtain the Quercetin 3-galactoside product.

Hypericin has another name called hypericum red, Hai Palixin, and chemistry is called 4,4,5,5,7,7-hexahydroxy--2,2-dimethyl-meta-meso-naphthadianthrene ketone, molecular formula is C ₃₀H ₁₆O ₆Molecular weight 504.43.Its structural formula is as follows:

The dianthrone compounds is dissolved in solution such as ethanol, methyl alcohol, chloroform, ether, benzene, sherwood oil, pyridine, acetone, sulphuric acid soln, hydrochloric acid soln and sodium hydroxide, yellow soda ash, sodium bicarbonate, ammonium hydroxide.Available these solvent extractions.

When using reverse micelle to separate Quercetin 3-galactoside,, can not form electrostatic interaction, therefore, separate with Quercetin 3-galactoside with reverse micelle because hypericin molecule neutral and molecular volume are big.With extraordinary polymeric adsorbent hypericin is carried out selective adsorption, wash-out can be further purified hypericin then.

The preparation method of Quercetin 3-galactoside and hypericin in a kind of Herba Hyperici perforati, its concrete method steps is as follows:

(1) preparation of Fructus Forsythiae extractum

After the Herba Hyperici perforati fruit is ground into capsule of weeping forsythia powder, in the ratio of capsule of weeping forsythia grain weight amount and 85～95% ethanol volume is 1: 10～20 ratio, adds 85～95% ethanol in capsule of weeping forsythia powder, under 70～85 ℃ of temperature, refluxing extraction 4～6 hours, filter again, collect filtrate, filter residue, it in the ratio of filter residue weight and 70～80% ethanol volume 1: 5～10 ratio, ethanol with 70～80% carries out refluxing extraction after 2～3 hours again, refilters and collect filtrate, abandons filter residue.Then, the filtrate of twice collection is positioned in the vaporizer ,-0.08～-ethanol that is condensed into Herba Hyperici perforati medicinal extract and reclaims under the 0.05MPa vacuum.To reclaiming distillatory ethanol with alcoholic strength instrumentation alcohol concn wherein surely, being adjusted to alcohol concn with dehydrated alcohol again is 85～90% solution, is used to prepare Fructus Forsythiae extractum once more.

(2) preparation of Quercetin 3-galactoside concentrated solution

1. washing

In the Fructus Forsythiae extractum of (1) step preparation, add the ether agitator treating, the lipid material in the dissolving Fructus Forsythiae extractum carries out centrifugation again; Collect degreasing Fructus Forsythiae extractum and ether washings respectively.The degreasing Fructus Forsythiae extractum is carried out ether agitator treating and separation more once more, carry out so repeatedly 2～4 times, prepare the degreasing Fructus Forsythiae extractum.Each ether washings that adds is 1: 3～5 in the ratio of the volume of the weight of Fructus Forsythiae extractum and ether.Ether washings to each collection is used to prepare hypericin after the merging, to preparing the degreasing Fructus Forsythiae extractum, be used for next step and extract the absorption Quercetin 3-galactoside.

2. absorption

To the degreasing Fructus Forsythiae extractum of (2)-1. step preparation, in the liquid reflux device of belt stirrer, repeat 2～4 times with boiling distillated water and stir extraction, each extraction time is 15～30 minutes, collects the Quercetin 3-galactoside extracting solution.Then, after the Quercetin 3-galactoside extracting solution merging of at every turn collecting, when treating that its temperature is reduced to 40～50 ℃, it in polymeric adsorbent weight and Quercetin 3-galactoside extracting liquid volume ratio 1: 15～25 ratio, in the Quercetin 3-galactoside extracting solution, add polymeric adsorbent such as HPD600 or HZ-841, whip attachment 30～60 minutes is prepared HPD600 or the HZ-841 polymeric adsorbent that is adsorbed with Quercetin 3-galactoside after abandoning filtrate.

3. wash-out

Go on foot HPD600 that is adsorbed with Quercetin 3-galactoside or the HZ-841 polymeric adsorbent of preparing to (2)-2., after washing with the distilled water of 4～6 times of weight, be 1: 10～15 ratio again in the HPD600 that is adsorbed with Quercetin 3-galactoside or HZ-841 polymeric adsorbent weight and 70～80% alcoholic acid volume ratios, ethanol with 70～80% stirs wash-out, stirring elution time is 30～45 minutes, filter again, and collect filtrate and filter residue respectively, its filter residue is HPD600 or the HZ-841 polymeric adsorbent behind the wash-out Quercetin 3-galactoside.To polymeric adsorbent, be 1: 10～15 ratio again in polymeric adsorbent weight and 70～80% alcoholic acid volume ratios, the ethanol with 70～80% stirs wash-out once more, filters once more, collects filtrate and filter residue once more respectively, so repeats 2～4 times.Regenerate to having carried out 2～4 polymeric adsorbent filter residues behind the agitator treating at last.Each filtrate of collecting is Quercetin 3-galactoside solution, carries out next step vacuum concentration after the Quercetin 3-galactoside solution merging to each collection.

4. concentrate

Quercetin 3-galactoside solution to collection of (2)-3. step and merging, in vacuum concentrator ,-0.08～-carry out vacuum concentration under the 0.05MPa, after waiting to be condensed into paste, be 8.50～9.0 dissolved in distilled water again with the pH value, remove by filter impurity then, prepare Quercetin 3-galactoside concentration and be 2.31～2.80% Quercetin 3-galactoside concentrated solution.

5. polymeric adsorbent regeneration

With HPD600 or the HZ-841 polymeric adsorbent behind the wash-out Quercetin 3-galactoside of (2)-3. step collection, earlier with weight be 10～15 times, the pH value is that 5～6 aqueous solution agitator treating is regenerated, the agitator treating time is 30～60 minutes, after filter, abandon filtrate, collect regeneration polymeric adsorbent filter residue, can be used to handle the Quercetin 3-galactoside extracting solution once more.

(3) preparation of extraction agent

In cetyl trimethylammonium bromide (CTAB) cats product weight: octane volume: normal heptane volume: the distilled water volume is 1: 27～54: 3～6: 0.3～0.6 ratio, in the CTAB cats product, add octane and normal heptane earlier, heated and stirred, its Heating temperature is 40～60 ℃, the back adds distilled water, continues to be stirred to transparence, and just preparing CTAB concentration is the CTAB inverse micelle abstraction agent of 0.05～0.1mol/L.

(4) extracting and separating

1. extracting and separating

In the Quercetin 3-galactoside concentrated solution of (2)-4. step preparation, the CTAB inverse micelle abstraction agent that adds the preparation of (3) step, its Quercetin 3-galactoside concentrated solution: the volume ratio of CTAB inverse micelle abstraction agent is 1: 3～5, after the mixing, be to stir extraction 1～1.5 hour under 200～300 rev/mins the slow speed of revolution at rotating speed, use whizzer then under 6500～8000 rev/mins high rotating speed, centrifugation 10～20 minutes, mixed solution is separated into tangible upper and lower two-phase, and the inverse micelle abstraction liquid that collecting extraction mutually respectively has Quercetin 3-galactoside reaches the phase Quercetin 3-galactoside raffinate solution first time down.

2. extracting and separating again

In the following phase Quercetin 3-galactoside raffinate solution first time of (4)-1. step collection, the CTAB inverse micelle abstraction agent that adds the preparation of (3) step again, its Quercetin 3-galactoside is the raffinate liquor capacity for the first time: the volume ratio of CTAB inverse micelle abstraction agent is 1: 1～3, after the mixing, be under 200～300 rev/mins the slow speed of revolution at rotating speed, stir extraction 1～1.5 hour once more, and then with whizzer under 6500～8000 rev/mins high speed, recentrifuge separated 10～20 minutes, on mixed solution is separated into significantly, following two-phase, collecting extraction mutually once more has the inverse micelle abstraction liquid of Quercetin 3-galactoside to reach the phase Quercetin 3-galactoside raffinate solution second time down.Following phase Quercetin 3-galactoside raffinate solution for the second time is used to prepare hypericin.

(5) preparation of Quercetin 3-galactoside lyophilized powder

1. water is stripped and is separated

(4)-1. with 2. go on foot twice collection on mutually the extraction have in the inverse micelle abstraction liquid of Quercetin 3-galactoside, with extraction the volume ratio of the inverse micelle abstraction liquid of Quercetin 3-galactoside being arranged by water is 1: 1～3, add aqueous solution strippant and mixing, under rotating speed is 200～300 rev/mins rotating speed, stir earlier and stripped 15～30 minutes, the back uses whizzer under 6500～8000 rev/mins high speed, centrifugation 30～60 minutes, mixed solution obviously is divided into, following two-phase, inverse micelle abstraction liquid after stripping mutually in the collection respectively reaches the Quercetin 3-galactoside solution after stripping mutually down, and the inverse micelle abstraction liquid after the last reextraction is mutually regenerated.

2. concentrated freeze-dried

To the Quercetin 3-galactoside solution after the following reextraction mutually of (5)-1. step collection, earlier with vaporizer-0.08～-the 0.05MPa vacuum concentrates, the back under-50～-60 ℃ of low temperature, is frozen into Quercetin 3-galactoside content and is 83.6～87.3% with Freeze Drying Equipment, the Quercetin 3-galactoside lyophilized powder of moisture content≤7.26～8.76%, ash content≤0.44～8.94%.

3. inverse micelle abstraction liquid regeneration

To the inverse micelle abstraction liquid after stripping mutually in the collection of (5)-1. step, in 0.2～0.5mol/L potassiumiodide (KI) solution and the volume ratio of inverse micelle abstraction liquid is that 1: 100～150 ratio adds 0.2～0.5mol/LKI solution and mixes, be under 200～300 rev/mins the rotating speed at rotating speed, carried out stir process 30～60 minutes, then under 4000～6000 rev/mins of rotating speeds, centrifugation 15～30 minutes, collect upper and lower layer solution respectively, the upper strata inverse micelle abstraction liquid of collecting, can be used to extract Quercetin 3-galactoside solution once more, save the reverse micelle resource; The KI solution of the lower floor of collecting replenishes an amount of KI, and making its concentration is 0.2～0.5mol/L, can be once more as the regeneration of inverse micelle abstraction liquid.

(6) preparation of hypericin lyophilized powder

1. absorption washing

The ether washings that (2)-1. step collect was merged is behind 50～65 ℃ the steam distillation recovery ether, to prepare hypericin medicinal extract with temperature.Use 0.5～1%NaHCO then ₃Aqueous solution dissolving hypericin medicinal extract is prepared the NaHCO that contains hypericin ₃The aqueous solution, hypericin medicinal extract weight and 0.5～1%NaHCO ₃The ratio of aqueous solution volume is 1: 15～25.With the NaHCO that contains hypericin for preparing ₃The following Quercetin 3-galactoside mutually of the aqueous solution and (4)-2. step collection raffinate solution is for the second time merged into hypericin solution, in hypericin solution, add nonpolar adsorption resin (as HPD100 or HPD200 etc.) then, be under 200～300 rev/mins the speed at rotating speed, carry out whip attachment, the time of whip attachment is 1～2 hour, and the volume ratio of nonpolar adsorption resin weight and hypericin solution is 1: 10～15.After removing by filter filtrate then, collection is adsorbed with the polymeric adsorbent of hypericin, again with the pH value be 8.50～9.50, concentration is 90～95% ethanol, under 200～300 rev/mins of stirring velocitys, stir wash-out, stirring elution time is 30～60 minutes, filter, collect elutriant filtrate and polymeric adsorbent filter residue respectively, to the polymeric adsorbent filter residue of collecting, stir wash-out with 90～95% ethanol once more, the ratio of polymeric adsorbent weight and ethanol volume is 1: 10～and 15, filter once more and collect filtrate and filter residue respectively, carry out so repeatedly 2～4 times.The elutriant filtrate of each time collection is called the hypericin purification solution after merging, and the hypericin purification solution is carried out next step is concentrated freeze-dried; To having carried out the polymeric adsorbent filter residue behind the wash-out hypericin 2～4 times, carry out manipulation of regeneration.

2. concentrated freeze-dried

The hypericin purification solution that (6)-1. step was collected, earlier with vaporizer-0.08～-vacuum of 0.05Mpa under, reclaim ethanol, be condensed into the paste hypericin, use 0.5～1% NaHCO then ₃The aqueous solution dissolves the paste hypericin, and dissolving becomes hypericin NaHCO ₃The aqueous solution, paste hypericin weight and 0.5～1%NaHCO ₃The ratio of aqueous solution volume is 1: 20～30.NaHCO to hypericin ₃The aqueous solution removes by filter impurity again, and its filtrate is used Freeze Drying Equipment, is frozen into hypericin content and is 22.82～26.35% hypericin lyophilized powder under-50～-60 ℃ low temperature.

3. polymeric adsorbent regeneration

The HPD100 or the HPD200 polymeric adsorbent of the wash-out hypericin that (6)-1. step was collected are 5～6 aqueous solution agitator treating with the pH value, carry out filtering separation again.Abandon filtrate, collect the polymeric adsorbent filter residue, be 5～6 aqueous solution agitator treating once more with the pH value to the polymeric adsorbent of collecting, filter and collect polymeric adsorbent once more, carry out so repeatedly 2～4 times, polymeric adsorbent weight and pH value be the ratio of 5～6 aqueous solution volume be 1: 10 at every turn～20, the time of each agitator treating is 30～60 minutes.To through the polymeric adsorbent filter residue behind 2～4 agitator treatings, can reuse.

After the present invention adopts technique scheme, mainly have following characteristics:

1. from the Herba Hyperici perforati fruit, carry simultaneously and prepare Quercetin 3-galactoside and two kinds of active pharmaceutical ingredientss of hypericin; Fully utilized the Herba Hyperici perforati resource of China's abundant;

2. total recovery rate and the product purity of preparing product are all high, are respectively: total recovery rate of Quercetin 3-galactoside product is 90.1～93.6%, product purity 83.6～87.3%; Total recovery rate of hypericin product is 85.7～91.5% product purities 22.83%～29.63%, and production cost is low;

3. in process of production, the recovery of multiple solvent such as ethanol, ether and use have repeatedly once more been realized; Realize the regeneration of inverse micelle abstraction agent and polymeric adsorbent and use repeatedly, make full use of resource, reduce discharging of waste liquid, help environment protection.

The medical active product that adopts the inventive method to prepare, green product for natural plants, can be widely used in the medicines such as clearing heat and detoxicating, astringing to arrest bleeding, diuresis and depressed treatment, to prevention and treatment human diseases, the guarantee HUMAN HEALTH has important effect.

Four, embodiment

Below in conjunction with embodiment, further specify the present invention.

Embodiment 1

(1) preparation of Fructus Forsythiae extractum

After the Herba Hyperici perforati fruit is ground into capsule of weeping forsythia powder, be 1: 10 ratio in the ratio of capsule of weeping forsythia grain weight amount and 85% ethanol volume, add 85% ethanol in capsule of weeping forsythia powder, under 70 ℃ of temperature, refluxing extraction 4 hours is filtered again, collects filtrate.To filter residue, it in the ratio of filter residue weight and 70% ethanol volume 1: 5 ratio, ethanol with 70% carries out refluxing extraction after 2 hours again, refilter and collect filtrate, abandon filter residue, then, the filtrate of twice collection is positioned in the vaporizer ethanol that under-0.08MPa vacuum, is condensed into Herba Hyperici perforati medicinal extract and reclaims.To reclaiming distillatory ethanol with alcoholic strength instrumentation alcohol concn wherein surely, being adjusted to alcohol concn with dehydrated alcohol again is 85% solution, is used to prepare Fructus Forsythiae extractum once more.

(2) preparation of Quercetin 3-galactoside concentrated solution

1. washing

In the Fructus Forsythiae extractum of (1) step preparation, add the ether agitator treating, the lipid material in the dissolving Fructus Forsythiae extractum carries out centrifugation again; Collect degreasing Fructus Forsythiae extractum and ether washings respectively.The degreasing Fructus Forsythiae extractum is carried out ether agitator treating and separation more once more, carry out so repeatedly 2 times, prepare the degreasing Fructus Forsythiae extractum.Each ether washings that adds is 1: 3 in the ratio of the volume of the weight of Fructus Forsythiae extractum and ether.Ether washings to each collection is used to prepare hypericin after the merging, to preparing the degreasing Fructus Forsythiae extractum, be used for next step and extract the absorption Quercetin 3-galactoside.

2. absorption

To the degreasing Fructus Forsythiae extractum of (2)-1. step preparation, in the liquid reflux device of belt stirrer, repeat 2 times with boiling distillated water and stir extraction, each extraction time is 15 minutes, collects the Quercetin 3-galactoside extracting solution.Then, after the Quercetin 3-galactoside extracting solution merging of at every turn collecting, when treating that its temperature is reduced to 40 ℃, it in polymeric adsorbent weight and Quercetin 3-galactoside extracting liquid volume ratio 1: 15 ratio, in the Quercetin 3-galactoside extracting solution, add polymeric adsorbent such as HPD600, whip attachment 30 minutes is prepared the HPD600 polymeric adsorbent that is adsorbed with Quercetin 3-galactoside after abandoning filtrate.

3. wash-out

Go on foot the HPD600 polymeric adsorbent of preparing that is adsorbed with Quercetin 3-galactoside to (2)-2., after washing with the distilled water of 4 times of weight, be 1: 10 ratio again in HPD600 polymeric adsorbent weight that is adsorbed with Quercetin 3-galactoside and 70% alcoholic acid volume ratio, ethanol with 70% stirs wash-out, stirring elution time is 30 minutes, filter, and collect filtrate and filter residue respectively, its filter residue is the HPD600 polymeric adsorbent behind the wash-out Quercetin 3-galactoside.To polymeric adsorbent, be 1: 10 ratio again in polymeric adsorbent weight and 70% alcoholic acid volume ratio, the ethanol with 70% stirs wash-out once more, filters once more, collects filtrate and filter residue once more respectively.Regenerate to having carried out 2 polymeric adsorbent filter residues behind the agitator treating at last.The filtrate of collecting for 2 times is Quercetin 3-galactoside solution, carries out next step vacuum concentration after the Quercetin 3-galactoside solution merging to 2 collections.

4. concentrate

Quercetin 3-galactoside solution to collection of (2)-3. step and merging, in vacuum concentrator, under-0.08MPa, carry out vacuum concentration, after waiting to be condensed into paste, be 8.50 dissolved in distilled water again with the pH value, remove by filter impurity then, prepare Quercetin 3-galactoside concentration and be 2.31% Quercetin 3-galactoside concentrated solution.

5. polymeric adsorbent regeneration

With the HPD600 polymeric adsorbent behind the wash-out Quercetin 3-galactoside of (2)-3. step collection, earlier with weight be 10 times, the pH value is that 5 aqueous solution agitator treating is regenerated, the agitator treating time is 30 minutes, after filter, abandon filtrate, collect regeneration polymeric adsorbent filter residue, can be used to handle the Quercetin 3-galactoside extracting solution once more.

(3) preparation of extraction agent

In cetyl trimethylammonium bromide (CTAB) cats product weight: octane volume: normal heptane volume: the distilled water volume is 1: 54: 6: 0.6 ratio, in the CTAB cats product, add octane and normal heptane earlier, heated and stirred, its Heating temperature is 40 ℃, the back adds distilled water, continues to be stirred to transparence, and just preparing CTAB concentration is the CTAB inverse micelle abstraction agent of 0.05mol/L.

(4) extracting and separating

1. extracting and separating

In the Quercetin 3-galactoside concentrated solution of (2)-4. step preparation, the CTAB inverse micelle abstraction agent that adds the preparation of (3) step, its Quercetin 3-galactoside concentrated solution: the volume ratio of CTAB inverse micelle abstraction agent is 1: 3, after the mixing, be to stir extraction 1 hour under 200 rev/mins the rotating speed at rotating speed, use whizzer then under 6500 rev/mins high rotating speed, centrifugation 10 minutes, mixed solution is separated into tangible upper and lower two-phase, and the inverse micelle abstraction liquid that collecting extraction mutually respectively has Quercetin 3-galactoside reaches the phase Quercetin 3-galactoside raffinate solution first time down;

2. extracting and separating again

In the following phase Quercetin 3-galactoside raffinate solution first time of (4)-1. step collection, the CTAB inverse micelle abstraction agent that adds the preparation of (3) step again, its Quercetin 3-galactoside is the raffinate liquor capacity for the first time: the volume ratio of CTAB inverse micelle abstraction agent is 1: 1, after the mixing, be under 200 rev/mins the slow speed of revolution at rotating speed, stir extraction 1 hour once more, and then with whizzer under 6500 rev/mins high speed, recentrifuge separated 10 minutes, on mixed solution is separated into significantly, following two-phase, collecting extraction mutually once more has the inverse micelle abstraction liquid of Quercetin 3-galactoside to reach the phase Quercetin 3-galactoside raffinate solution second time down.Following phase Quercetin 3-galactoside raffinate solution for the second time is used to prepare hypericin.

(5) preparation of Quercetin 3-galactoside lyophilized powder

1. water is stripped and is separated

(4)-1. with 2. go on foot twice collection on mutually the extraction have in the inverse micelle abstraction liquid of Quercetin 3-galactoside, with extraction the volume ratio of the inverse micelle abstraction liquid of Quercetin 3-galactoside being arranged by water is 1: 1, add aqueous solution strippant and mixing, under rotating speed is 200 rev/mins low speed, stir earlier and stripped 15 minutes, the back uses whizzer under 6500 rev/mins high speed, centrifugation 30 minutes, mixed solution obviously is divided into, following two-phase, inverse micelle abstraction liquid after stripping mutually in the collection respectively reaches the Quercetin 3-galactoside solution after stripping mutually down, and the inverse micelle abstraction liquid after the last reextraction is mutually regenerated.

2. concentrated freeze-dried

To the Quercetin 3-galactoside solution after the following reextraction mutually of (5)-1. step collection, concentrate in-0.08MPa vacuum earlier with vaporizer, the back under-50 ℃ of low temperature, is frozen into Quercetin 3-galactoside content and is 83.6% with Freeze Drying Equipment, the Quercetin 3-galactoside lyophilized powder of moisture content≤7.26%, ash content≤0.44%;

3. inverse micelle abstraction liquid regeneration

To the inverse micelle abstraction liquid after stripping mutually in the collection of (5)-1. step, in 0.2mol/L potassiumiodide (KI) solution and the volume ratio of inverse micelle abstraction liquid is that 1: 100 ratio adds 0.2mol/L KI solution and mixes, be under 200 rev/mins the rotating speed at rotating speed, carried out stir process 30 minutes, then under 4000 rev/mins of rotating speeds, centrifugation 15 minutes, collect upper and lower layer solution respectively, the upper strata inverse micelle abstraction liquid of collecting can be used to extract Quercetin 3-galactoside solution once more, saves the reverse micelle resource; The KI solution of the lower floor of collecting replenishes an amount of KI, and making its concentration is 0.2mol/L, can be once more as the regeneration of inverse micelle abstraction liquid.

(6) preparation of hypericin lyophilized powder

1. absorption washing

The ether washings that (2)-1. step collect was merged is behind 50 ℃ the steam distillation recovery ether, to prepare hypericin medicinal extract with temperature.Use 0.5%NaHCO then ₃Aqueous solution dissolving hypericin medicinal extract is prepared the NaHCO that contains hypericin ₃The aqueous solution, hypericin medicinal extract weight and 0.5%NaHCO ₃The ratio of aqueous solution volume is 1: 15.With the NaHCO that contains hypericin for preparing ₃The following Quercetin 3-galactoside mutually of the aqueous solution and (4)-2. step collection raffinate solution is for the second time merged into hypericin solution, in hypericin solution, add nonpolar adsorption resin HPD100 then, at rotating speed is under 200 rev/mins of speed, carry out whip attachment, the time of whip attachment is 1 hour, and the volume ratio of nonpolar adsorption resin weight and hypericin solution is 1: 10.After removing by filter filtrate then, collection is adsorbed with the polymeric adsorbent of hypericin, again with the pH value be 8.50, concentration is 90% ethanol, stirs wash-out under 200 rev/mins stirring velocity, stirring elution time is 30 minutes, filter, collect elutriant filtrate and polymeric adsorbent filter residue respectively,, stir wash-out with 90% ethanol once more the polymeric adsorbent filter residue of collecting, the ratio of polymeric adsorbent weight and ethanol volume is 1: 10, filters and collect respectively filtrate and filter residue once more.The elutriant filtrate of collecting for 2 times is called the hypericin purification solution after merging, and the hypericin purification solution is carried out next step is concentrated freeze-dried; To having carried out the polymeric adsorbent filter residue behind the wash-out hypericin 2 times, carry out manipulation of regeneration.

2. concentrated freeze-dried

The hypericin purification solution that (6)-1. step was collected, earlier with vaporizer under the vacuum of-0.08Mpa, reclaim ethanol, be condensed into the paste hypericin, use 0.5% NaHCO then ₃The aqueous solution dissolves the paste hypericin, and dissolving becomes hypericin NaHCO ₃The aqueous solution, paste hypericin weight and 0.5%NaHCO ₃The ratio of aqueous solution volume is 1: 20.NaHCO to hypericin ₃The aqueous solution removes by filter impurity again, and its filtrate is used Freeze Drying Equipment, is frozen into hypericin content and is 22.82% hypericin lyophilized powder under-50 ℃ low temperature.

3. polymeric adsorbent regeneration

The HPD100 polymeric adsorbent of the wash-out hypericin that (6)-1. step was collected is 5 aqueous solution agitator treating with the pH value, carries out filtering separation again.Abandon filtrate, collect the polymeric adsorbent filter residue, be 5 aqueous solution agitator treating once more with the pH value to the polymeric adsorbent of collecting, filter and collect polymeric adsorbent once more, carry out so repeatedly 2 times, polymeric adsorbent weight and pH value are that the ratio of 5 aqueous solution volume is 1: 10 at every turn, and the time of each agitator treating is 30 minutes.To through the polymeric adsorbent filter residue behind 2 agitator treatings, can reuse.

Embodiment 2

(1) preparation of Fructus Forsythiae extractum

After the Herba Hyperici perforati fruit is ground into capsule of weeping forsythia powder, be 1: 20 ratio in the ratio of capsule of weeping forsythia grain weight amount and 95% ethanol volume, add 95% ethanol in capsule of weeping forsythia powder, under 85 ℃ of temperature, refluxing extraction 6 hours is filtered again, collects filtrate.To filter residue, be 1: 10 ratio in the ratio of filter residue weight and 80% ethanol volume, the ethanol with 80% carries out refluxing extraction after 3 hours again, refilters and collect filtrate, abandons filter residue.Then, the filtrate of twice collection is positioned in the vaporizer ethanol that under-0.05MPa vacuum, is condensed into Herba Hyperici perforati medicinal extract and reclaims.To reclaiming distillatory ethanol with alcoholic strength instrumentation alcohol concn wherein surely, being adjusted to alcohol concn with dehydrated alcohol again is 90% solution, is used to prepare Fructus Forsythiae extractum once more.

(2) preparation of Quercetin 3-galactoside concentrated solution

1. washing

In the Fructus Forsythiae extractum of (1) step preparation, add the ether agitator treating, the lipid material in the dissolving Fructus Forsythiae extractum carries out centrifugation again; Collect degreasing Fructus Forsythiae extractum and ether washings respectively.The degreasing Fructus Forsythiae extractum is carried out ether agitator treating and separation more once more, carry out so repeatedly 4 times, prepare the degreasing Fructus Forsythiae extractum.Each ether washings that adds is 1: 5 in the ratio of the volume of the weight of Fructus Forsythiae extractum and ether.Ether washings to each collection is used to prepare hypericin after the merging, to preparing the degreasing Fructus Forsythiae extractum, be used for next step and extract the absorption Quercetin 3-galactoside.

2. absorption

To the degreasing Fructus Forsythiae extractum of (2)-1. step preparation, in the liquid reflux device of belt stirrer, repeat 4 times with boiling distillated water and stir extraction, each extraction time is 30 minutes, collects the Quercetin 3-galactoside extracting solution.Then, after the Quercetin 3-galactoside extracting solution merging of at every turn collecting, when treating that its temperature is reduced to 50 ℃, it in polymeric adsorbent weight and Quercetin 3-galactoside extracting liquid volume ratio 1: 25 ratio, in the Quercetin 3-galactoside extracting solution, add polymeric adsorbent such as HZ-841, whip attachment 60 minutes is prepared the HZ-841 polymeric adsorbent that is adsorbed with Quercetin 3-galactoside after abandoning filtrate.

3. wash-out

Go on foot the HZ-841 polymeric adsorbent of preparing that is adsorbed with Quercetin 3-galactoside to (2)-2., after washing with the distilled water of 6 times of weight, be 1: 15 ratio again in HZ-841 polymeric adsorbent weight that is adsorbed with Quercetin 3-galactoside and 80% alcoholic acid volume ratio, ethanol with 80% stirs wash-out, stirring elution time is 45 minutes, filter, and collect filtrate and filter residue respectively, its filter residue is the HZ-841 polymeric adsorbent behind the wash-out Quercetin 3-galactoside.To polymeric adsorbent, be 1: 15 ratio again in polymeric adsorbent weight and 80% alcoholic acid volume ratio, the ethanol with 80% stirs wash-out once more, filters once more, collects filtrate and filter residue once more respectively, so repeats 4 times.Regenerate to having carried out 4 polymeric adsorbent filter residues behind the agitator treating at last.The filtrate of collecting for 4 times is Quercetin 3-galactoside solution, carries out next step vacuum concentration after the Quercetin 3-galactoside solution merging to 4 collections.

4. concentrate

Quercetin 3-galactoside solution to collection of (2)-3. step and merging, in vacuum concentrator, under-0.05MPa, carry out vacuum concentration, after waiting to be condensed into paste, be 9.0 dissolved in distilled water again with the pH value, remove by filter impurity then, prepare Quercetin 3-galactoside concentration and be 2.80% Quercetin 3-galactoside concentrated solution.

5. polymeric adsorbent regeneration

With the HZ-841 polymeric adsorbent behind the wash-out Quercetin 3-galactoside of (2)-3. step collection, earlier with weight be 15 times, the pH value is that 6 aqueous solution agitator treating is regenerated, the agitator treating time is 60 minutes, after filter, abandon filtrate, collect regeneration polymeric adsorbent filter residue, can be used to handle the Quercetin 3-galactoside extracting solution once more.

(3) preparation of extraction agent

In cetyl trimethylammonium bromide (CTAB) cats product weight: octane volume: normal heptane volume: the distilled water volume is 1: 27: 3: 0.6 ratio, in the CTAB cats product, add octane and normal heptane earlier, heated and stirred, its Heating temperature is 60 ℃, the back adds distilled water, continues to be stirred to transparence, and just preparing CTAB concentration is the CTAB inverse micelle abstraction agent of 0.1mol/L.

(4) extracting and separating

1. extracting and separating

In the Quercetin 3-galactoside concentrated solution of (2)-4. step preparation, the CTAB inverse micelle abstraction agent that adds the preparation of (3) step, its Quercetin 3-galactoside concentrated solution: the volume ratio of CTAB inverse micelle abstraction agent is 1: 5, after the mixing, be to stir extraction 1.5 hours under 300 rev/mins the rotating speed at rotating speed, use whizzer then under 8000 rev/mins high rotating speed, centrifugation 20 minutes, mixed solution is separated into tangible upper and lower two-phase, and the inverse micelle abstraction liquid that collecting extraction mutually respectively has Quercetin 3-galactoside reaches the phase Quercetin 3-galactoside raffinate solution first time down;

2. extracting and separating again

In the following phase Quercetin 3-galactoside raffinate solution first time of (4)-1. step collection, the CTAB inverse micelle abstraction agent that adds the preparation of (3) step again, its Quercetin 3-galactoside is the raffinate liquor capacity for the first time: the volume ratio of CTAB inverse micelle abstraction agent is 1: 3, after the mixing, be under 300 rev/mins the slow speed of revolution at rotating speed, stir extraction 1.5 hours once more, and then with whizzer under 8000 rev/mins high speed, recentrifuge separated 20 minutes, on mixed solution is separated into significantly, following two-phase, collecting extraction mutually once more has the inverse micelle abstraction liquid of Quercetin 3-galactoside to reach the phase Quercetin 3-galactoside raffinate solution second time down.Following phase Quercetin 3-galactoside raffinate solution for the second time is used to prepare hypericin.

(5) preparation of Quercetin 3-galactoside lyophilized powder

1. water is stripped and is separated

(4)-1. with 2. go on foot twice collection on mutually the extraction have in the inverse micelle abstraction liquid of Quercetin 3-galactoside, with extraction the volume ratio of the inverse micelle abstraction liquid of Quercetin 3-galactoside being arranged by water is 1: 3, add aqueous solution strippant and mixing, under rotating speed is 300 rev/mins low speed, stir earlier and stripped 30 minutes, the back uses whizzer under 8000 rev/mins high speed, centrifugation 60 minutes, mixed solution obviously is divided into, following two-phase, inverse micelle abstraction liquid after stripping mutually in the collection respectively reaches the Quercetin 3-galactoside solution after stripping mutually down, and the inverse micelle abstraction liquid after the last reextraction is mutually regenerated.

2. concentrated freeze-dried

To the Quercetin 3-galactoside solution after the following reextraction mutually of (5)-1. step collection, concentrate in-0.05MPa vacuum earlier with vaporizer, the back under-60 ℃ of low temperature, is frozen into Quercetin 3-galactoside content and is 87.3% with Freeze Drying Equipment, the Quercetin 3-galactoside lyophilized powder of moisture content≤7.26%, ash content≤0.44%;

3. inverse micelle abstraction liquid regeneration

To the inverse micelle abstraction liquid after stripping mutually in the collection of (5)-1. step, in 0.5mol/L potassiumiodide (KI) solution and the volume ratio of inverse micelle abstraction liquid is that 1: 150 ratio adds 0.5mol/L KI solution and mixes, be under 300 rev/mins the rotating speed at rotating speed, carried out stir process 60 minutes, then under 6000 rev/mins of rotating speeds, centrifugation 30 minutes, collect upper and lower layer solution respectively, the upper strata inverse micelle abstraction liquid of collecting can be used to extract Quercetin 3-galactoside solution once more, saves the reverse micelle resource; The KI solution of the lower floor of collecting replenishes an amount of KI, and making its concentration is 0.5mol/L, can be once more as the regeneration of inverse micelle abstraction liquid.

(6) preparation of hypericin lyophilized powder

1. absorption washing

The ether washings that (2)-1. step collect was merged is behind 65 ℃ the steam distillation recovery ether, to prepare hypericin medicinal extract with temperature.Use 1%NaHCO then ₃Aqueous solution dissolving hypericin medicinal extract is prepared the NaHCO that contains hypericin ₃The aqueous solution, hypericin medicinal extract weight and 1%NaHCO ₃The ratio of aqueous solution volume is 1: 25.With the NaHCO that contains hypericin for preparing ₃The following Quercetin 3-galactoside mutually of the aqueous solution and (4)-2. step collection raffinate solution is for the second time merged into hypericin solution, in hypericin solution, add nonpolar adsorption resin HPD200 etc. then, at rotating speed is under 300 rev/mins of speed, carry out whip attachment, the time of whip attachment is 2 hours, and the volume ratio of nonpolar adsorption resin weight and hypericin solution is 1: 15.After removing by filter filtrate then, collection is adsorbed with the polymeric adsorbent of hypericin, again with the pH value be 9.50, concentration is 95% ethanol, under 300 rev/mins of stirring velocitys, stir wash-out, stirring elution time is 60 minutes, filter, collect elutriant filtrate and polymeric adsorbent filter residue respectively, to the polymeric adsorbent filter residue of collecting, stir wash-out with 95% ethanol once more, the ratio of polymeric adsorbent weight and ethanol volume is 1: 15, filters once more and collects filtrate and filter residue respectively, carries out so repeatedly 4 times.The elutriant filtrate of each time collection is called the hypericin purification solution after merging, and the hypericin purification solution is carried out next step is concentrated freeze-dried; To having carried out the polymeric adsorbent filter residue behind the wash-out hypericin 4 times, carry out manipulation of regeneration.

2. concentrated freeze-dried

The hypericin purification solution that (6)-1. step was collected, earlier with vaporizer under the vacuum of-0.05Mpa, reclaim ethanol, be condensed into the paste hypericin, use 1% NaHCO then ₃The aqueous solution dissolves the paste hypericin, and dissolving becomes hypericin NaHCO ₃The aqueous solution, paste hypericin weight and 0.5～1%NaHCO ₃The ratio of aqueous solution volume is 1: 30.NaHCO to hypericin ₃The aqueous solution removes by filter impurity again, and its filtrate is used Freeze Drying Equipment, is frozen into hypericin content and is 26.35% hypericin lyophilized powder under-60 ℃ low temperature.

3. polymeric adsorbent regeneration

The HPD200 polymeric adsorbent of the wash-out hypericin that (6)-1. step was collected is 6 aqueous solution agitator treating with the pH value, carries out filtering separation again.Abandon filtrate, collect the polymeric adsorbent filter residue, be 6 aqueous solution agitator treating once more with the pH value to the polymeric adsorbent of collecting, filter and collect polymeric adsorbent once more, carry out so repeatedly 4 times, polymeric adsorbent weight and pH value are that the ratio of 6 aqueous solution volume is 1: 20 at every turn, and the time of each agitator treating is 60 minutes.To through the polymeric adsorbent filter residue behind 4 agitator treatings, can reuse.

Description of drawings

Accompanying drawing is a process flow sheet of the present invention.

Claims

1. the preparation method of Quercetin 3-galactoside and hypericin in the Herba Hyperici perforati is characterized in that concrete method steps is as follows:

(1) preparation of Fructus Forsythiae extractum

After the Herba Hyperici perforati fruit is ground into capsule of weeping forsythia powder, be 1: 10～20 ratio, in capsule of weeping forsythia powder, add 85～95% ethanol in the ratio of capsule of weeping forsythia grain weight amount and 85～95% ethanol volume, under 70～85 ℃ of temperature, refluxing extraction 4～6 hours is filtered again, collects filtrate.To filter residue, it in the ratio of filter residue weight and 70～80% ethanol volume 1: 5～10 ratio, ethanol with 70～80% carries out refluxing extraction after 2～3 hours again, refilter and collect filtrate, abandon filter residue, then, the filtrate of twice collection is positioned in the vaporizer,-0.08～-ethanol that is condensed into Herba Hyperici perforati medicinal extract and reclaims under the 0.05MPa vacuum, to reclaiming distillatory ethanol with alcoholic strength instrumentation alcohol concn wherein surely, being adjusted to alcohol concn with dehydrated alcohol again is 85～90% solution;

(2) preparation of Quercetin 3-galactoside concentrated solution

1. washing

In the Fructus Forsythiae extractum of (1) step preparation, add the ether agitator treating, carry out centrifugation again; Collect degreasing Fructus Forsythiae extractum and ether washings respectively, the degreasing Fructus Forsythiae extractum is carried out ether agitator treating and separation more once more, carry out so repeatedly 2～4 times, each ether washings that adds is 1: 3～5 in the ratio of the volume of the weight of Fructus Forsythiae extractum and ether;

2. absorption

Degreasing Fructus Forsythiae extractum to the preparation of (2)-1. step, in the liquid reflux device of belt stirrer, repeat 2～4 times with boiling distillated water and stir extraction, each extraction time is 15～30 minutes, collect the Quercetin 3-galactoside extracting solution, then, after the Quercetin 3-galactoside extracting solution merging of at every turn collecting, when treating that its temperature is reduced to 40～50 ℃, in polymeric adsorbent weight and Quercetin 3-galactoside extracting liquid volume ratio is 1: 15～25 ratio, in the Quercetin 3-galactoside extracting solution, adds HPD600 or HZ-841 polymeric adsorbent, whip attachment 30～60 minutes is abandoned filtrate;

3. wash-out

Go on foot HPD600 that is adsorbed with Quercetin 3-galactoside or the HZ-841 polymeric adsorbent of preparing to (2)-2., after washing with the distilled water of 4～6 times of weight, be 1: 10～15 ratio again in the HPD600 that is adsorbed with Quercetin 3-galactoside or HZ-841 polymeric adsorbent weight and 70～80% alcoholic acid volume ratios, ethanol with 70～80% stirs wash-out, stirring elution time is 30～45 minutes, filter again, and collect filtrate and filter residue respectively, to HPD600 or the HZ-841 polymeric adsorbent filter residue behind the wash-out Quercetin 3-galactoside of collecting, be 1: 10～15 ratio again in polymeric adsorbent weight and 70～80% alcoholic acid volume ratios, ethanol with 70～80% stirs wash-out once more, filter once more, collect filtrate and filter residue once more respectively, so repeat 2～4 times;

4. concentrate

Quercetin 3-galactoside solution to collection of (2)-3. step and merging, in vacuum concentrator ,-0.08～-carry out vacuum concentration under the 0.05MPa, after waiting to be condensed into paste, be 8.50～9.0 dissolved in distilled water again with the pH value, remove by filter impurity then, prepare Quercetin 3-galactoside concentration and be 2.31～2.80% Quercetin 3-galactoside concentrated solution;

5. polymeric adsorbent regeneration

With HPD600 or the HZ-841 polymeric adsorbent behind the wash-out Quercetin 3-galactoside of (2)-3. step collection, earlier with weight be 10～15 times, the pH value is that 5～6 aqueous solution agitator treating is regenerated, the agitator treating time is 30～60 minutes, after filter, abandon filtrate, collect regeneration polymeric adsorbent filter residue;

(3) preparation of extraction agent

In cetyl trimethylammonium bromide (CTAB) cats product weight: octane volume: normal heptane volume: the distilled water volume is 1: 27～54: 3～6: 0.3～0.6 ratio, in the CTAB cats product, add octane and normal heptane earlier, heated and stirred, its Heating temperature is 40～60 ℃, the back adds distilled water, continues to be stirred to transparence, and just preparing CTAB concentration is the CTAB inverse micelle abstraction agent of 0.05～0.1mol/L;

(4) extracting and separating

1. extracting and separating

In the Quercetin 3-galactoside concentrated solution of (2)-4. step preparation, the CTAB inverse micelle abstraction agent that adds the preparation of (3) step, its Quercetin 3-galactoside concentrated solution: the volume ratio of CTAB inverse micelle abstraction agent is 1: 3～5, after the mixing, be to stir extraction 1～1.5 hour under 200～300 rev/mins the slow speed of revolution at rotating speed, use whizzer then under 6500～8000 rev/mins high rotating speed, centrifugation 10～20 minutes, mixed solution is separated into tangible upper and lower two-phase, and the inverse micelle abstraction liquid that collecting extraction mutually respectively has Quercetin 3-galactoside reaches the phase Quercetin 3-galactoside raffinate solution first time down;

2. extracting and separating again

In the following phase Quercetin 3-galactoside raffinate solution first time of (4)-1. step collection, the CTAB inverse micelle abstraction agent that adds the preparation of (3) step again, its Quercetin 3-galactoside is the raffinate liquor capacity for the first time: the volume ratio of CTAB inverse micelle abstraction agent is 1: 1～3, after the mixing, be under 200～300 rev/mins the slow speed of revolution at rotating speed, stir extraction 1～1.5 hour once more, and then with whizzer under 6500～8000 rev/mins high speed, recentrifuge separated 10～20 minutes, on mixed solution is separated into significantly, following two-phase, collecting extraction mutually once more has the inverse micelle abstraction liquid of Quercetin 3-galactoside to reach the phase Quercetin 3-galactoside raffinate solution second time down;

(5) preparation of Quercetin 3-galactoside lyophilized powder

1. water is stripped and is separated

(4)-1. with 2. go on foot twice collection on mutually the extraction have in the inverse micelle abstraction liquid of Quercetin 3-galactoside, with extraction the volume ratio of the inverse micelle abstraction liquid of Quercetin 3-galactoside being arranged by water is 1: 1～3, add aqueous solution strippant and mixing, under rotating speed is 200～300 rev/mins rotating speed, stir earlier and stripped 15～30 minutes, the back uses whizzer under 6500～8000 rev/mins high speed, centrifugation 30～60 minutes, mixed solution obviously is divided into upper and lower two-phase, and the inverse micelle abstraction liquid after stripping mutually in the collection respectively reaches the Quercetin 3-galactoside solution after stripping mutually down;

2. concentrated freeze-dried

To the Quercetin 3-galactoside solution after the following reextraction mutually of (5)-1. step collection, earlier with vaporizer-0.08～-the 0.05MPa vacuum concentrates, the back under-50～-60 ℃ of low temperature, is frozen into Quercetin 3-galactoside content and is 83.6～87.3% with Freeze Drying Equipment, the Quercetin 3-galactoside lyophilized powder of moisture content≤7.26～8.76%, ash content≤0.44～8.94%;

3. inverse micelle abstraction liquid regeneration

To the inverse micelle abstraction liquid after stripping mutually in the collection of (5)-1. step, in the 0.2～0.5mol/L liquor kalii iodide and the volume ratio of inverse micelle abstraction liquid is that 1: 100～150 ratio adds 0.2～0.5mol/L KI solution and mixes, be under 200～300 rev/mins the rotating speed at rotating speed, carried out stir process 30～60 minutes, then under 4000～6000 rev/mins of rotating speeds, centrifugation 15～30 minutes, collect upper strata inverse micelle abstraction liquid and the KI of lower floor solution respectively, to KI solution, replenish an amount of KI, making its concentration is 0.2～0.5mol/L;

(6) preparation of hypericin lyophilized powder

1. absorption washing

The ether washings that (2)-1. step collect was merged is 50～65 ℃ a steam distillation recovery ether with temperature, uses 0.5～1%NaHCO then ₃Aqueous solution dissolving hypericin medicinal extract, hypericin medicinal extract weight and 0.5～1%NaHCO ₃The ratio of aqueous solution volume is 1: 15～25, with the NaHCO that contains hypericin for preparing ₃The following Quercetin 3-galactoside mutually of the aqueous solution and (4)-2. step collection raffinate solution is for the second time merged into hypericin solution, in hypericin solution, add HPD100 or HPD200 nonpolar adsorption resin then, be under 200～300 rev/mins the speed at rotating speed, carry out whip attachment, the time of whip attachment is 1～2 hour, the volume ratio of nonpolar adsorption resin weight and hypericin solution is 1: 10～15, after removing by filter filtrate then, collection is adsorbed with the polymeric adsorbent of hypericin, be 8.50～9.50 with the pH value again, concentration is 90～95% ethanol, under 200～300 rev/mins of stirring velocitys, stir wash-out, stirring elution time is 30～60 minutes, filter, collect elutriant filtrate and polymeric adsorbent filter residue respectively, to the polymeric adsorbent filter residue of collecting, stir wash-out with 90～95% ethanol once more, the ratio of polymeric adsorbent weight and ethanol volume is 1: 10～and 15, filter once more and collect filtrate and filter residue respectively, carry out so repeatedly 2～4 times;

2. concentrated freeze-dried

The hypericin purification solution that (6)-1. step was collected, earlier with vaporizer-0.08～-vacuum of 0.05Mpa under, reclaim ethanol, be condensed into the paste hypericin, use 0.5～1% NaHCO then ₃The aqueous solution dissolves the paste hypericin, and dissolving becomes hypericin NaHCO ₃The aqueous solution, paste hypericin weight and 0.5～1%NaHCO ₃The ratio of aqueous solution volume is 1: 20～30, to the NaHCO of hypericin ₃The aqueous solution removes by filter impurity again, and its filtrate is used Freeze Drying Equipment, is frozen into hypericin content and is 22.82～26.35% hypericin lyophilized powder under-50～-60 ℃ low temperature;

3. polymeric adsorbent regeneration

The HPD100 or the HPD200 polymeric adsorbent of the wash-out hypericin that (6)-1. step was collected, it with the pH value 5～6 aqueous solution agitator treating, carry out filtering separation again, abandon filtrate, collect the polymeric adsorbent filter residue, be 5～6 aqueous solution agitator treating once more with the pH value to the polymeric adsorbent of collecting, filter and collect polymeric adsorbent once more, carry out so repeatedly 2～4 times, polymeric adsorbent weight and pH value be the ratio of 5～6 aqueous solution volume be 1: 10 at every turn～20, the time of each agitator treating is 30～60 minutes.

2. according to the preparation method of Quercetin 3-galactoside and hypericin in the described Herba Hyperici perforati of claim 1., it is characterized in that the preparation method of Quercetin 3-galactoside and hypericin in a kind of Herba Hyperici perforati, its concrete method steps is as follows:

(1) preparation of Fructus Forsythiae extractum

After the Herba Hyperici perforati fruit is ground into capsule of weeping forsythia powder, it in the ratio of capsule of weeping forsythia grain weight amount and 85% ethanol volume 1: 10 ratio, in capsule of weeping forsythia powder, add 85% ethanol, under 70 ℃ of temperature, refluxing extraction 4 hours, filter again, collect filtrate, to filter residue, in the ratio of filter residue weight and 70% ethanol volume is 1: 5 ratio, and the ethanol with 70% carries out refluxing extraction after 2 hours again, refilters and collect filtrate, abandon filter residue, then, the filtrate of twice collection is positioned in the vaporizer ethanol that under-0.08MPa vacuum, is condensed into Herba Hyperici perforati medicinal extract and reclaims, to reclaiming distillatory ethanol with alcoholic strength instrumentation alcohol concn wherein surely, being adjusted to alcohol concn with dehydrated alcohol again is 85% solution;

(2) preparation of Quercetin 3-galactoside concentrated solution

1. washing

In the Fructus Forsythiae extractum of (1) step preparation, add the ether agitator treating, carry out centrifugation again, collect degreasing Fructus Forsythiae extractum and ether washings respectively, the degreasing Fructus Forsythiae extractum is carried out ether agitator treating and separation more once more, carry out so repeatedly 2 times, each ether washings that adds is 1: 3 in the ratio of the volume of the weight of Fructus Forsythiae extractum and ether;

2. absorption

To the degreasing Fructus Forsythiae extractum of (2)-1. step preparation, in the liquid reflux device of belt stirrer, repeat 2 times with boiling distillated water and stir extraction, each extraction time is 15 minutes, collect the Quercetin 3-galactoside extracting solution, then, after the Quercetin 3-galactoside extracting solution merging of at every turn collecting, when treating that its temperature is reduced to 40 ℃, in polymeric adsorbent weight and Quercetin 3-galactoside extracting liquid volume ratio is 1: 15 ratio, in the Quercetin 3-galactoside extracting solution, adds the HPD600 polymeric adsorbent, whip attachment 30 minutes is abandoned filtrate;

3. wash-out

Go on foot the HPD600 polymeric adsorbent of preparing that is adsorbed with Quercetin 3-galactoside to (2)-2., after washing with the distilled water of 4 times of weight, be 1: 10 ratio again in HPD600 polymeric adsorbent weight that is adsorbed with Quercetin 3-galactoside and 70% alcoholic acid volume ratio, ethanol with 70% stirs wash-out, stirring elution time is 30 minutes, filter again, and collect filtrate and filter residue respectively, to the HPD600 polymeric adsorbent filter residue behind the wash-out Quercetin 3-galactoside of collecting, be 1: 10 ratio again in polymeric adsorbent weight and 70% alcoholic acid volume ratio, ethanol with 70% stirs wash-out once more, filters once more, collects filtrate and filter residue once more respectively;

4. concentrate

Quercetin 3-galactoside solution to collection of (2)-3. step and merging, in vacuum concentrator, under-0.08MPa, carry out vacuum concentration, after waiting to be condensed into paste, be 8.50 dissolved in distilled water again with the pH value, remove by filter impurity then, prepare Quercetin 3-galactoside concentration and be 2.31% Quercetin 3-galactoside concentrated solution;

5. polymeric adsorbent regeneration

HPD600 polymeric adsorbent behind the wash-out Quercetin 3-galactoside that (2)-3. step was collected, earlier with weight be 10 times, pH value is 5 aqueous solution agitator treating regeneration, the agitator treating time is 30 minutes, after filter, abandon filtrate, the collection polymeric adsorbent filter residue of regenerating;

(3) preparation of extraction agent

In cetyl trimethylammonium bromide (CTAB) cats product weight: octane volume: normal heptane volume: the distilled water volume is 1: 54: 6: 0.6 ratio, in the CTAB cats product, add octane and normal heptane earlier, heated and stirred, its Heating temperature is 40 ℃, the back adds distilled water, continues to be stirred to transparence, and just preparing CTAB concentration is the CTAB inverse micelle abstraction agent of 0.05mol/L;

(4) extracting and separating

1. extracting and separating

2. extracting and separating again

In the following phase Quercetin 3-galactoside raffinate solution first time of (4)-1. step collection, the CTAB inverse micelle abstraction agent that adds the preparation of (3) step again, its Quercetin 3-galactoside is the raffinate liquor capacity for the first time: the volume ratio of CTAB inverse micelle abstraction agent is 1: 1, after the mixing, be under 200 rev/mins the slow speed of revolution at rotating speed, stir extraction 1 hour once more, and then with whizzer under 6500 rev/mins high speed, recentrifuge separated 10 minutes, on mixed solution is separated into significantly, following two-phase, collecting extraction mutually once more has the inverse micelle abstraction liquid of Quercetin 3-galactoside to reach the phase Quercetin 3-galactoside raffinate solution second time down;

(5) preparation of Quercetin 3-galactoside lyophilized powder

1. water is stripped and is separated

(4)-1. with 2. go on foot twice collection on mutually the extraction have in the inverse micelle abstraction liquid of Quercetin 3-galactoside, with extraction the volume ratio of the inverse micelle abstraction liquid of Quercetin 3-galactoside being arranged by water is 1: 1, add aqueous solution strippant and mixing, under rotating speed is 200 rev/mins low speed, stir earlier and stripped 15 minutes, the back uses whizzer under 6500 rev/mins high speed, centrifugation 30 minutes, mixed solution obviously is divided into upper and lower two-phase, and the inverse micelle abstraction liquid after stripping mutually in the collection respectively reaches the Quercetin 3-galactoside solution after stripping mutually down;

2. concentrated freeze-dried

3. inverse micelle abstraction liquid regeneration

To the inverse micelle abstraction liquid after stripping mutually in the collection of (5)-1. step, in the 0.2mol/L liquor kalii iodide and the volume ratio of inverse micelle abstraction liquid is that 1: 100 ratio adds 0.2mol/L KI solution and mixes, be under 200 rev/mins the rotating speed at rotating speed, carried out stir process 30 minutes, then under 4000 rev/mins rotating speed, centrifugation 15 minutes, collect upper and lower layer solution respectively, upper strata inverse micelle abstraction liquid of Shou Jiing and the KI of lower floor solution respectively, to KI solution, replenish an amount of KI, making its concentration is 0.2mol/L;

(6) preparation of hypericin lyophilized powder

1. absorption washing

The ether washings that (2)-1. step collect was merged is behind 50 ℃ the steam distillation recovery ether, to use 0.5%NaHCO then with temperature ₃Aqueous solution dissolving hypericin medicinal extract, hypericin medicinal extract weight and 0.5%NaHCO ₃The ratio of aqueous solution volume is 1: 15, with the NaHCO that contains hypericin for preparing ₃The following Quercetin 3-galactoside mutually of the aqueous solution and (4)-2. step collection raffinate solution is for the second time merged into hypericin solution, in hypericin solution, add the HPD100 nonpolar adsorption resin then, at rotating speed is under 200 rev/mins of speed, carry out whip attachment, the time of whip attachment is 1 hour, the volume ratio of nonpolar adsorption resin weight and hypericin solution is 1: 10, after removing by filter filtrate then, collection is adsorbed with the polymeric adsorbent of hypericin, be 8.50 with the pH value again, concentration is 90% ethanol, under 200 rev/mins of stirring velocitys, stir wash-out, stirring elution time is 30 minutes, filter, collect elutriant filtrate and polymeric adsorbent filter residue respectively,, stir wash-out with 90% ethanol once more the polymeric adsorbent filter residue of collecting, the ratio of polymeric adsorbent weight and ethanol volume is 1: 10, filters and collect respectively filtrate and filter residue once more;

2. concentrated freeze-dried

The hypericin purification solution that (6)-1. step was collected, earlier with vaporizer under the vacuum of-0.08Mpa, reclaim ethanol, be condensed into the paste hypericin, use 0.5% NaHCO then ₃The aqueous solution dissolves the paste hypericin, and dissolving becomes hypericin NaHCO ₃The aqueous solution, paste hypericin weight and 0.5%NaHCO ₃The ratio of aqueous solution volume is 1: 20.NaHCO to hypericin ₃The aqueous solution removes by filter impurity again, and its filtrate is used Freeze Drying Equipment, is frozen into hypericin content and is 22.82% hypericin lyophilized powder under-50 ℃ low temperature;

3. polymeric adsorbent regeneration

The HPD100 polymeric adsorbent of the wash-out hypericin that (6)-1. step was collected is 5 aqueous solution agitator treating with the pH value, carries out filtering separation again.Abandon filtrate, collecting the polymeric adsorbent filter residue, is 5 aqueous solution agitator treating with the pH value to the polymeric adsorbent of collecting once more, filters and collect polymeric adsorbent once more, polymeric adsorbent weight and pH value are that the ratio of 5 aqueous solution volume is 1: 10 at every turn, and the time of each agitator treating is 30 minutes.

3. according to the preparation method of Quercetin 3-galactoside and hypericin in the described Herba Hyperici perforati of claim 1., it is characterized in that the preparation method of Quercetin 3-galactoside and hypericin in a kind of Herba Hyperici perforati, its concrete method steps is as follows:

(1) preparation of Fructus Forsythiae extractum

After the Herba Hyperici perforati fruit is ground into capsule of weeping forsythia powder, it in the ratio of capsule of weeping forsythia grain weight amount and 95% ethanol volume 1: 20 ratio, in capsule of weeping forsythia powder, add 95% ethanol, under 85 ℃ of temperature, refluxing extraction 6 hours, filter again, collect filtrate, to filter residue, in the ratio of filter residue weight and 80% ethanol volume is 1: 10 ratio, and the ethanol with 80% carries out refluxing extraction after 3 hours again, refilters and collect filtrate, abandon filter residue, then, the filtrate of twice collection is positioned in the vaporizer ethanol that under-0.05MPa vacuum, is condensed into Herba Hyperici perforati medicinal extract and reclaims, to reclaiming distillatory ethanol with alcoholic strength instrumentation alcohol concn wherein surely, being adjusted to alcohol concn with dehydrated alcohol again is 90% solution;

(2) preparation of Quercetin 3-galactoside concentrated solution

1. washing

In the Fructus Forsythiae extractum of (1) step preparation, add the ether agitator treating, carry out centrifugation again, collect degreasing Fructus Forsythiae extractum and ether washings respectively, the degreasing Fructus Forsythiae extractum is carried out ether agitator treating and separation more once more, carry out so repeatedly 4 times, each ether washings that adds is 1: 5 in the ratio of the volume of the weight of Fructus Forsythiae extractum and ether;

2. absorption

To the degreasing Fructus Forsythiae extractum of (2)-1. step preparation, in the liquid reflux device of belt stirrer, repeat 4 times with boiling distillated water and stir extraction, each extraction time is 30 minutes, collect the Quercetin 3-galactoside extracting solution, then, after the Quercetin 3-galactoside extracting solution merging of at every turn collecting, when treating that its temperature is reduced to 50 ℃, in polymeric adsorbent weight and Quercetin 3-galactoside extracting liquid volume ratio is 1: 25 ratio, in the Quercetin 3-galactoside extracting solution, adds the HZ-841 polymeric adsorbent, whip attachment 60 minutes is abandoned filtrate;

3. wash-out

Go on foot the HZ-841 polymeric adsorbent of preparing that is adsorbed with Quercetin 3-galactoside to (2)-2., after washing with the distilled water of 6 times of weight, be 1: 15 ratio again in HZ-841 polymeric adsorbent weight that is adsorbed with Quercetin 3-galactoside and 80% alcoholic acid volume ratio, ethanol with 80% stirs wash-out, stirring elution time is 45 minutes, filter again, and collect filtrate and filter residue respectively, to the HZ-841 polymeric adsorbent filter residue behind the wash-out Quercetin 3-galactoside of collecting, be 1: 15 ratio again in polymeric adsorbent weight and 80% alcoholic acid volume ratio, the ethanol with 80% stirs wash-out once more, filters once more, collect filtrate and filter residue once more respectively, so repeat 4 times;

4. concentrate

Quercetin 3-galactoside solution to collection of (2)-3. step and merging, in vacuum concentrator, under-0.05MPa, carry out vacuum concentration, after waiting to be condensed into paste, be 9.0 dissolved in distilled water again with the pH value, remove by filter impurity then, prepare Quercetin 3-galactoside concentration and be 2.80% Quercetin 3-galactoside concentrated solution;

5. polymeric adsorbent regeneration

HZ-841 polymeric adsorbent behind the wash-out Quercetin 3-galactoside that (2)-3. step was collected, earlier with weight be 15 times, pH value is 6 aqueous solution agitator treating regeneration, the agitator treating time is 60 minutes, after filter, abandon filtrate, the collection polymeric adsorbent filter residue of regenerating;

(3) preparation of extraction agent

In cetyl trimethylammonium bromide (CTAB) cats product weight: octane volume: normal heptane volume: the distilled water volume is 1: 27: 3: 0.6 ratio, in the CTAB cats product, add octane and normal heptane earlier, heated and stirred, its Heating temperature is 60 ℃, the back adds distilled water, continues to be stirred to transparence, and just preparing CTAB concentration is the CTAB inverse micelle abstraction agent of 0.1mol/L;

(4) extracting and separating

1. extracting and separating

2. extracting and separating again

In the following phase Quercetin 3-galactoside raffinate solution first time of (4)-1. step collection, the CTAB inverse micelle abstraction agent that adds the preparation of (3) step again, its Quercetin 3-galactoside is the raffinate liquor capacity for the first time: the volume ratio of CTAB inverse micelle abstraction agent is 1: 3, after the mixing, be under 300 rev/mins the slow speed of revolution at rotating speed, stir extraction 1.5 hours once more, and then with whizzer under 8000 rev/mins high speed, recentrifuge separated 20 minutes, on mixed solution is separated into significantly, following two-phase, collecting extraction mutually once more has the inverse micelle abstraction liquid of Quercetin 3-galactoside to reach the phase Quercetin 3-galactoside raffinate solution second time down;

(5) preparation of Quercetin 3-galactoside lyophilized powder

1. water is stripped and is separated

(4)-1. with 2. go on foot twice collection on mutually the extraction have in the inverse micelle abstraction liquid of Quercetin 3-galactoside, with extraction the volume ratio of the inverse micelle abstraction liquid of Quercetin 3-galactoside being arranged by water is 1: 3, add aqueous solution strippant and mixing, under rotating speed is 300 rev/mins low speed, stir earlier and stripped 30 minutes, the back uses whizzer under 8000 rev/mins high speed, centrifugation 60 minutes, mixed solution obviously is divided into upper and lower two-phase, and the inverse micelle abstraction liquid after stripping mutually in the collection respectively reaches the Quercetin 3-galactoside solution after stripping mutually down;

2. concentrated freeze-dried

3. inverse micelle abstraction liquid regeneration

To the inverse micelle abstraction liquid after stripping mutually in the collection of (5)-1. step, in the 0.5mol/L liquor kalii iodide and the volume ratio of inverse micelle abstraction liquid is that 1: 150 ratio adds 0.5mol/L KI solution and mixes, be under 300 rev/mins the rotating speed at rotating speed, carried out stir process 60 minutes, then under 6000 rev/mins of rotating speeds, centrifugation 30 minutes, collect upper strata inverse micelle abstraction liquid and the KI of lower floor solution respectively, to KI solution, replenish an amount of KI, making its concentration is 0.5mol/L;

(6) preparation of hypericin lyophilized powder

1. absorption washing

The ether washings that (2)-1. step collect was merged is behind 65 ℃ the steam distillation recovery ether, to use 1%NaHCO then with temperature ₃Aqueous solution dissolving hypericin medicinal extract, hypericin medicinal extract weight and 1%NaHCO ₃The ratio of aqueous solution volume is 1: 25, with the NaHCO that contains hypericin for preparing ₃The following Quercetin 3-galactoside mutually of the aqueous solution and (4)-2. step collection raffinate solution is for the second time merged into hypericin solution, in hypericin solution, add the HPD200 nonpolar adsorption resin then, be under 300 rev/mins the speed at rotating speed, carry out whip attachment, the time of whip attachment is 2 hours, the volume ratio of nonpolar adsorption resin weight and hypericin solution is 1: 15, after removing by filter filtrate then, collection is adsorbed with the polymeric adsorbent of hypericin, be 9.50 with the pH value again, concentration is 95% ethanol, under 300 rev/mins of stirring velocitys, stir wash-out, stirring elution time is 60 minutes, filter, collect elutriant filtrate and polymeric adsorbent filter residue respectively, to the polymeric adsorbent filter residue of collecting, stir wash-out with 95% ethanol once more, the ratio of polymeric adsorbent weight and ethanol volume is 1: 15, filters once more and collects filtrate and filter residue respectively, carries out so repeatedly 4 times;

2. concentrated freeze-dried

The hypericin purification solution that (6)-1. step was collected, earlier with vaporizer under the vacuum of-0.05Mpa, reclaim ethanol, be condensed into the paste hypericin, use 1% NaHCO then ₃The aqueous solution dissolves the paste hypericin, and dissolving becomes hypericin NaHCO ₃The aqueous solution, paste hypericin weight and 0.5～1%NaHCO ₃The ratio of aqueous solution volume is 1: 30.NaHCO to hypericin ₃The aqueous solution removes by filter impurity again, and its filtrate is used Freeze Drying Equipment, is frozen into hypericin content and is 26.35% hypericin lyophilized powder under-60 ℃ low temperature;

3. polymeric adsorbent regeneration

The HPD200 polymeric adsorbent of the wash-out hypericin that (6)-1. step was collected, it with the pH value 6 aqueous solution agitator treating, carry out filtering separation again, abandoning filtrate, collect the polymeric adsorbent filter residue, is 6 aqueous solution agitator treating once more with the pH value to the polymeric adsorbent of collecting, filter and collect polymeric adsorbent once more, carry out so repeatedly 4 times, polymeric adsorbent weight and pH value are that the ratio of 6 aqueous solution volume is 1: 20 at every turn, and the time of each agitator treating is 60 minutes.