CN103524589B - Method for extracting and separating triterpenic acid and polyprenol from fir needle - Google Patents
Method for extracting and separating triterpenic acid and polyprenol from fir needle Download PDFInfo
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- CN103524589B CN103524589B CN201310481703.6A CN201310481703A CN103524589B CN 103524589 B CN103524589 B CN 103524589B CN 201310481703 A CN201310481703 A CN 201310481703A CN 103524589 B CN103524589 B CN 103524589B
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Abstract
The invention discloses a method for extracting and separating triterpenic acid and polyprenol from fir needles. The method comprises extracting folium fir with nonpolar solvent to obtain liposoluble extract, and saponifying with sodium hydroxide solution to obtain organic acid salt and unsaponifiable matter; adding hydrochloric acid into organic acid salt of folium Pini, acidifying, adding ethyl acetate, extracting, washing the extractive solution with water to neutrality, and concentrating under reduced pressure to obtain triterpenic acid; dissolving needle-leaf unsaponifiable substance in acetone, standing for layering, collecting supernatant, concentrating, adding ethanol for dissolving, standing for layering to obtain needle-leaf ethanol insoluble substance, subjecting to silica gel column chromatography, eluting with nonpolar solvent and ethyl acetate mixed solution, collecting polyprenol eluate, and concentrating under reduced pressure to obtain needle-leaf polyprenol. The invention adopts a solvent extraction method and a column chromatography method, so that the extraction selectivity and the extraction rate are greatly improved, the purity of the obtained product is higher, the solvent can be recycled, the production cost is lower, and the environment is more friendly.
Description
Technical field
The invention belongs to technical field of natural product extraction, especially utilize fir-needle to extract valuable biologically active substance---the method for triterpenic acid and polyprenol, can be used for medicine, protective foods and agriculture production.
Background technology
Pinaceae plant is a section maximum in gymnosperm, comprise Pinus, Picea, Abies, Pseudotsuga, Larix, Pseudolarix, Cedrus, Hemlock, keteleeria and silver-colored araucaria, having 10 genus 230 kinds, is form one of maximum seeds of earth timber reserves.Under complicated and diversified natural condition and specifically in history evolution process, pinaceae plant produces ecological adaptation with its biological characteristics alone to different environment, and in long-term natural selection process, define a set of perfect defense system, except safeguarding balance of nature and producing except the useful timber of the mankind, also contain novel structure and the significant compound of biological activity, especially pine needle (also name needle, pine needle, pine tag etc.) lipid-soluble substance, their economic worth and pharmaceutical potential are more and more subject to people and pay attention to.As: needle polyprenol is the long-chain multi-diterpene quasi-compound extracted from pinaceae plant needle unsaponifiables; to dolichol contained in human internal organ, there is similar constitutional features; great effect is played in the immunity system of Cell protection film, stabilized cell protein and support human body; in polysaccharide synthesis and Protein-Carbohydrate metabolism, also serve as the effect of coenzyme, can be used as the medicine of the various chronic hepatopathy of prevention and therapy and alzheimer's disease.Needle triterpenic acid is the lanostane-type tetracyclic triterpenoid extracted from Abies plant needle acidic substance, there is the biological effect similar to plant hormone, crop yield can be improved, reduction bacterium and fungi are to the sickness rate of plant, increase plant cold-resistant power and drought resistance, and accelerate fruit maturation etc.
Chinese patent ZL201010298504.8 discloses a kind of pine needle fat soluble extract preparation method and the application in preparation treatment Gastric Ulcer Treatment thereof.The method take pine needle as raw material, through chopping, drying, pulverizing, non-polar solvent extract, concentrating under reduced pressure, sodium hydroxide solution saponification, adds water and makes the pine needle fat soluble extract of dry matter content >=55%.Chinese patent ZL200910034931.2 discloses a kind of method extracting high purity polyprenol from plant needle raw material.The method, is extracted by petroleum ether solvent for raw material with the needle of the plants such as Pinus, Picea, Abies, Cunninghamia, oxygenation sodium hydroxide solution saponification after extracting solution is concentrated, saponification liquor petroleum ether solvent extracts, acetone solution is added, cooling, filtering and impurity removing after extraction liquid is concentrated, ethanolic soln extraction is added after filtrate is concentrated, alcohol-insoluble substance adds acetone solution, freezing, filtering and impurity removing, filter cake, after vacuum-drying, obtains highly purified needle polyprenol.As can be seen from above-described embodiment, product yield >=5% of pine needle fat soluble extract, but the product yield of needle polyprenol is only about 0.5%.Therefore, in extraction and isolation needle polyprenol process, also should pay attention to the other biological activeconstituents utilizing pine needle lipid-soluble substance, fully the pharmaceutical use of these biologically active substances of exploitation, makes needle lipid-soluble substance obtain more good utilisation.Chinese patent ZL200910049924.X discloses a kind of new fir triterpene lactone compound and its preparation method and application.The method extraction using alcohol fir branches and leaves, after extracting solution concentrating under reduced pressure, obtain medicinal extract thin up, then with chloroform extraction, chloroform extraction position is through silica gel column chromatography, collect petrol ether/ethyl acetate elutriant, again through dextrane gel column chromatography, collect chloroform/methanol elutriant, finally by C18 reversed phase column chromatography, collect methanol/water elutriant, obtain fir triterpene lactone compound.But from pine needle, extraction and isolation has the method for bioactive triterpenic acid and polyprenol, has had not yet to see bibliographical information simultaneously.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art part, provide a kind of method of extraction and isolation triterpenic acid and polyprenol from fir-needle, take fir-needle as raw material, the triterpenic acid simultaneously in extraction and isolation fir-needle and polyprenol.The method increase the total yield of product, reduce production cost, products obtained therefrom purity is also higher, is easy to realize suitability for industrialized production.
Technical scheme of the present invention is: a kind of method of simultaneously extraction and isolation triterpenic acid and polyprenol from fir-needle, comprise with fir-needle is raw material, by non-polar solvent extract, extracting solution concentrates after saponification, saponification liquor uses nonpolar solvent extraction again, upper strata is unsaponifiables solution, and lower floor is acylate solution; It is 2 that acylate solution adds dilute hydrochloric acid to pH value, under 50 ~ 70 DEG C of conditions, acidification reaction 10 ~ 30min, add equal-volume extraction into ethyl acetate again 3 ~ 4 times, combined ethyl acetate extraction liquid, being washed to pH value is 7 only, after concentrating under reduced pressure recycling design, obtains purity >=70% cyan paste needle triterpenic acid; Acetone solution, cooling, stratification is added after the washing of unsaponifiables solution, concentrating under reduced pressure, after getting supernatant liquor concentrating under reduced pressure, extract with ethanolic soln again, alcohol-insoluble substance proceeds to silica gel column chromatography, with non-polar solvent and ethyl acetate mixtures drip washing, collect polyprenol elutriant, after concentrating under reduced pressure recycling design, obtain purity >=90%wt flaxen oily needle polyprenol.
Described dilute hydrochloric acid concentration is percent by volume 10% ~ 15%.
Described non-polar solvent and ethyl acetate mixtures are the mixed solutions according to volume ratio 19:1 ~ 9:1 ratio mixing.
Described non-polar solvent is any one solvent in sherwood oil, normal hexane, No. 6 solvent oils.
Preparing as the application in crop growth promoter according to the described needle triterpenic acid that the method for extraction and isolation triterpenic acid and polyprenol obtains from fir-needle simultaneously.
Preparing as the application in tomato growth promotor according to the described needle triterpenic acid that the method for extraction and isolation triterpenic acid and polyprenol obtains from fir-needle simultaneously.
Preparing as the application in wheat growth promotor according to the described needle triterpenic acid that the method for extraction and isolation triterpenic acid and polyprenol obtains from fir-needle simultaneously.
From fir-needle, the needle triterpenic acid that obtains of the method for extraction and isolation triterpenic acid and polyprenol and first willow triazolone conbined usage are preparing the application in wheat growth promotor simultaneously according to described.
Beneficial effect:
1) the present invention take fir-needle as raw material, and the triterpenic acid simultaneously in extraction and isolation fir-needle and polyprenol, develop the pharmaceutical use of these biologically active substances, make needle lipid-soluble substance obtain more Appropriate application.
2) the present invention adopts solvent extration and column chromatography, and selectivity and the extraction yield of extraction improve greatly, and products obtained therefrom purity is also higher, and the recyclable recycling of solvent, and environment is comparatively friendly.
3) the present invention makes full use of triterpenic acid in needle lipid-soluble substance and polyprenol, and improve the total yield of product, reduce production cost, is a kind of extraction and separation method with popularizing application prospect.
4) the present invention is from the needle triterpenic acid of fir extraction and isolation, uses very little dosage, can affect the physiological process of plant-growth and growth, is mainly manifested in the output improving farm crop.
5) the needle triterpenic acid that the present invention obtains has for tomato and wheat etc. and significantly promotes production-increasing function, and time particularly for wheat and other agricultural chemicals conbined usage existing, effect of increasing production clearly.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but they are not limitation of the present invention.
A method for extraction and isolation triterpenic acid and polyprenol the while of from fir-needle, comprises step as follows:
1, take fir-needle as raw material, after chopping, drying and pulverizing, be that 1g:4 ~ 10ml adds non-polar solvent in the ratio of raw materials quality and solvent volume, refluxing extraction 2 times under 50 ~ 70 DEG C of conditions, each 2 ~ 6h, filters, merges No. 2 extracting solutions, after concentrating under reduced pressure recycling design, obtain needle liposoluble extract.
2, be that 1g:1 ~ 2ml adds 20 ~ 40% sodium hydroxide (w/v) in the ratio of extract quality and solvent volume, under 50 ~ 70 DEG C of conditions, saponification reaction 1 ~ 2h is that 1g:1 ~ 2ml adds non-polar solvent by mass volume ratio, re-extract 4 ~ 5 times, upper strata is unsaponifiables solution, lower floor is acylate solution, merges unsaponifiables solution, and being washed to pH value is 7 only, concentrating under reduced pressure recycling design, obtains needle unsaponifiables.
3, needle acylate solution adds 10 ~ 15% hydrochloric acid (v/v), adjust ph to 2, under 50 ~ 70 DEG C of conditions, acidification reaction 10 ~ 30min, add equal-volume extraction into ethyl acetate again 3 ~ 4 times, combined ethyl acetate extraction liquid, being washed to pH value is 7 only, after concentrating under reduced pressure recycling design, obtain purity >=70% cyan paste needle triterpenic acid.
4, needle unsaponifiables is that 1g:4 ~ 8ml adds acetone by mass volume ratio, after being heated to 40 ~ 50 DEG C of stirring and dissolving, be cooled to 0 ~ 5 DEG C, stratification, Aspirate supernatant, after concentrating under reduced pressure recycling design, be that 1g:3 ~ 6ml adds 85 ~ 90% ethanol (v/v) by mass volume ratio again, after being heated to 50 ~ 60 DEG C of stirring and dissolving, be cooled to 20 ~ 25 DEG C, stratification, after sucking supernatant liquor, throw out adds 85 ~ 90% ethanol (v/v) again, repetitive operation 4 ~ 5 times, obtain needle alcohol-insoluble substance (can with reference to the method recorded in ZL200910034931.2).
5, alcohol-insoluble substance proceeds to silica gel column chromatography, is the drip washing of 19:1 ~ 9:1 mixed solution by non-polar solvent and ethyl acetate volume ratio, collects polyprenol elutriant, after concentrating under reduced pressure recycling design, obtains purity >=90% flaxen oily needle polyprenol.
Described non-polar solvent is any one solvent in sherwood oil, normal hexane, No. 6 solvent oils.
Embodiment 1
Take fir-needle as raw material, after chopping, drying and pulverizing, obtain fir-needle powder.Get the round-bottomed flask that 200g needle powder is placed in 2000ml, add 1000ml sherwood oil, be heated to 60 DEG C of refluxing extraction 2h, filter, filter residue adds 600ml sherwood oil again, repeats extraction 1 time, merge No. 2 extracting solutions, concentrating under reduced pressure obtains needle liposoluble extract after reclaiming sherwood oil.Needle liposoluble extract adds 15ml30%NaOH solution, saponification reaction 1h at 60 DEG C of temperature, with 150ml petroleum ether extraction 5 times, upper strata is petroleum ether solution (unsaponifiables solution), lower floor is alkali aqueous solution (acylate solution), merges petroleum ether extraction liquid, and being washed to pH value is 7 only, concentrating under reduced pressure obtains needle unsaponifiables after reclaiming sherwood oil.Acylate solution adds the hydrochloric acid that concentration of volume percent is 15%, adjust ph to 2.0, at 60 DEG C of temperature, acidification reaction 10min, add 100ml extraction into ethyl acetate again 3 times, combined ethyl acetate extraction liquid, being washed to pH value is 7 only, after concentrating under reduced pressure reclaims ethyl acetate, obtaining 5.5g triterpenic acid content is 78.2% cyan paste.Needle unsaponifiables adds 50ml acetone, is heated to 40 DEG C of stirring and dissolving, then is cooled to 2 DEG C, stratification, gets upper strata acetone soln, after concentrating under reduced pressure reclaims acetone, add 40ml87% ethanol again, be heated to 50 DEG C of stirring and dissolving, then be cooled to 20 DEG C, stratification, suck upper strata ethanolic soln, throw out adds 87% ethanol again, and repetitive operation 4 times, obtains needle alcohol-insoluble substance.Needle alcohol-insoluble substance proceeds to silica gel column chromatography, and with normal hexane and the drip washing of ethyl acetate (9:1) mixed solution, collect polyprenol elutriant, after concentrating under reduced pressure reclaims eluent, obtaining 0.7g polyprenol content is 95.7% flaxen oily matter.
Embodiment 2
Get the round-bottomed flask that fir-needle powder 700g is placed in 5000ml, add 3000ml6 solvent oil, be heated to 70 DEG C of refluxing extraction 3h, filter, filter residue adds 2000ml6 solvent oil again, repeats extraction 1 time, merges No. 2 extracting solutions, concentrating under reduced pressure obtains needle liposoluble extract after reclaiming No. 6 solvent oils.Needle liposoluble extract adds 20%NaOH solution, adjust ph to 10.0, saponification reaction 1h at 65 DEG C of temperature, extract 5 times with 500ml6 solvent oil, upper strata is No. 6 petroleum spirit (unsaponifiables solution), and lower floor is alkali aqueous solution (acylate solution), merge No. 6 solvent oil extraction liquids, being washed to pH value is 7 only, and concentrating under reduced pressure obtains needle unsaponifiables after reclaiming No. 6 solvent oils.Needle acylate solution adds 10% hydrochloric acid, adjust ph to 2.0, at 65 DEG C of temperature, acidification reaction 20min, add 300ml extraction into ethyl acetate again 4 times, combined ethyl acetate extraction liquid, being washed to pH value is 7 only, after concentrating under reduced pressure reclaims ethyl acetate, obtaining 19.5g triterpenic acid content is 72.2% cyan paste.Needle unsaponifiables adds 200ml acetone, is heated to 45 DEG C of stirring and dissolving, then is cooled to 1 DEG C, stratification, gets upper strata acetone soln, after concentrating under reduced pressure reclaims acetone, add 120ml86% ethanol again, be heated to 55 DEG C of stirring and dissolving, then be cooled to 22 DEG C, stratification, suck upper strata ethanolic soln, throw out adds 86% ethanol again, and repetitive operation 4 times, obtains needle alcohol-insoluble substance.Needle alcohol-insoluble substance proceeds to silica gel column chromatography, and with sherwood oil and the drip washing of ethyl acetate (volume ratio 12:1) mixed solution, collect polyprenol elutriant, after concentrating under reduced pressure reclaims eluent, obtaining 2.8g polyprenol content is 93.7% flaxen oily matter.
Effect experiment:
1, the effect of fir-needle triterpenic acid on tomato
Get above-mentioned fir-needle triterpenic acid, making triterpenic acid content is 10%(w/v) needle triterpenic acid water miscible liquid.Tomato test kind: Di Fenni.Test arranges experiment 1 group, tests 2 groups and control group totally 3 treatment group, and each treatment group establishes 3 replicated plots, each community 15m
2, random district group arranges.The needle triterpenic acid application process of each treatment group is in table 1.
Table 1 needle triterpenic acid biotechnological formulation application process
The testing data of tomato harvesting time is in table 2.Use the heavy and maximum diameter of the First of the experimental group of needle triterpenic acid preparation fruit gross weight, total fruit number, maximum fruit and most fruitlet is heavy and minimum diameter comparatively control group be all significantly improved, test 1 group to compare with control group with experiment 2 groups, tomato yield improves 9.5% and 10.8% respectively.As can be seen here, fir-needle triterpenic acid has effect of increasing production to tomato.
Table 2 tomato First fruit yield trials data
2, the effect of fir-needle triterpenic acid on wheat
Get above-mentioned fir-needle triterpenic acid, making triterpenic acid content is 10%(w/v) needle triterpenic acid biotechnological formulation.Wheat test kind: raise spoke wheat No. 3.Test arranges experiment 1 group, tests 2 groups, tests 3 groups and control group totally 4 treatment group, and each treatment group establishes 3 replicated plots, each community 30m
2, random district group arranges.The needle triterpenic acid biotechnological formulation application process of each treatment group is in table 3.
Table 3 needle triterpenic acid biotechnological formulation application process
The testing data of wheat harvest is in table 4.Use the experimental group comparatively control group seed weight raising 1.5% ~ 2.3% of needle triterpenic acid preparation; Average grain number per spike improves 0.1 ~ 1; Number of productive ear every mu about improves 4.78% ~ 11.94%; Wheat yield improves 6.7% ~ 16.5%.Test 2 groups and be all better than other treatment group on seed weight, number of productive ear, wheat yield, illustrate that needle triterpenic acid is combined other agricultural chemicals (as first willow triazolone) and had synergism when seed treatment.
The testing data of table 4 wheat harvest
Therefore, the fir-needle triterpenic acid of patent extraction and isolation of the present invention, uses very little dosage, can affect the physiological process of plant-growth and growth, is mainly manifested in the output improving farm crop.
Claims (4)
1. a method for extraction and isolation triterpenic acid and polyprenol the while of from fir-needle, comprising with fir-needle is raw material, by non-polar solvent extract, extracting solution concentrates after saponification, saponification liquor uses nonpolar solvent extraction again, and upper strata is unsaponifiables solution, and lower floor is acylate solution; It is characterized in that, it is 2 that acylate solution adds dilute hydrochloric acid to pH value, under 50 ~ 70 DEG C of conditions, acidification reaction 10 ~ 30 min, add equal-volume extraction into ethyl acetate again 3 ~ 4 times, combined ethyl acetate extraction liquid, being washed to pH value is 7 only, after concentrating under reduced pressure recycling design, obtain purity >=70 % wt cyan paste needle triterpenic acid; Acetone solution, cooling, stratification is added after the washing of unsaponifiables solution, concentrating under reduced pressure, after getting supernatant liquor concentrating under reduced pressure, extract with ethanolic soln again, alcohol-insoluble substance proceeds to silica gel column chromatography, with non-polar solvent and ethyl acetate mixtures drip washing, collect polyprenol elutriant, after concentrating under reduced pressure recycling design, obtain purity >=90 % wt flaxen oily needle polyprenol.
2. the method for simultaneously extraction and isolation triterpenic acid and polyprenol from fir-needle according to claim 1, it is characterized in that, described dilute hydrochloric acid concentration is percent by volume 10 % ~ 15 %.
3. the method for simultaneously extraction and isolation triterpenic acid and polyprenol from fir-needle according to claim 1, it is characterized in that, described non-polar solvent and ethyl acetate mixtures are the mixed solutions according to volume ratio 19:1 ~ 9:1 ratio mixing.
4. the method for simultaneously extraction and isolation triterpenic acid and polyprenol from fir-needle according to claim 1, it is characterized in that, described non-polar solvent is any one solvent in sherwood oil, normal hexane, No. 6 solvent oils.
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| CN106857695A (en) * | 2016-12-31 | 2017-06-20 | 新昌县迪斯曼科技有限公司 | Plant growth regulator composition and preparation method thereof |
| RU2673951C1 (en) * | 2017-11-15 | 2018-12-03 | Российская Федерация в лице Федеральное государственное бюджетное образовательное учреждение высшего образования "Поволжский государственный технологический университет" | Method for stimulating growth and stability of wood and bush plants |
| CN112546079A (en) * | 2021-01-28 | 2021-03-26 | 广西壮族自治区中医药研究院 | Preparation and quality detection method of total organic acid extract in Chinese fir leaves |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2161149C1 (en) * | 1999-07-22 | 2000-12-27 | Институт химии Коми научного центра Уральского отделения РАН | Method of isolation of biologically active sum of acids from fir wood greens |
| MD2414F1 (en) * | 2003-03-19 | 2004-04-30 | Inst De Fiziol A Plantelor Al | Process for vine cultivation |
| RU2248700C2 (en) * | 2003-05-21 | 2005-03-27 | Чекуров Виктор Михайлович | Method for obtaining biologically active sum of triterpene acids |
| RU2321197C2 (en) * | 2006-04-19 | 2008-04-10 | Николай Эдуардович Нифантьев | Farm crop growth and development promoter |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2161149C1 (en) * | 1999-07-22 | 2000-12-27 | Институт химии Коми научного центра Уральского отделения РАН | Method of isolation of biologically active sum of acids from fir wood greens |
| MD2414F1 (en) * | 2003-03-19 | 2004-04-30 | Inst De Fiziol A Plantelor Al | Process for vine cultivation |
| RU2248700C2 (en) * | 2003-05-21 | 2005-03-27 | Чекуров Виктор Михайлович | Method for obtaining biologically active sum of triterpene acids |
| RU2321197C2 (en) * | 2006-04-19 | 2008-04-10 | Николай Эдуардович Нифантьев | Farm crop growth and development promoter |
Non-Patent Citations (1)
| Title |
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| 针叶生物活性物质提取中间试验;周维纯等;《林化科技通讯》;19810829;1-7 * |
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Effective date of registration: 20220506 Address after: 512200 No. 66, Baisha bridge, Pingshi Town, Lechang City, Shaoguan City, Guangdong Province Patentee after: ZHONGJIANHANG GROUP CO.,LTD. Address before: Five suojin village of Nanjing city in Jiangsu province 210042 No. 16 Patentee before: INSTITUTE OF CHEMICAL INDUSTRY OF FOREST PRODUCTS, CAF |