CN101775028B - Method for gathering and purifying agrimonine in agrimony - Google Patents
Method for gathering and purifying agrimonine in agrimony Download PDFInfo
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- CN101775028B CN101775028B CN 200910216881 CN200910216881A CN101775028B CN 101775028 B CN101775028 B CN 101775028B CN 200910216881 CN200910216881 CN 200910216881 CN 200910216881 A CN200910216881 A CN 200910216881A CN 101775028 B CN101775028 B CN 101775028B
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Abstract
The invention belongs to the filed of natural organic chemistry and relates to a method for purifying agrimonine, in particular to a method for gathering and purifying the agrimonine in agrimony by utilizing high-speed counter current chromatography. The method is characterized in that leaching liquor of natural plant agrimony is purified twice by utilizing the high-speed counter current chromatography, thus obtaining the agrimonine with the purity of 98 percent. The method is suitable for preparing the high-purity agrimonine by adopting various natural plants and extracts of the natural plants containing the agrimonine as the main materials. The method is suitable for separating and preparing the agrimonine by adopting a counter current chromatograph of various types, and the method for preparing the agrimonine by utilizing the high-speed counter current chromatography can carry out continuous, efficient and rapid liquid-liquid partition chromatographic separation and has the advantages of large separation amount, no sample loss, high recovery rate, mild separation environment, saving solvent and the like.
Description
Technical field:
The invention belongs to the natural organic chemistry field, relate to a kind of purification process of agrimonine, particularly relate to a kind of preparation method who utilizes agrimonine in the high speed adverse current chromatogram partition method enriching and purifying Herba Agrimoniae.
Background technology:
Herba Agrimoniae: the Rosaceae (Rosaceae) Radix Agrimoniae belongs to the common name of (Agrimonia) plant, refers to European Radix Agrimoniae (A.eupatoria) especially.This kind originates in Europe for cold-resistant perennial herb, and also there is cultivation in other warm areas.High 30-100cm, complete stool tool white becomes mildewed, and rhizome is horizontal to be walked, cylindrical, and autumn end is given birth to the white section bud that a taper shape is bent upwards from tip.Stem is upright.Odd number pinnately compound leaf alternate, leaflet differs in size, and is spaced, and oval is to obovate, and stipule is avette.Give birth on raceme top or armpit is given birth to, spend little, yellow, there are groove and hairiness in calyx Tong outside, the hook-shaped seta of a circle, sliver 5 are given birth in the top; Petal 5; Stamen 10; Carpel 2.The achene turbination, deposit the calyx lobe place.The florescence 7-8 month, the fruit phase 9-10 month.All produce all parts of the country, is distributed in wasteland, hillside, bend, meadow.Be used as medicine with over-ground part, be called Herba Agrimoniae, Xia Qiu gathers, and its bud also is used as medicine.Herb contains agrimonine, agrimonolide, tannin (for Jiao's property catechol tannin, gallotannin etc.), sterol, organic acid, phenolic constituent, saponin etc.Root contains tannin 8.9%, and stem contains tannin 6.5%, and leaf contains tannin 16.4%.Stem, leaf also contain luteolin-7-β-glycoside and apigenin-7-β-glycoside.
Agrimonine is a kind of human health to be had the natural active matter of remarkable health-care effect, has caused the common concern of international community.Prove that through scientific research and clinical application agrimonine has hemostasis, cardiac stimulant, strong, end dysentery and antiinflammation.Cure mainly that the power of taking off is tired, menoxenia, red leukorrhea, stomach cold stomachache, dysentery, haematemesis, spitting of blood, intestines wind, hematuria, uterine hemorrhage, the symptoms such as duodenal hemorrhage of collapsing.In recent years, it is found that and contain a large amount of agrimonines in the natural phant Herba Agrimoniae, therefrom extract the agrimonine first and obtained encouraging progress that because its raw material Herba Agrimoniae is Chinese medicine, raw material sources are wider.Name is called just to disclose the patent application of " extracting the method for agrimonine from Herba Agrimoniae " extracts the agrimonine technical process with Herba Agrimoniae through solvent extration optimization.Agrimonine extraction process in the above-mentioned patent documentation mainly is through solvent extraction, and adsorption resin column carries out processing step such as purifying and extracts and form, and its separating effect is nothing like the separating effect of high speed adverse current chromatogram partition method.
Summary of the invention:
The objective of the invention is to overcome shortcomings such as the routine techniques extraction yield is relatively low, dna purity is low, a kind of preparation method who utilizes agrimonine in the high speed adverse current chromatogram partition method enriching and purifying Herba Agrimoniae is provided.For achieving the above object, the technical solution used in the present invention is:
A kind of preparation method who utilizes agrimonine in the high speed adverse current chromatogram partition method enriching and purifying Herba Agrimoniae.
Its step is as follows:
(1) with 70% acetone-water lixiviate Herba Agrimoniae, after vat liquor boils off acetone, gets primary extract;
(2) preliminary purification of agrimonine: primary extract is carried out initial gross separation with the high speed adverse current chromatogram partition method, collect the component that contains agrimonine, solvent evaporated;
(3) Herba Agrimoniae must be made with extra care: again (2) obtained component is made the pure product high-speed countercurrent chromatography of the agrimonine of high purity more than 98% with the high speed adverse current chromatogram partition method Herba Agrimoniae is carried out preliminary purification, the solvent system of selecting for use mainly contains three, be stationary phase mutually all, be moving phase mutually down, No. one solvent system is made of three components, and the A1 component is selected fatty lipids such as ethyl acetate, propyl acetate, isopropyl acetate, n-butyl acetate for use; The B1 component is selected Fatty Alcohol(C12-C14 and C12-C18) such as propyl carbinol, isopropylcarbinol, the trimethyl carbinol for use; The C1 component is water, ethyl acetate-n-butanol-water system.A1, B1, C1 volume ratio are 0.5-2: 2-10: 2-10; No. two solvent system is made of four components, and the A2 component is selected fatty lipids such as ethyl acetate, propyl acetate, isopropyl acetate, n-butyl acetate for use; B2, C2 component are selected Fatty Alcohol(C12-C14 and C12-C18) or aliphatic ketones such as methyl alcohol, ethanol, propyl alcohol, Virahol, acetone, propyl carbinol, isopropylcarbinol, the trimethyl carbinol for use; The D2 component is water, ethyl acetate-propyl carbinol-methanol-water system; A2, B2, C2, D2 volume ratio are 0.5-5: 10-100: 0.5-5: 10-100; No. three solvent system is made of two components, and the A3 component is selected Fatty Alcohol(C12-C14 and C12-C18) such as propyl carbinol, isopropylcarbinol, the trimethyl carbinol for use; The B3 component is water, preferred n-butanol-water system; A3, B3 volume ratio are 1-100: 1-100.
The high speed adverse current chromatogram partition method mainly contains three to agrimonine refining solvent system, be stationary phase mutually more than all, time is moving phase mutually, and No. four solvent system is made of three components, and the A4 component is selected halohydrocarbon such as chloroform, methylene dichloride, tetracol phenixin for use; The B4 component is selected Fatty Alcohol(C12-C14 and C12-C18) or aliphatic ketones such as methyl alcohol, ethanol, propyl alcohol, acetone for use; The C4 component is water, preferred chloroform-methanol-aqueous systems; A4, B4, C4 volume ratio are 2-15: 2-25: 1-15; No. five solvent system is made of four components, and the A5 component is selected halohydrocarbon such as chloroform, methylene dichloride, tetracol phenixin for use; B5, C5 component are selected Fatty Alcohol(C12-C14 and C12-C18) or aliphatic ketones such as methyl alcohol, ethanol, propyl alcohol, Virahol, acetone, propyl carbinol, isopropylcarbinol, the trimethyl carbinol for use; The D5 component is water, preferred chloroform-Virahol-methanol-water system; A5, B5, C5, D5 volume ratio are 2-10: 0.5-5: 2-10: 1-10; No. six solvent system is made of five components, and A6, C6 component are selected halohydrocarbon such as chloroform, methylene dichloride, tetracol phenixin for use; B6, D6 component are selected Fatty Alcohol(C12-C14 and C12-C18) or aliphatic ketones such as methyl alcohol, ethanol, propyl alcohol, Virahol, acetone, propyl carbinol, isopropylcarbinol, the trimethyl carbinol for use; The E6 component is water, preferred methylene dichloride-Virahol-chloroform-methanol-aqueous systems; A6, B6, C6, D6, E6 volume ratio are 0.5-2: 0.5-2: 1-10: 2-10: 1-10.
Experiment is applicable to that room temperature is to carry out under 15-30 ℃.
Agrimonine purity with this law preparation can reach more than 98%.This law is applicable to the natural phant that contains agrimonine with various, and the extract of natural phant is the highly purified agrimonine of feedstock production.Be applicable to that the counter current chromatograph that adopts various models separates the preparation agrimonine, preparing agrimonine with high-speed countercurrent chromatography can be continuously, efficiently, liquid liquid distribution chromatography separates fast, have that fractional dose is big, sample free of losses, rate of recovery height, isolating environment relax, save characteristics such as solvent.
Embodiment:
Embodiment 1:
Adopt ethyl acetate-n-butanol-water and chloroform-methanol-Virahol-water two solvent systems to prepare purity and be higher than 98% agrimonine: use half countercurrent chromatography instrument, is furnished with the NS-1007 pump, the 20ml sampling valve, the tetrafluoroethylene post, the volume of post is 240ml, 8823A-UV UV-detector Yokogawa 3057 potable recording instrument.Before the sample introduction, be full of whole pillar with stationary phase earlier, the adjustment engine speed is 800rpm, flow velocity with 2.0ml/min pumps into moving phase in the post, treat that whole system is set up running balance after, by the sampling valve sample introduction, then according to the detector uv-spectrogram, the receiving target composition.The preparation of agrimonine is carried out in two steps: (1) is that ethyl acetate-n-butanol-water of 1: 2: 3 is miscible in separating funnel with volume ratio, shakes up the back static layering.Get its upper solution (going up phase) and be stationary phase, lower floor's solution (following phase) is moving phase.The crude extract 100mg that obtains with 1: 1 upper and lower phase mixed solution 20ml dissolving separates, and collects the component that contains agrimonine, evaporate to dryness.(2) be 5: 6: 0.5 with volume ratio: chloroform-methanol-Virahol of 4-water is miscible in separating funnel, shakes up the back static layering.Get its upper solution (going up phase) and be stationary phase, lower floor's solution (following phase) is moving phase.Upper and lower phase mixed solution 2ml dissolving (1) gained sample with 1: 1 separates, and collects the component peaks that contains agrimonine, lyophilize.Get white agrimonine solid, analyze through HPLC, its purity reaches more than 98%.
Embodiment 2:
Adopt ethyl acetate-isopropylcarbinol-acetone-water and chloroform-methanol-water two solvent systems to prepare purity and be higher than 98% agrimonine: use half countercurrent chromatography instrument, is furnished with the NS-1007 pump, the 20ml sampling valve, the tetrafluoroethylene post, the volume of post is 240ml, 8823A-UV UV-detector Yokogawa 3057 potable recording instrument.Before the sample introduction, be full of whole pillar with stationary phase earlier, the adjustment engine speed is 800rpm, flow velocity with 2.0ml/min pumps into moving phase in the post, treat that whole system is set up running balance after, by the sampling valve sample introduction, then according to the detector uv-spectrogram, the receiving target composition.The preparation of agrimonine is carried out in two steps: (1) is 5: 40: 1 with volume ratio: ethyl acetate-isopropylcarbinol of 60-acetone-water is miscible in separating funnel, shakes up the back static layering.Get its upper solution (going up phase) and be stationary phase, lower floor's solution (following phase) is moving phase.The crude extract 200mg that obtains with 1: 1 upper and lower phase mixed solution 20ml dissolving separates, and collects the component that contains agrimonine, evaporate to dryness.(2) be that chloroform-methanol-water of 7: 13: 8 is miscible in separating funnel with volume ratio, shake up the back static layering.Get its upper solution (going up phase) and be stationary phase, lower floor's solution (following phase) is moving phase.Upper and lower phase mixed solution 2ml dissolving (1) gained sample with 1: 1 separates, and collects the component peaks that contains agrimonine, lyophilize.Get white agrimonine solid, analyze through HPLC, its purity reaches more than 98.23%.
Embodiment 3:
Adopt n-butanol-water and methylene dichloride-Virahol-chloroform-methanol-water two solvent systems to prepare purity and be higher than 98% agrimonine: use half countercurrent chromatography instrument, is furnished with the NS-1007 pump, the 20ml sampling valve, the tetrafluoroethylene post, the volume of post is 240ml, 8823A-UV UV-detector Yokogawa 3057 potable recording instrument.Before the sample introduction, be full of whole pillar with stationary phase earlier, the adjustment engine speed is 800rpm, flow velocity with 2.0ml/min pumps into moving phase in the post, treat that whole system is set up running balance after, by the sampling valve sample introduction, then according to the detector uv-spectrogram, the receiving target composition.The preparation of agrimonine is carried out in two steps: (1) is that 45: 53 n-butanol-water is miscible in separating funnel with volume ratio, shakes up the back static layering.Get its upper solution (going up phase) and be stationary phase, lower floor's solution (following phase) is moving phase.The crude extract 150mg that obtains with 1: 1 upper and lower phase mixed solution 20ml dissolving separates, and collects the component that contains agrimonine, evaporate to dryness.(2) be 1: 1: 4 with volume ratio: methylene dichloride-Virahol of 7: 5-chloroform-methanol-water is miscible in separating funnel, shakes up the back static layering.Get its upper solution (going up phase) and be stationary phase, lower floor's solution (following phase) is moving phase.Upper and lower phase mixed solution 2ml dissolving (1) gained sample with 1: 1 separates, and collects the component peaks that contains agrimonine, lyophilize.Get white agrimonine solid, analyze through HPLC, its purity reaches more than 98.02%.
Claims (2)
1. method of utilizing agrimonine in the high-speed countercurrent chromatography enriching and purifying Herba Agrimoniae is characterized in that its step is as follows:
(1) with 70% acetone-water lixiviate Herba Agrimoniae, after vat liquor boils off acetone, gets primary extract;
(2) preliminary purification of agrimonine: primary extract is carried out initial gross separation with the high speed adverse current chromatogram partition method, collect the component that contains agrimonine, solvent evaporated;
(3) Herba Agrimoniae must be made with extra care: again (2) obtained component is made the pure product of highly purified agrimonine with the high speed adverse current chromatogram partition method.
Wherein, when adopting the high speed adverse current chromatogram partition method that Aloe polysaccharide is carried out preliminary purification in the step (2), the solvent system that uses is selected from any one in a following solvent system, No. two solvent systems and No. three solvent systems, and the composition of described No. one, No. two and No. three solvent system and the volume ratio of each composition are as follows:
Solvent system a: A1+B1+C1
A1 is selected from: ethyl acetate, propyl acetate, isopropyl acetate, n-butyl acetate
B1 is selected from: propyl carbinol, isopropylcarbinol, the trimethyl carbinol
C1: water
Wherein the volume ratio of A1, B1, C1 is 0.5-2: 2-10: 2-10;
No. two solvent system: A2+B2+C2+D2
A2 is selected from: ethyl acetate, propyl acetate, isopropyl acetate, n-butyl acetate
B2 and C2 are selected from: methyl alcohol, ethanol, propyl alcohol, Virahol, acetone, propyl carbinol, isopropylcarbinol, the trimethyl carbinol
D2: water
Wherein the volume ratio of A2, B2, C2, D2 is 0.5-5: 10-100: 0.5-5: 10-100;
No. three solvent system: A3+B3
A3 is selected from: propyl carbinol, isopropylcarbinol, the trimethyl carbinol
B3: water
Wherein the volume ratio of A3, B3 is 1-100: 1-100;
When wherein adopting the high speed adverse current chromatogram partition method that Aloe polysaccharide is made with extra care in the step (3), the solvent system that uses is selected from any one in following No. four solvent systems, No. five solvent systems and No. six solvent systems, and the composition of described No. four, No. five and No. six solvent systems and the volume ratio of each composition are as follows:
No. four solvent system: A4+B4+C4
A4 is selected from: chloroform, methylene dichloride, tetracol phenixin
B4 is selected from: methyl alcohol, ethanol, propyl alcohol, acetone
C4: water
Wherein the volume ratio of A4, B4, C4 is 2-15: 2-25: 1-15;
No. five solvent system: A5+B5+C5+D5
A5 is selected from: chloroform, methylene dichloride, tetracol phenixin
B5 and C5 are selected from: methyl alcohol, ethanol, propyl alcohol, Virahol, acetone, propyl carbinol, isopropylcarbinol, the trimethyl carbinol
D5: water
The volume ratio of A5, B5, C5, D5 is 2-10: 0.5-5: 2-10: 1-10;
No. six solvent system: A6+B6+C6+D6+E6
A6, C6 are selected from: chloroform, methylene dichloride, tetracol phenixin
B6, D6 are selected from: methyl alcohol, ethanol, propyl alcohol, Virahol, acetone, propyl carbinol, isopropylcarbinol, the trimethyl carbinol
E6: water
Wherein the volume ratio of A6, B6, C6, D6, E6 is 0.5-2: 0.5-2: 1-10: 2-10: 1-10.
2. a kind of method of utilizing agrimonine in the high-speed countercurrent chromatography enriching and purifying Herba Agrimoniae according to claim 1, it is characterized in that, No. one, No. two, No. three solvent systems are respectively ethyl acetate-n-butanol-water system, ethyl acetate-propyl carbinol-methanol-water system and n-butanol-water system described in the step (2), and No. four, No. five, No. six solvent systems are respectively described in the step (3): chloroform-methanol-aqueous systems, chloroform-Virahol-methanol-water system and methylene dichloride-Virahol-chloroform-methanol-aqueous systems.
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| CN102532242A (en) * | 2010-12-24 | 2012-07-04 | 苏州宝泽堂医药科技有限公司 | Method for preparing aescine A |
| CN103044424B (en) * | 2012-12-13 | 2015-12-02 | 大兴安岭林格贝寒带生物科技股份有限公司 | A kind of method of matrine in enriching and purifying kuh-seng |
| CN103735659B (en) * | 2014-01-09 | 2014-12-03 | 广东幸美化妆品股份有限公司 | Preparation method and use of hairyvein agrimony effective ingredient |
| CN104987285B (en) * | 2014-11-18 | 2017-05-03 | 浙江工业大学 | Method for separating and purifying m-trihydroxybenzene compounds in Agrimonia polosa Ledeb |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101229252A (en) * | 2008-01-18 | 2008-07-30 | 重庆大学 | Agrimony total flavone extract, preparing method and applications thereof |
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| CN101229252A (en) * | 2008-01-18 | 2008-07-30 | 重庆大学 | Agrimony total flavone extract, preparing method and applications thereof |
Non-Patent Citations (1)
| Title |
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| 王洪江.仙鹤草药用成分与提取工艺的研究.《中国优秀博硕士学位论文全文数据库（硕士）工程科技Ⅰ辑》.2002,第2002卷(第1期),第B016-150页. * |
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