CN110183508A - The method of licoflavone and glycyrrhizic acid is separated from licorice - Google Patents
The method of licoflavone and glycyrrhizic acid is separated from licorice Download PDFInfo
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- CN110183508A CN110183508A CN201910545325.0A CN201910545325A CN110183508A CN 110183508 A CN110183508 A CN 110183508A CN 201910545325 A CN201910545325 A CN 201910545325A CN 110183508 A CN110183508 A CN 110183508A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
- C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
- C07D311/28—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only
- C07D311/30—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only not hydrogenated in the hetero ring, e.g. flavones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
- C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
- C07D311/40—Separation, e.g. from natural material; Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
- C07H1/06—Separation; Purification
- C07H1/08—Separation; Purification from natural products
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/20—Carbocyclic rings
- C07H15/24—Condensed ring systems having three or more rings
- C07H15/256—Polyterpene radicals
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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 method that the invention discloses a kind of to separate licoflavone and glycyrrhizic acid from licorice, licorice is dissolved with ethanol water, pH is adjusted with dilute hydrochloric acid, is separated with Simulated Moving Bed Chromatography technology, the filler of Optimized Simulated moving bed obtains the product of licoflavone.It is an advantage of the invention that the product purity of obtained liquorice flavonoids compound is high using flavone compound and glycyrrhizic acid in Simulated Moving Bed Chromatography isolation technics licorice, it is lower than 0.2% containing glycyrrhizic acid.Liquorice flavonoids compound prepared by the present invention can be widely applied to health food and cosmetic field.
Description
Technical field
The invention belongs to field of natural organic chemistry, it is related to a kind of using licorice being raw material separation licoflavone and sweet
The method of oxalic acid.
Background technique
Radix Glycyrrhizae (Glycyrrhiza uraiensis Fisch.) also known as Glycyrrhiza Uralensis (Glycyrrhiza
Uralensis Fisch.), herbaceos perennial belongs to pulse family, is a kind of dual-purpose of drug and food resource.Radix Glycyrrhizae is mainly distributed on northwest
Arid and semi-arid lands, soil neutral or slightly alkaline, resistance is strong, adaptable, is plant drought expert, desertification dust storm
Soldier.Xinjiang is main place of production China Radix Glycyrrhizae, and Radix Glycyrrhizae purchases 6,000,000 tons of production capacity, and yield accounts for national more than half, middle and south height
In the north, it is mainly distributed on Kongquehe, therefore, Kongquehe two sides are also called " township of Radix Glycyrrhizae ".In the Radix Glycyrrhizae of China's export,
Xinjiang Radix Glycyrrhizae accounts for therein 80% or more, is exported to the continents such as Asia, beauty, Europe.Radix glycyrrhizae taste is sweet, it is mild-natured and, enter the heart, spleen, lung, stomach four
Through.It is raw with cooler, can purging fire for removing toxin, relieving spasm to stop pain；Toast partial temperature, can dissipate exterior cold, tonifying middle-Jiao and Qi.In addition, Radix Glycyrrhizae is also good at adjusting
And pharmacological property, solve the poison of hundred medicines.
Physiologically active ingredient in Radix Glycyrrhizae mainly has triterpene compound (glycyrrhizin also glycyrrhetate, enoxolone
Deng), flavone compound (liquiritin, isoliquiritigenin, glycyrrhizin etc.) and licorice polysaccharide class compound three categories ingredient.
Glycyrrhizin is Radix Glycyrrhizae sweet taste main component, is made of 1 molecule glycyrrhizic acid and 2 molecule glucuronic acids, and sugariness is sucrose
200 times, be a kind of sweetening agent.Licoflavone has the function of antibacterial, antitumor, anti-mutagenesis, antiviral, anti-oxidant etc..
Licorice is the waste material generated after producing mono-ammonium glycyrrhizinate, wherein flavonoid rich in
Object and a small amount of glycyrrhizic acid affect making for licorice currently, licorice is not further separated direct marketing
With range and value.China has a large amount of licorice to generate every year, not by the maximization of economic benefit of licorice,
Cause the very big wasting of resources.Therefore, the flavones and glycyrrhizic acid in licorice are separated, the comprehensive benefit of Licorice is conducive to
With the added value of Radix Glycyrrhizae can be improved.
Summary of the invention
The method that the purpose of the present invention is to provide a kind of to separate licoflavone and glycyrrhizic acid from licorice.
Technical solution of the present invention the following steps are included:
The method of licoflavone and glycyrrhizic acid is separated from licorice, comprising the following steps:
(1) licorice is completely dissolved with ethanol water, adjusts pH=5 with dilute hydrochloric acid；
(2) solution for obtaining step (1) selects different macroporous absorbent resins as filler fill mould as sample solution
Quasi- moving bed；
(3) Simulated Moving Bed Chromatography is used, the sample in step (2) is separated with 65% concentration of alcohol；
(4) ethanol water of various concentration in step (3) is concentrated, recycling design obtains licoflavone medicinal extract
And glycyrrhizic acid；
(5) film is crossed after dissolving licoflavone and glycyrrhizic acid that step (4) obtains with methanol carries out high performance liquid chromatography point
Analysis；
(6) analysis obtained step (5) is as a result, determine concentration of alcohol and macroporous absorbent resin；
(7) it prepared by the condition after step (6) optimization, obtains the mobile phase containing licoflavone, concentration, drying obtain
Licoflavone.
In the step (1), the ethyl alcohol of ethanol water and the v/v concentration of water are 30:70；
In the step (2), macroporous absorbent resin filler includes D101, AB-8, S-8；
In the step (3), the ethyl alcohol of ethanol water and the v/v concentration of water are respectively as follows: 40:60,50:50,60:40,
70:30,80:20；
In the step (4), using vacuum concentration, vacuum degree is -0.05~-0.08Mpa, and temperature is 45~50 DEG C, institute
It obtains moisture content in medicinal extract and is lower than 5%；The content of glycyrrhizic acid is lower than 0.2% in gained licoflavone medicinal extract；The part of glycyrrhizic acid
The content of glycyrrhizic acid is not less than 20%.
In the step (5), high performance liquid chromatography chromatography flow velocity is 1ml/min, and mobile phase is A:0.1% formic acid water
Solution；B: methanol；Gradient elution program condition are as follows: 0~45min, 5%~100%B；
In the step (7), Radix Glycyrrhizae Huang is isolated and purified from licorice using Simulated Moving Bed Chromatography isolation technics
Ketone and glycyrrhizic acid, Simulation moving bed used are IV band structure, are made of 4~8 Flash chromatographic columns, each band is by 1~2
Coupled columns composition, mobile phase is ethyl alcohol: water volume ratio 30:70, and sample introduction flow velocity is 1~3ml/min, eluent flow rate
For 20~40ml/min, flushing flow velocity is 10~30ml/min, and switching time is 17~19min, chromatographic system operation temperature
It is 28~32 DEG C.
The method provided by the invention that licoflavone and glycyrrhizic acid are separated from licorice, first uses licorice
After ethanol water is completely dissolved, optimizes different macroporous absorbent resin difference gradients to isolated influence, parameter is determined, with simulation
Mobile bed chromatic isolation technics is separated, and licoflavone and Radix Glycyrrhizae acid product are obtained, obtained liquorice flavonoids compound
Product purity is high, is lower than 0.2% containing glycyrrhizic acid, licoflavone can be widely applied to health food and cosmetic field, be conducive to
The comprehensive utilization of Licorice improves the added value of Radix Glycyrrhizae.
Specific embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
Material as used in the following examples, reagent etc. are commercially available unless otherwise specified.
The assay of flavone compound in following embodiments method particularly includes: take sample 0.5mg, be dissolved in 0.5mL
It in ethyl alcohol, is added in scale test tube, is supplemented to 4mL with distilled water, 0.3mL 5% (w/v) sodium nitrite in aqueous solution is added and shakes up,
1% (w/v) aluminum chloride aqueous solution is added after 5min to shake up, the sodium hydrate aqueous solution of the 1moL/L of 2mL is added after 6min, is adding
Enter distilled water to 10mL, 510nm goes out to measure light absorption value after 10min；Blank control replaces sample to be reacted with ethyl alcohol；Flavonoids
The content of compound is with rutin equivalent (Rutin Equivalent, RE/g butt) expression.
The preparation of standard solution: rutin standard items 0.100g accurately is weighed, as in 25mL volumetric flask, is determined with methanol
Hold to graduation mark.Then 5mL, 4mL, 3mL, 2mL, 1mL are pipetted respectively with pipette in 10mL volumetric flask, is stopped with methanol constant volume
Scale obtains the solution that concentration is respectively 2,1.6,1.2,0.8 and 0.4mg/mL, is measured according to the above method, at 510nm
There is absorption maximum, obtains the standard curve between the absorbance value at 510nm and the concentration of rutin mark product.
Obtained isolate in embodiment one is measured according to the method described above, according to obtained standard curve
Obtain the content of flavone compound in isolate.
Embodiment one
It is 50:50 dissolution by licorice ethanol water (v/v), concentration 20mg/ml adjusts pH=5 with dilute hydrochloric acid,
Then it is separated with Simulation moving bed, filler D101, different concentration of alcohol elution is obtained eluent, subtracted using vacuum
Pressure concentration, vacuum degree are -0.08Mpa, and thickening temperature is 45 DEG C, and recycling design obtains medicinal extract.Obtained medicinal extract methanol is molten
Solution, efficient liquid phase chromatographic analysis determine whether licoflavone and glycyrrhizic acid separate completely.Skill is separated using Simulated Moving Bed Chromatography
Art separates licoflavone and glycyrrhizic acid from licorice, and Simulation moving bed used is IV band structure, by 8 resin chromatographies
Column composition, each band are composed in series by 2 root chromatogram columns, and mobile phase is ethyl alcohol: water=60:40, and sample introduction flow velocity is 2ml/min,
Eluent flow rate is 40ml/min, and flushing flow velocity is 30ml/min, switching time 19min, and chromatographic system operation temperature is
30℃；Vacuum-concentrcted and spray drying are carried out to the obtained eluent containing licoflavone, obtain flavone compound
Content be 36.2mgRE/g.
Embodiment two
It is 50:50 dissolution by licorice ethanol water (v/v), concentration 20mg/ml adjusts pH=5 with dilute hydrochloric acid,
Then it is separated with Simulation moving bed, filler AB-8, different concentration of alcohol elution is obtained eluent, subtracted using vacuum
Pressure concentration, vacuum degree are -0.08Mpa, and thickening temperature is 45 DEG C, and recycling design obtains medicinal extract.Obtained medicinal extract methanol is molten
Solution, efficient liquid phase chromatographic analysis determine whether licoflavone and glycyrrhizic acid separate completely.Skill is separated using Simulated Moving Bed Chromatography
Art separates licoflavone and glycyrrhizic acid from licorice, and Simulation moving bed used is IV band structure, by 8 resin chromatographies
Column composition, each band are composed in series by 2 root chromatogram columns, and mobile phase is ethyl alcohol: water=60:40, and sample introduction flow velocity is 2ml/min,
Eluent flow rate is 40ml/min, and flushing flow velocity is 30ml/min, switching time 19min, and chromatographic system operation temperature is
30℃；Vacuum-concentrcted and spray drying are carried out to the obtained eluent containing licoflavone, obtain flavone compound
Content be 51.4mgRE/g.
Embodiment three
It is 50:50 dissolution by licorice ethanol water (v/v), concentration 20mg/ml adjusts pH=5 with dilute hydrochloric acid,
Then it is separated with Simulation moving bed, filler S-8, different concentration of alcohol elution obtains eluent, using vacuum decompression
Concentration, vacuum degree are -0.08Mpa, and thickening temperature is 45 DEG C, and recycling design obtains medicinal extract.Obtained medicinal extract methanol is molten
Solution, efficient liquid phase chromatographic analysis determine whether licoflavone and glycyrrhizic acid separate completely.Skill is separated using Simulated Moving Bed Chromatography
Art separates licoflavone and glycyrrhizic acid from licorice, and Simulation moving bed used is IV band structure, by 8 Flash colors
Column composition is composed, each band is composed in series by 2 root chromatogram columns, and mobile phase is ethyl alcohol: water=60:40, and sample introduction flow velocity is 2ml/
Min, eluent flow rate 40ml/min, flushing flow velocity are 30ml/min, switching time 19min, chromatographic system operation temperature
Degree is 30 DEG C；Vacuum-concentrcted and spray drying are carried out to the obtained eluent containing licoflavone, obtain flavonoids
The content for closing object is 43.6mgRE/g.
Claims (5)
1. separating the method for licoflavone and glycyrrhizic acid from licorice, which is characterized in that including the following steps:
(1) licorice is completely dissolved with ethanol water, adjusts pH=5 with dilute sulfuric acid；
(2) solution for obtaining step (1) is selected different macroporous absorbent resins to fill simulation as filler and is moved as sample solution
Dynamic bed；
(3) Simulated Moving Bed Chromatography is used, with the sample in different ethanol water concentration elution steps (2)；
(4) ethanol water of various concentration in step (3) is concentrated, recycling design, obtains licoflavone medicinal extract and sweet
Oxalic acid；
(5) film is crossed after dissolving the licoflavone medicinal extract that step (4) obtains with methanol carries out efficient liquid phase chromatographic analysis；
(6) analysis obtained step (5) is as a result, determine concentration of alcohol and macroporous absorbent resin；
(7) condition after step (6) optimization is subjected to Simulated Moving Bed Chromatography separation, obtains flowing respectively containing licoflavone
Phase, concentration, drying, obtains licoflavone and glycyrrhizic acid.
2. the method according to claim 1 for separating licoflavone and glycyrrhizic acid from licorice, it is characterised in that:
The v/v concentration of ethyl alcohol and water that step (1) dissolves the ethanol water of licorice is 30:70, sample concentration 20mg/ml.
3. the method according to claim 1 for separating licoflavone and glycyrrhizic acid from licorice, it is characterised in that:
In the step (2) and step (3), macroporous absorbent resin filler includes D101, AB-8, S-8；In the step (3), ethyl alcohol
The ethyl alcohol of aqueous solution and the v/v concentration of water are respectively as follows: 40:60,50:50,60:40,70:30,80:20.
4. the method according to claim 1 for separating licoflavone and glycyrrhizic acid from licorice, it is characterised in that:
In the step (4), using vacuum concentration, vacuum degree is -0.05~-0.08Mpa, and temperature is 45~50 DEG C, in gained medicinal extract
Moisture content is lower than 5%；The content of glycyrrhizic acid is lower than 0.2% in gained licoflavone medicinal extract；The part glycyrrhizic acid of glycyrrhizic acid
Content is not less than 20%.
5. the method according to claim 1 for separating licoflavone and glycyrrhizic acid from licorice, it is characterised in that:
In the step (7), licoflavone is isolated and purified from licorice using Simulated Moving Bed Chromatography isolation technics, it is used
Simulation moving bed is IV band structure, is made of 4~8 Flash chromatographic columns, and each band is composed in series by 1~2 root chromatogram column, stream
Dynamic is mutually ethyl alcohol: water volume ratio 30:70, and sample introduction flow velocity is 1~3ml/min, and eluent flow rate is 20~40ml/min, punching
Washing lotion flow velocity is 10~30ml/min, and switching time is 17~19min, and chromatographic system operation temperature is 28~32 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113425760A (en) * | 2021-07-23 | 2021-09-24 | 江苏大学 | Method for extracting and separating effective components from liquorice |
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| CN103570779A (en) * | 2012-08-04 | 2014-02-12 | 江苏汉邦科技有限公司 | Method for preparing glycyrrhizin by simulated moving bed separation |
| CN103724394B (en) * | 2014-01-02 | 2016-02-10 | 兰州理工大学 | Potenlini and licoflavone be continuously separated purification process |
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2019
- 2019-06-22 CN CN201910545325.0A patent/CN110183508A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103570779A (en) * | 2012-08-04 | 2014-02-12 | 江苏汉邦科技有限公司 | Method for preparing glycyrrhizin by simulated moving bed separation |
| CN103724394B (en) * | 2014-01-02 | 2016-02-10 | 兰州理工大学 | Potenlini and licoflavone be continuously separated purification process |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113425760A (en) * | 2021-07-23 | 2021-09-24 | 江苏大学 | Method for extracting and separating effective components from liquorice |
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