CN104817569A - Method for simultaneous separation of four gambogic acid components in Garcinia hanburyi - Google Patents
Method for simultaneous separation of four gambogic acid components in Garcinia hanburyi Download PDFInfo
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- CN104817569A CN104817569A CN201510111176.9A CN201510111176A CN104817569A CN 104817569 A CN104817569 A CN 104817569A CN 201510111176 A CN201510111176 A CN 201510111176A CN 104817569 A CN104817569 A CN 104817569A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/12—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains three hetero rings
- C07D493/20—Spiro-condensed systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J63/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton has been modified by expansion of only one ring by one or two atoms
- C07J63/008—Expansion of ring D by one atom, e.g. D homo steroids
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Abstract
The invention discloses a method for simultaneous separation of four gambogic acid components in Garcinia hanburyi. The method comprises the steps of: crushing Garcinia hanburyi medicinal material, then conducting extraction with acetone to obtain an extracted liquid, subjecting the extracted liquid to vacuum concentration, then adding water, carrying out fully stirring, dissolving, and filtering to obtain an insoluble matter; adding the insoluble matter into a 40% acetone solution, after complete dissolution, performing centrifugation to obtain the supernatant; introducing the supernatant into a well treated BS-16 type macroporous resin chromatographic column to conduct elution to obtain eluent, concentrating the eluent to an extract shape, then conducting dissolving with ethanol; and employing preparative liquid chromatography separation to obtain the four gambogic acid components, i.e. 2alpha-hydroxy-3beta-acetoxy betulinic acid, neogambogic acid, R-gambogic acid and S-gambogic acid. The method provided by the invention has a simple process, can obtain four gambogic acid components simultaneously, and improves the utilization value of Garcinia hanburyi.
Description
Technical field
The present invention relates to biomedicine technical field, be specifically related to a kind of method being simultaneously separated four kinds of gambogic acid compositions in gamboge.
Background technology
Colloidal resin secreted by Garcinia maingayii gamboge Garcinia hanburyi Hook.f., after drying, in cylindric or irregular block, containing acrylic component such as morellic acid, neogambogic acid, allogambogic acids.In recent years, Chinese scholar has done large quantifier elimination to the activeconstituents in Chinese medicine gamboge.Find after deliberation, the anti-tumor activity that morellic acid is stronger to kinds of tumors display, and in effective dosage ranges, toxic side effect is smaller, has very high selectivity to the suppression of tumour cell, optionally can kill cancer cells, and intact animal hemopoietic system and immunologic function are not affected.
Summary of the invention
The object of the present invention is to provide a kind of method being simultaneously separated four kinds of gambogic acid compositions in gamboge, improve the utility value to gamboge.
For achieving the above object, the technical scheme that the present invention takes is:
Be separated a method for four kinds of gambogic acid compositions in gamboge simultaneously, comprise the steps:
S1, by gamboge crude drug pulverize, quantitatively take 1Kg, be placed in 20L extractor, 10L acetone extraction twice, each 3h, filter, merge the filtrate of twice, obtain extracting solution;
S2, the extracting solution rotary evaporation of step S1 gained is concentrated into 800mL, obtains gamboge acetone concentrated solution, add 1600mL water, abundant stirring and dissolving, after room temperature leaves standstill 24h, filter, obtain insolubles;
S3, add in the insolubles of step S2 gained 40% acetone soln, until after insolubles dissolves completely, cross high speed centrifuge, obtain supernatant liquor;
S4, by the supernatant liquor sample introduction of step S3 gained in processed good BS-16 type macroporous resin chromatography column, use the distilled water wash-out of 3 times of column volumes successively, 40% acetone wash-out of 3 times of column volumes, 100% acetone wash-out of 3 times of column volumes, obtain gambogic acid macroporous resin elutriant, be concentrated into medicinal extract shape, with dissolve with ethanol (20g/100mL);
S5, get step S4 gained solution adopt preparative liquid chromatography be separated.To balance each other chromatographic column 20min by initial flow, each sampling volume 5mL, by setting gradient elution, gradient is in table 1, UV-detector is monitored in real time, collects 3 components that retention time is 8.0min, 10.3min, 17min (biased sample for 17.5min and 17.9min); After 20min, according to gradient initial proportion balance chromatographic column, again sample introduction, sample introduction 6 times altogether, same section is merged by retention time by collecting the elution fraction obtained, concentrated, reclaim under reduced pressure, room temperature leaves standstill 8h, separate out a large amount of powder, filter, 50 DEG C of dryings 12 hours, obtain product;
S6, collected sample when being 17min by the retention time of step S5 gained, concentration is become to be the sample of 5mg/mL with dissolve with ethanol, under condition described in step S5 repeatedly sample introduction repeatedly, each sampling volume 1mL, collect retention time be the effluent liquid of 17.5min and 17.9min, effluent liquid concentrating under reduced pressure, room temperature leaves standstill 8h, separates out powder, filters, 50 DEG C of dryings 12 hours, obtain R-morellic acid and S-morellic acid;
S7, gained each component product are 98.5% through HPLC purity check; Analysis condition is: c18 (5 μm, 250mm × 4.6mm), and moving phase is acetonitrile: water: phosphoric acid=85: 14.8: 0.2, and determined wavelength is 360nm, and flow velocity is 1mL/min, and column temperature is 25 DEG C.
Wherein, the frequency of described step S3 high speed whizzer is 25000r/min.
Wherein, the chromatographic column in described step S5 is c18 (10 μm, 250mm × 50mm); Ultraviolet detection wavelength is 360nm; Elution flow rate is 60mL/min; Gradient is: eluent adopts acetonitrile-water-Phosphoric Acid, and be first the acetonitrile of 70% by volume percent, volume percent is the phosphoric acid wash-out of 0.2%; Be the acetonitrile of 80% by volume percent again, volume percent is the phosphoric acid wash-out of 0.2%; Be finally 95% acetonitrile by volume percent, volume percent is the phosphoric acid wash-out of 0.2%, and 20min completes a separation cycle.
Wherein, the product in described step S5 is: retention time 8.0min is 2 Alpha-hydroxy-3 β-acetoxyl group Betulinic acid, and 10.3min is neogambogic acid, and 17min is the mixture of R-morellic acid and S-morellic acid two kinds of isomer.
After testing: gained gambogic acid each component, retention time 8.0min is 2 Alpha-hydroxy-3 β-acetoxyl group Betulinic acid, and 10.3min is neogambogic acid, 17.5min and 17.9min is respectively R-morellic acid and S-morellic acid.
The present invention has following beneficial effect:
Present invention process is simple, can obtain four kinds of gambogic acid compositions, improve the utility value to gamboge.
Accompanying drawing explanation
Fig. 1 is the HPLC collection of illustrative plates of gamboge macroporous resin acetone elution fraction in the embodiment of the present invention.
Fig. 2 is the preparative HPLC collection of illustrative plates that in the embodiment of the present invention, in gamboge, various gambogic acid monomer component is separated.
Embodiment
In order to make objects and advantages of the present invention clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Embodiments provide a kind of method being simultaneously separated four kinds of gambogic acid compositions in gamboge, comprise the steps:
S1, by gamboge crude drug pulverize, quantitatively take 1Kg, be placed in 20L extractor, 10L acetone extraction twice, each 3h, filter, merge the filtrate of twice, obtain extracting solution;
S2, the extracting solution rotary evaporation of step S1 gained is concentrated into 800mL, obtains gamboge acetone concentrated solution, add 1600mL water, abundant stirring and dissolving, after room temperature leaves standstill 24h, filter, obtain insolubles;
S3, add in the insolubles of step S2 gained 40% acetone soln, until after insolubles dissolves completely, cross high speed centrifuge, the frequency of whizzer is 25000r/min, obtains supernatant liquor;
S4, by the supernatant liquor sample introduction of step S3 gained in processed good BS-16 type macroporous resin chromatography column, use the distilled water wash-out of 3 times of column volumes successively, 40% acetone wash-out of 3 times of column volumes, 3 times of column volume 100% acetone wash-outs, obtain gambogic acid macroporous resin elutriant, be concentrated into medicinal extract shape, with dissolve with ethanol (20g/100mL);
S5, get step S4 gained solution adopt preparative liquid chromatography be separated.To balance each other chromatographic column 20min by initial flow, chromatographic column is c18 (10 μm, 250mm × 50mm); Ultraviolet detection wavelength is 360nm; Elution flow rate is 60mL/min; Gradient is as shown in table 1: eluent adopts acetonitrile-water-Phosphoric Acid, and be first the acetonitrile of 70% by volume percent, volume percent is the phosphoric acid wash-out of 0.2%; Be the acetonitrile of 80% by volume percent again, volume percent is the phosphoric acid wash-out of 0.2%; Be finally 95% acetonitrile by volume percent, volume percent is the phosphoric acid wash-out of 0.2%, and 20min completes a separation cycle.
The gradient of table 1 preparative liquid chromatography
| Time | Acetonitrile | Water | Phosphoric acid |
| 0 | 70 | 29.8 | 0.2 |
| 10 | 80 | 19.8 | 0.2 |
| 20 | 95 | 4.8 | 0.2 |
Each sampling volume 5mL, by setting gradient elution, UV-detector is monitored in real time, collects 3 components that retention time is 8.0min, 10.3min, 17min (biased sample for 17.5min and 17.9min); After 20min, according to gradient initial proportion balance chromatographic column, again sample introduction, sample introduction 6 times altogether, same section is merged by retention time by collecting the elution fraction obtained, concentrated, reclaim under reduced pressure, room temperature leaves standstill 8h, separate out a large amount of powder, filter, 50 DEG C of dryings obtain product for 12 hours, and (retention time 8.0min is 2 Alpha-hydroxy-3 β-acetoxyl group Betulinic acid, 10.3min is neogambogic acid, and 17min is the mixture of R-morellic acid and S-morellic acid two kinds of isomer);
S6, collected sample when being 17min by the retention time of the step S5 gained mixture of S-morellic acid two kinds of isomer (the R-morellic acid with) dissolve with ethanol becomes concentration to be the sample of 5mg/mL, under condition described in step S5, sample introduction is repeatedly repeatedly, each sampling volume 1mL, collecting retention time is the effluent liquid of 17.5min and 17.9min, effluent liquid concentrating under reduced pressure, and room temperature leaves standstill 8h, separate out powder, filter, 50 DEG C of dryings 12 hours, obtain R-morellic acid and S-morellic acid;
S7, gained each component product are 98.5% through HPLC purity check; Analysis condition is: c18 (5 μm, 250mm × 4.6mm), and moving phase is acetonitrile: water: phosphoric acid=85: 14.8: 0.2, and determined wavelength is 360nm, and flow velocity is 1mL/min, and column temperature is 25 DEG C.
After testing, gained gambogic acid each component, retention time 8.0min is 2 Alpha-hydroxy-3 β-acetoxyl group Betulinic acid, and 10.3min is neogambogic acid, 17.5min and 17.9min is respectively R-morellic acid and S-morellic acid.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (4)
1. be separated a method for four kinds of gambogic acid compositions in gamboge simultaneously, it is characterized in that, comprise the steps:
S1, by gamboge crude drug pulverize, quantitatively take 1Kg, be placed in 20L extractor, 10L acetone extraction twice, each 3h, filter, merge the filtrate of twice, obtain extracting solution;
S2, the extracting solution of step S1 gained is evaporated to 800mL, obtain gamboge acetone concentrated solution, add water 1600mL, abundant stirring and dissolving, after room temperature leaves standstill 24h, filters, obtain insolubles;
S3, add in the insolubles of step S2 gained 40% acetone soln, until after insolubles dissolves completely, centrifugal with supercentrifuge, obtain supernatant liquor;
In S4, BS-16 type macroporous resin chromatography column that the supernatant liquor sample introduction of step S3 gained is handled well to oneself, use the distilled water wash-out of 3 times of column volumes successively, 3 times of column volume 40% acetone wash-outs, 3 times of column volume 100% acetone wash-outs, obtain gambogic acid macroporous resin elutriant, be concentrated into medicinal extract shape, with dissolve with ethanol;
S5, get step S4 gained solution adopt preparative liquid chromatography be separated.First to balance each other chromatographic column 20min by initial flow, each sampling volume 5mL, by setting gradient elution, UV-detector is monitored in real time, collects 3 components that retention time is 8.0min, 10.3min, 17min (biased sample for 17.5min and 17.9min); After 20min, according to gradient initial proportion balance chromatographic column, again sample introduction, sample introduction 6 times altogether, same section is merged by retention time by collecting the elution fraction obtained, concentrated, reclaim under reduced pressure, room temperature leaves standstill 8h, separate out a large amount of powder, filter, 50 DEG C of dryings 12 hours, obtain product;
S6, collected sample when being 17min by the retention time of step S5 gained, concentration is become to be the sample of 5mg/mL with dissolve with ethanol, under condition described in step S5 repeatedly sample introduction repeatedly, each sampling volume 1mL, collect retention time be the effluent liquid of 17.Smin and 17.9min, effluent liquid concentrating under reduced pressure, room temperature leaves standstill 8h, separates out powder, filters, 50 DEG C of dryings 12 hours, obtain R-morellic acid and S-morellic acid;
S7, gained each component product are 98.5% through HPLC purity check; Analysis condition is: c18 (5 μm, 250mm × 4.6mm), and moving phase is acetonitrile: water: phosphoric acid=85: 14.8: 0.2, and determined wavelength is 360nm, and flow velocity is 1mL/min, and column temperature is 25 DEG C.
2. a kind of method being simultaneously separated four kinds of gambogic acid compositions in gamboge according to claim 1, it is characterized in that, the frequency of described step S3 high speed whizzer is 25000r/min.
3. a kind of method being simultaneously separated four kinds of gambogic acid compositions in gamboge according to claim 1, it is characterized in that, the chromatographic column in described step S5 is c18 (10 μm, 250mm × 50mm); Ultraviolet detection wavelength is 360nm; Elution flow rate is 60mL/min; Gradient is: eluent adopts acetonitrile-water-Phosphoric Acid, and be first the acetonitrile of 70% by volume percent, volume percent is the phosphoric acid wash-out of 0.2%; Be the acetonitrile of 80% by volume percent again, volume percent is the phosphoric acid wash-out of 0.2%; Be finally 95% acetonitrile by volume percent, volume percent is the phosphoric acid wash-out of 0.2%, and 20min completes a separation cycle.
4. a kind of method being simultaneously separated four kinds of gambogic acid compositions in gamboge according to claim 1, it is characterized in that, product in described step S5 is: retention time 8.0min is 2 Alpha-hydroxy-3 β-acetoxyl group Betulinic acid, 10.3min is neogambogic acid, and 17min is the mixture of R-morellic acid and S-morellic acid two kinds of isomer.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510111176.9A CN104817569B (en) | 2015-03-07 | 2015-03-07 | It is a kind of at the same separate gamboge in four kinds of gambogic acid compositions method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109053761A (en) * | 2018-09-16 | 2018-12-21 | 湖州展舒生物科技有限公司 | The preparation method of gambogicacid |
| CN110437246A (en) * | 2019-08-19 | 2019-11-12 | 济宁医学院 | The method that mesolow gradient silica gel dry column chromatography separates Neo-garcinolic acid, gambogicacid and the preparation of N- aryl gamboge amide |
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2015
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109053761A (en) * | 2018-09-16 | 2018-12-21 | 湖州展舒生物科技有限公司 | The preparation method of gambogicacid |
| CN110437246A (en) * | 2019-08-19 | 2019-11-12 | 济宁医学院 | The method that mesolow gradient silica gel dry column chromatography separates Neo-garcinolic acid, gambogicacid and the preparation of N- aryl gamboge amide |
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| CN104817569B (en) | 2017-11-03 |
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