CN103040880B - A kind of isolation and purification method of tribuloside - Google Patents
A kind of isolation and purification method of tribuloside Download PDFInfo
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- CN103040880B CN103040880B CN201210595557.5A CN201210595557A CN103040880B CN 103040880 B CN103040880 B CN 103040880B CN 201210595557 A CN201210595557 A CN 201210595557A CN 103040880 B CN103040880 B CN 103040880B
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- tribuloside
- ethanol water
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Abstract
The present invention discloses a kind of isolation and purification method of tribuloside, and this method is：From cast hopper input after raw material is cleaned, extractor group main frame rotates, material is slowly advanced backward from unit front end, the feed tube of Extraction solvent slave group end enters in extractor simultaneously, flowed by tank rear end through mobile material forward end, solid-liquid two-phase material is fully contacted in this reverse movement, so that extracts active ingredients in medicinal material be come out.The dregs of a decoction are pushed to slag notch through discharge conveyor pressure and discharged, and special Juice squeezer is extruded the dregs of a decoction, and dregs of a decoction Shen residual liquor is extruded into medicinal material tissue, reduce dregs of a decoction Shen residual liquor content.Extraction efficiency is higher, extract more complete.The present invention is simultaneously from macroporous absorbent resin and the purifying of binding silica gel column chromatography, and separating effect is more preferably.It is 2% that highest yield, which can be obtained, and content is more than 95% tribuloside finished product.
Description
Technical field：
The invention belongs to field of natural organic chemistry, it is related to a kind of isolation and purification method of tribuloside, particularly relates to
And a kind of method that joint macroporous absorbent resin coupling silica gel column chromatography separating purification tribuloside is extracted using adverse current.
Background technology：
Tribulus terrestris, alias thatch, puncture vine, Fructus Tribuli, bypass, drawer people, only row, jackal plumage, rise push away, i.e. lamb's-quarters, tribulus terrestris, shut out puncture
Lamb's-quarters, stop plumage, non-irrigated grass, triangle puncture vine, triangle thorn, anistree thorn, puncture frame, open country water caltrop, water chestnut, hard puncture vine, Ji Li Follicle radish etc., be puncture
The dry mature fruit of chenopod puncture vine.Fruit is containing Kaempferol, Kaempferol 3- glucosides, Kaempferol 3- rutinosides, thorn
Puncture vine glycosides, peroxidase etc..The effects such as with diuresis, anti arteriosclerosis, anti-aging.
Tribuloside is mainly steroid oside compound, and its sapogenin is diosgenin (diosgenin), Lu Qi
Can the another glucoside containing puncture vine such as sapogenin (ruscogenin), hecogenin (hecogenin), gitogenin (gitoogenin)
(tribuloside), Kaempferol-rutinoside (kaempferol-rutinoside), astragalin (astragalin),
Harmane (harmine) etc..Tribuloside can lift ketone testis naturally, increase strength, improve overall competitive state, nontoxic
Side effect, there is hypotensive, and reducing blood lipid etc. is acted on, peroxide decomposition enzyme contained therein, with obvious anti-aging effects.Long term usage
Can be dispelled scar on the face, and allow the tender lubrication of skin.In recent years, it has been found that contain substantial amounts of tribulus terrestris in natural plants tribulus terrestris
Saponin(e, therefrom extracts tribuloside and achieves encouraging progress, raw material tribulus terrestris source is wider.
The content of the invention
Present invention aims at provide a kind of isolation and purification method of tribuloside；The object of the invention also resides in offer one
Plant abundant convenient and swift, raw material sources, extraction efficiency height, isolate and purify the utilization continuous flow upstream that effect is obvious, DNA purity is high
Extract the production technology with enriching and purifying macroporous resin tribuloside.
The present invention seeks to what is be achieved through the following technical solutions.
A kind of isolation and purification method of tribuloside, its step is as follows：
(1) continuous countercurrent extracting tank ethanol water refluxing extraction is added after tribulus terrestris is cleaned；
(2) extract solution that will be handled through (1) is filtered, and obtains tribuloside crude extract；
(3) gained tribuloside crude extract is concentrated, obtains the thick concentrate of tribuloside；
(4) the thick concentrate of gained tribuloside is diluted with water, and filtered, obtain filtrate；
(5) by the upper broad spectrum type macroporous resin adsorption post of gained filtrate, absorption, which is finished, is washed with water impurity, then with the second of low powered posterior chamber
Alcohol solution washes impurity, is then eluted with the ethanol water of the high number of degrees, obtains tribuloside eluent；
(6) gained eluent is condensed into cream, obtains tribuloside condensed cream；
(7) tribuloside condensed cream is mixed into silica gel, and by the mixture mixed as above silicagel column, through ethyl acetate
With the elution of petroleum ether mixed liquor, eluent is obtained；
(8) tribuloside semi-finished product will be concentrated and dried to obtain after eluent recycling design；
(9) tribuloside semi-finished product ethanol water is dissolved, filtered, reclaim ethanol, concentration places precipitation brilliant
Body, suction filtration obtains tribuloside finished product.
In the step (1), tribulus terrestris carries out ethanol water refluxing extraction again after cleaning, and Extraction solvent is 50%~
85% ethanol water.
In the step (1), the equipment of extraction extracts production line for adverse current, including elevator, charging are transmitted, adverse current is extracted
Tank group main frame 1, draw glassware 1, Juice squeezer 1, countercurrent extraction tank group main frame 2, draw glassware 2, Juice squeezer 2, discharging transmission, line pump,
Pump for giving-out, temporary storage tank, heat exchanger, liquid flowing valve etc..The rear raw material that pulverizes and sieves at the uniform velocity is added by elevator charge door, extract solution
Continuously pumped out via Pump for giving-out from temporary storage tank is flow to.
In the step (1), adverse current production line parameter is to lift 15~30Hz of unit frequency, the 18~20Hz of frequency of main frame 1,
45~the 50Hz of frequency of Juice squeezer 1, the 20~22Hz of frequency of main frame 2, Juice squeezer 2 40~45Hz of frequency, 0.5~2T/ of Pump for giving-out flow
H, feeds 100~400kg/h.
In the step (4), dilution water is 5 times of the volume of concentrate, filter impurity is discarded.
In the step (5), macroporous resin adsorption step uses wet method dress post, retains liquid level, by filtrate by adsorption column,
Flow velocity 0.05ml/g resins per minute, resin model is HPD400, HPD100, DM-130 or AB-8 broad spectrum type macroporous absorption tree
Fat.
In the step (5), large pore resin absorption column ratio of height to diameter is 10~5：1, the ethanol water of low powered posterior chamber for 5%~
20% ethanol water, the ethanol water of the high number of degrees is 50%~80% ethanol water, washes impurity water for 3~5BV, washes
The ethanol water amount of impurity low powered posterior chamber is 1~2BV, and the ethanol water amount for eluting the high number of degrees is 4BV.
In the step (7), silica gel column chromatography step uses wet method dress post, retains liquid level, by condensed cream by weight 1：1 mixes work
Silica gel after change, and the mixture mixed is placed in above silicagel column, eluent is ethyl acetate：Petroleum ether volume ratio be 50~
85:15 ethyl acetate and petroleum ether mixtures, elution flow rate 0.1ml/g silica gel per minute, elution volume is 5BV, and silica gel is lived
Change condition is 110 DEG C of 30min.
In the step (9), tribuloside semi-finished product 12~16 times of amount 50% ethanol water, 60 DEG C of thermosols, concentration
Density is d=1.03~1.05.
The present invention discloses a kind of isolation and purification method of tribuloside, and this method is：From cast hopper after raw material is cleaned
Input, extractor group main frame rotation, material is slowly advanced backward from unit front end, while Extraction solvent slave group end enters
Liquid pipe enters in extractor, is flowed by tank rear end through mobile material forward end, solid-liquid two-phase material is in this reverse movement
In fully contact, so that extracts active ingredients in medicinal material be come out.The dregs of a decoction are pushed to slag notch through discharge conveyor pressure and arranged
Go out, special Juice squeezer is extruded the dregs of a decoction, residual liquor in the dregs of a decoction is extruded into medicinal material tissue, reduce dregs of a decoction Shen residual liquor
Content.Extraction efficiency is higher, extract more complete.
The present invention is simultaneously from macroporous absorbent resin and the purifying of binding silica gel column chromatography, and separating effect is more preferably.
Embodiment：
Embodiment 1：
Tribulus terrestris 2T is weighed, is at the uniform velocity added with 400kg/h speed by elevator charge door after cleaning, 75% ethanol is water-soluble
Liquid is added with pipeline pump with 2T/h flow by feed tube, and elevator frequency setting is 30Hz, and the frequency setting of main frame 1 is 20Hz,
The frequency setting of Juice squeezer 1 is 50Hz, and the frequency setting of main frame 2 is 22Hz, and the frequency setting of Juice squeezer 2 is 45Hz, obtains tribuloside
Crude extract 10T；Tribuloside crude extract is concentrated from temporary storage tank is flow to via the continuous pump of Pump for giving-out to concentration tank, obtains tribulus terrestris soap
The thick concentrate 600L of glycosides；Add 3T water to dilute gained concentrate, be filtered to remove impurity；Filtrate crosses HPD400 macroporous absorbent resins,
Resin column ratio of height to diameter is 5:1,6T washes impurity, 2T5% ethanol aqueous wash impurity, 8T80% ethanol waters after adsorption saturation
Elution, obtains tribuloside eluent 7.8T；Eluent is concentrated to give tribuloside condensed cream 400kg；Tribuloside is concentrated
Cream mixes 400kg activated silica gels, is placed in above silicagel column, eluent is ethyl acetate：Petroleum ether volume ratio is 85:15 acetic acid
Ethyl ester and petroleum ether mixtures, elution flow rate 0.1ml/g silica gel per minute, obtain eluent 2000kg；After eluent recycling design
It is concentrated and dried to obtain tribuloside semi-finished product 120kg；Tribuloside semi-finished product 60 DEG C of heat of 1500L50% ethanol waters
Molten, ethanol is reclaimed in filtering, is concentrated into d=1.05, is placed and is separated out crystal, and suction filtration obtains tribuloside finished product 40kg, content
96.5%.
Embodiment 2：
Tribulus terrestris 800kg is weighed, is at the uniform velocity added with 200kg/h speed by elevator charge door after cleaning, 65% ethanol
The aqueous solution is added with pipeline pump with 1T/h flow by feed tube, and elevator frequency setting is 25Hz, and the frequency setting of main frame 1 is
18Hz, the frequency setting of Juice squeezer 1 is 50Hz, and the frequency setting of main frame 2 is 22Hz, and the frequency setting of Juice squeezer 2 is 45Hz, obtains tribulus terrestris
Saponin(e crude extract 4T；Tribuloside crude extract is concentrated from temporary storage tank is flow to via the continuous pump of Pump for giving-out to concentration tank, obtains thorn puncture
The thick concentrate 250L of lamb's-quarters saponin(e；Add 1.25T water to dilute gained concentrate, be filtered to remove impurity；Filtrate crosses AB-8 macroporous absorptions
Resin, resin column ratio of height to diameter is 5:1,6T washes impurity, 2T20% ethanol aqueous wash impurity, 8T60% ethanol after adsorption saturation
The aqueous solution is eluted, and obtains tribuloside eluent 7.8T；Eluent is concentrated to give tribuloside condensed cream 150kg；Tribulus terrestris soap
Glycosides condensed cream mixes 150kg activated silica gels, is placed in above silicagel column, eluent is ethyl acetate：Petroleum ether volume ratio is 65:15
Ethyl acetate and petroleum ether mixtures, elution flow rate 0.1ml/g silica gel per minute obtains eluent 750kg；Eluent reclaims molten
Tribuloside semi-finished product 50kg is concentrated and dried to obtain after agent；Tribuloside semi-finished product 60 DEG C of heat of 600L50% ethanol waters
Molten, ethanol is reclaimed in filtering, is concentrated into d=1.04, is placed and is separated out crystal, and suction filtration obtains tribuloside finished product 14kg, content
95%.
Embodiment 3：
Tribulus terrestris 1.6T is weighed, is at the uniform velocity added with 100kg/h speed by elevator charge door after cleaning, 75% ethanol water
Solution is added with pipeline pump with 500kg/h flow by feed tube, and elevator frequency setting is 25Hz, and the frequency setting of main frame 1 is
18Hz, the frequency setting of Juice squeezer 1 is 50Hz, and the frequency setting of main frame 2 is 22Hz, and the frequency setting of Juice squeezer 2 is 45Hz, obtains tribulus terrestris
Saponin(e crude extract 8T；Tribuloside crude extract is concentrated from temporary storage tank is flow to via the continuous pump of Pump for giving-out to concentration tank, obtains thorn puncture
The thick concentrate 500L of lamb's-quarters saponin(e；Add 2.5T water to dilute gained concentrate, be filtered to remove impurity；Filtrate crosses DM-130 macroporous absorptions
Resin, resin column ratio of height to diameter is 5:1,6T washes impurity, 2T15% ethanol aqueous wash impurity, 8T70% ethanol after adsorption saturation
The aqueous solution is eluted, and obtains tribuloside eluent 7.8T；Eluent is concentrated to give tribuloside condensed cream 310kg；Tribulus terrestris soap
Glycosides condensed cream mixes 310kg activated silica gels, is placed in above silicagel column, eluent is ethyl acetate：Petroleum ether volume ratio is 75:15
Ethyl acetate and petroleum ether mixtures, elution flow rate 0.1ml/g silica gel per minute obtains eluent 1.5T；Eluent reclaims molten
Tribuloside semi-finished product 110kg is concentrated and dried to obtain after agent；60 DEG C of 1.6T50% ethanol waters of tribuloside semi-finished product
Ethanol is reclaimed in thermosol, filtering, is concentrated into d=1.03, is placed and is separated out crystal, and suction filtration obtains tribuloside finished product 28kg, content
98%.
Claims (8)
1. a kind of isolation and purification method of tribuloside, it is characterised in that this method comprises the following steps：
(1) continuous countercurrent extracting tank ethanol water Continuous Countercurrent Extraction is added after tribulus terrestris is cleaned；
(2) extract solution that will be handled through (1) is filtered, and obtains tribuloside crude extract；
(3) gained tribuloside crude extract is concentrated, obtains the thick concentrate of tribuloside；
(4) the thick concentrate of gained tribuloside is diluted with water, and filtered, obtain filtrate；
(5) by the upper broad spectrum type macroporous resin adsorption post of gained filtrate, absorption, which is finished, is washed with water impurity, then with the ethanol water of low powered posterior chamber
Solution washes impurity, is then eluted with the ethanol water of the high number of degrees, obtains tribuloside eluent；Wherein in macroporous resin adsorption
Step uses wet method dress post, retains liquid level, by filtrate by adsorption column, flow velocity 0.05ml/g resins per minute, and resin model is
HPD400 or DM-130 broad spectrum type macroporous absorbent resins；Wherein the ethanol water of low powered posterior chamber is 5%~20% ethanol water,
The ethanol water of the high number of degrees is 50%~80% ethanol water；
(6) gained eluent is condensed into cream, obtains tribuloside condensed cream；
(7) tribuloside condensed cream is mixed into silica gel, and the mixture mixed is placed in above silicagel column, through ethyl acetate and stone
Oily ether mixed liquor elution, obtains eluent；
(8) tribuloside semi-finished product will be concentrated and dried to obtain after eluent recycling design；
(9) tribuloside semi-finished product ethanol water is dissolved, filtered, reclaim ethanol, concentration is placed and separates out crystal, takes out
Filter to obtain tribuloside finished product.
2. the isolation and purification method of tribuloside according to claim 1, it is characterised in that in described step (1),
Tribulus terrestris carries out ethanol water Continuous Countercurrent Extraction again after cleaning, Extraction solvent is 50%~85% ethanol water.
3. the isolation and purification method of tribuloside according to claim 1, it is characterised in that in described step (1),
The equipment of extraction extracts production line for adverse current, including elevator, charging transmission, countercurrent extraction tank group main frame 1, draws glassware 1, crowded juice
Machine 1, countercurrent extraction tank group main frame 2, draw glassware 2, Juice squeezer 2, discharging transmission, line pump, Pump for giving-out, temporary storage tank, heat exchanger, enter
Fluid valve；The rear raw material that pulverizes and sieves at the uniform velocity is added by elevator charge door, and extract solution flow to temporary storage tank certainly and connected via Pump for giving-out
It is continuous to pump out.
4. the isolation and purification method of tribuloside according to claim 3, it is characterised in that in described step (1),
Adverse current extracts production line parameter to lift 15~30Hz of unit frequency, the 18~20Hz of frequency of main frame 1, the 45~50Hz of frequency of Juice squeezer 1,
20~the 22Hz of frequency of main frame 2, Juice squeezer 2 40~45Hz of frequency, Pump for giving-out 0.5~2T/h of flow, feed 100~400kg/h.
5. the isolation and purification method of tribuloside according to claim 1, it is characterised in that in described step (4),
It is 5 times of the volume of concentrate to dilute water, filter impurity is discarded.
6. the isolation and purification method of tribuloside according to claim 1, it is characterised in that in described step (5),
Large pore resin absorption column ratio of height to diameter is 10~5：1, impurity water is washed for 3~5BV, and the ethanol water amount for washing impurity low powered posterior chamber is
1~2BV, the ethanol water amount for eluting the high number of degrees is 4BV.
7. the isolation and purification method of tribuloside according to claim 1, it is characterised in that in described step (7),
Silica gel column chromatography step uses wet method dress post, retains liquid level, by condensed cream by weight 1：1 mixes silica gel after activation, and mixed by what is mixed
Compound is placed in above silicagel column, and eluent is ethyl acetate：Petroleum ether volume ratio is 50~85:15 ethyl acetate and petroleum ether
Mixture, elution flow rate 0.1ml/g silica gel per minute, elution volume is 5BV, and silica gel activating condition is 110 DEG C, 30min.
8. the isolation and purification method of tribuloside according to claim 1, it is characterised in that in described step (9),
Tribuloside semi-finished product are d=1.03~1.05 with 12~16 times of amount 50% ethanol water, 60 DEG C of thermosols, concentration densities.
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| CN105125599B (en) * | 2015-08-14 | 2018-07-13 | 内蒙古昶辉生物科技股份有限公司 | A kind of preparation method of the tribulus terrestris extraction containing total saponins of tribulus |
| CN105582333A (en) * | 2016-02-22 | 2016-05-18 | 彭海英 | Okra wine capable of preserving health and tonifying kidneys and preparation method thereof |
| CN111494440A (en) * | 2020-04-24 | 2020-08-07 | 武汉轻工大学 | Extraction, purification and preparation technology of blood sugar reducing component saponin in caltrop, caltrop saponin extract and application |
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| CN1830459A (en) * | 2005-03-11 | 2006-09-13 | 上海医药工业研究院 | Tribulus terrestris extraction and its preparation method and use |
| CN101259153A (en) * | 2008-04-25 | 2008-09-10 | 江西远健药业有限公司 | Tribulus total steroid saponin and preparation thereof |
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| BG65737B1 (en) * | 2003-01-24 | 2009-09-30 | "Софарма" Ад | Standardized mixture of steroid saponins, method for the preparation and apllication thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1830459A (en) * | 2005-03-11 | 2006-09-13 | 上海医药工业研究院 | Tribulus terrestris extraction and its preparation method and use |
| CN101259153A (en) * | 2008-04-25 | 2008-09-10 | 江西远健药业有限公司 | Tribulus total steroid saponin and preparation thereof |
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| 甾体皂苷提取分离及结构研究方法;王莹莹等;《华中师范大学研究生学报》;20070331;第14卷(第1期);第144页左栏第3,5段，右栏第3段 * |
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