CN113603737A - Method for extracting and separating liquiritin and glycyrrhizic acid - Google Patents
Method for extracting and separating liquiritin and glycyrrhizic acid Download PDFInfo
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- CN113603737A CN113603737A CN202110903344.3A CN202110903344A CN113603737A CN 113603737 A CN113603737 A CN 113603737A CN 202110903344 A CN202110903344 A CN 202110903344A CN 113603737 A CN113603737 A CN 113603737A
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- ionic liquid
- glycyrrhizic acid
- extracting
- separating
- liquiritin
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Links
- 235000019410 glycyrrhizin Nutrition 0.000 title claims abstract description 75
- LPLVUJXQOOQHMX-UHFFFAOYSA-N glycyrrhetinic acid glycoside Natural products C1CC(C2C(C3(CCC4(C)CCC(C)(CC4C3=CC2=O)C(O)=O)C)(C)CC2)(C)C2C(C)(C)C1OC1OC(C(O)=O)C(O)C(O)C1OC1OC(C(O)=O)C(O)C(O)C1O LPLVUJXQOOQHMX-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229960004949 glycyrrhizic acid Drugs 0.000 title claims abstract description 74
- UYRUBYNTXSDKQT-UHFFFAOYSA-N glycyrrhizic acid Natural products CC1(C)C(CCC2(C)C1CCC3(C)C2C(=O)C=C4C5CC(C)(CCC5(C)CCC34C)C(=O)O)OC6OC(C(O)C(O)C6OC7OC(O)C(O)C(O)C7C(=O)O)C(=O)O UYRUBYNTXSDKQT-UHFFFAOYSA-N 0.000 title claims abstract description 74
- LPLVUJXQOOQHMX-QWBHMCJMSA-N glycyrrhizinic acid Chemical compound O([C@@H]1[C@@H](O)[C@H](O)[C@H](O[C@@H]1O[C@@H]1C([C@H]2[C@]([C@@H]3[C@@]([C@@]4(CC[C@@]5(C)CC[C@@](C)(C[C@H]5C4=CC3=O)C(O)=O)C)(C)CC2)(C)CC1)(C)C)C(O)=O)[C@@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@H]1O LPLVUJXQOOQHMX-QWBHMCJMSA-N 0.000 title claims abstract description 65
- VTAJIXDZFCRWBR-UHFFFAOYSA-N Licoricesaponin B2 Natural products C1C(C2C(C3(CCC4(C)CCC(C)(CC4C3=CC2)C(O)=O)C)(C)CC2)(C)C2C(C)(C)CC1OC1OC(C(O)=O)C(O)C(O)C1OC1OC(C(O)=O)C(O)C(O)C1O VTAJIXDZFCRWBR-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000001685 glycyrrhizic acid Substances 0.000 title claims abstract description 56
- KSDSYIXRWHRPMN-UHFFFAOYSA-N 4'-O-beta-D-Galactopyranoside-6''-p-Coumaroylprunin-4',5,7-Trihydroxyflavanone Natural products OC1C(O)C(O)C(CO)OC1OC1=CC=C(C2OC3=CC(O)=CC(O)=C3C(=O)C2)C=C1 KSDSYIXRWHRPMN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- DEMKZLAVQYISIA-ONJCETCRSA-N Liquiritin Natural products O([C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1)c1ccc([C@@H]2Oc3c(C(=O)C2)ccc(O)c3)cc1 DEMKZLAVQYISIA-ONJCETCRSA-N 0.000 title claims abstract description 44
- DEMKZLAVQYISIA-UHFFFAOYSA-N Liquirtin Natural products OC1C(O)C(O)C(CO)OC1OC1=CC=C(C2OC3=CC(O)=CC=C3C(=O)C2)C=C1 DEMKZLAVQYISIA-UHFFFAOYSA-N 0.000 title claims abstract description 44
- DEMKZLAVQYISIA-ZRWXNEIDSA-N liquiritin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=CC=C([C@H]2OC3=CC(O)=CC=C3C(=O)C2)C=C1 DEMKZLAVQYISIA-ZRWXNEIDSA-N 0.000 title claims abstract description 44
- GSZUGBAEBARHAW-UHFFFAOYSA-N sophoraflavone B Natural products OC1C(O)C(O)C(CO)OC1OC1=CC=C(C=2OC3=CC(O)=CC=C3C(=O)C=2)C=C1 GSZUGBAEBARHAW-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000002608 ionic liquid Substances 0.000 claims abstract description 70
- 238000000605 extraction Methods 0.000 claims abstract description 62
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 48
- 239000012071 phase Substances 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 235000006200 Glycyrrhiza glabra Nutrition 0.000 claims abstract description 14
- 235000001453 Glycyrrhiza echinata Nutrition 0.000 claims abstract description 7
- 235000017382 Glycyrrhiza lepidota Nutrition 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 229940010454 licorice Drugs 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 5
- 240000004670 Glycyrrhiza echinata Species 0.000 claims abstract 2
- 239000004378 Glycyrrhizin Substances 0.000 claims description 18
- LPLVUJXQOOQHMX-MOGLOQIBSA-N (2s,3s,4s,5r,6r)-6-[(2r,3r,4s,5s,6s)-2-[[(3s,4ar,6ar,6bs,8as,11s,12ar,14ar,14bs)-11-carboxy-4,4,6a,6b,8a,11,14b-heptamethyl-14-oxo-2,3,4a,5,6,7,8,9,10,12,12a,14a-dodecahydro-1h-picen-3-yl]oxy]-6-carboxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-c Chemical compound O([C@@H]1[C@@H](O)[C@H](O)[C@H](O[C@H]1O[C@@H]1C([C@H]2[C@]([C@@H]3[C@@]([C@@]4(CC[C@@]5(C)CC[C@@](C)(C[C@H]5C4=CC3=O)C(O)=O)C)(C)CC2)(C)CC1)(C)C)C(O)=O)[C@@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@H]1O LPLVUJXQOOQHMX-MOGLOQIBSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 14
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 10
- 239000001263 FEMA 3042 Substances 0.000 claims description 10
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 10
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 10
- 229940033123 tannic acid Drugs 0.000 claims description 10
- 235000015523 tannic acid Nutrition 0.000 claims description 10
- 229920002258 tannic acid Polymers 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 4
- FBYJOCBDWDVDOJ-UHFFFAOYSA-M 4-methylbenzenesulfonate;tetrabutylphosphanium Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1.CCCC[P+](CCCC)(CCCC)CCCC FBYJOCBDWDVDOJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 description 15
- 241000202807 Glycyrrhiza Species 0.000 description 13
- -1 flavonoid compounds Chemical class 0.000 description 11
- MPDGHEJMBKOTSU-YKLVYJNSSA-N 18beta-glycyrrhetic acid Chemical compound C([C@H]1C2=CC(=O)[C@H]34)[C@@](C)(C(O)=O)CC[C@]1(C)CC[C@@]2(C)[C@]4(C)CC[C@@H]1[C@]3(C)CC[C@H](O)C1(C)C MPDGHEJMBKOTSU-YKLVYJNSSA-N 0.000 description 8
- 244000303040 Glycyrrhiza glabra Species 0.000 description 7
- 235000011477 liquorice Nutrition 0.000 description 7
- 229930182470 glycoside Natural products 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- MPDGHEJMBKOTSU-UHFFFAOYSA-N Glycyrrhetinsaeure Natural products C12C(=O)C=C3C4CC(C)(C(O)=O)CCC4(C)CCC3(C)C1(C)CCC1C2(C)CCC(O)C1(C)C MPDGHEJMBKOTSU-UHFFFAOYSA-N 0.000 description 4
- 229960003720 enoxolone Drugs 0.000 description 4
- 229920001864 tannin Polymers 0.000 description 3
- 235000018553 tannin Nutrition 0.000 description 3
- 239000001648 tannin Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 206010011224 Cough Diseases 0.000 description 1
- 241000220485 Fabaceae Species 0.000 description 1
- 206010062717 Increased upper airway secretion Diseases 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- YNWXJFQOCHMPCK-UHFFFAOYSA-N Isoliquiritin Natural products OC1C(O)C(O)C(CO)OC1OC(C=C1)=CC=C1C=CC(=O)C1=CC=C(O)C=C1O YNWXJFQOCHMPCK-UHFFFAOYSA-N 0.000 description 1
- 206010028594 Myocardial fibrosis Diseases 0.000 description 1
- YNCRBFODOPHHAO-YUELXQCFSA-N Phaseic acid Natural products CC(=CC(=O)O)C=C[C@@H]1[C@@]2(C)CO[C@@]1(C)CC(=O)C2 YNCRBFODOPHHAO-YUELXQCFSA-N 0.000 description 1
- 208000005392 Spasm Diseases 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229930003935 flavonoid Natural products 0.000 description 1
- 229930182486 flavonoid glycoside Natural products 0.000 description 1
- 150000007955 flavonoid glycosides Chemical class 0.000 description 1
- 235000017173 flavonoids Nutrition 0.000 description 1
- 241000411851 herbal medicine Species 0.000 description 1
- 238000010262 high-speed countercurrent chromatography Methods 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- LTINPJMVDKPJJI-UHFFFAOYSA-N iodinated glycerol Chemical compound CC(I)C1OCC(CO)O1 LTINPJMVDKPJJI-UHFFFAOYSA-N 0.000 description 1
- YNWXJFQOCHMPCK-LXGDFETPSA-N isoliquiritin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC(C=C1)=CC=C1\C=C\C(=O)C1=CC=C(O)C=C1O YNWXJFQOCHMPCK-LXGDFETPSA-N 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000874 microwave-assisted extraction Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- IZGYIFFQBZWOLJ-UHFFFAOYSA-N neophaseic acid Natural products C1C(=O)CC2(C)OCC1(C)C2(O)C=CC(C)=CC(O)=O IZGYIFFQBZWOLJ-UHFFFAOYSA-N 0.000 description 1
- 230000004112 neuroprotection Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- IZGYIFFQBZWOLJ-CKAACLRMSA-N phaseic acid Chemical compound C1C(=O)C[C@@]2(C)OC[C@]1(C)[C@@]2(O)C=CC(/C)=C\C(O)=O IZGYIFFQBZWOLJ-CKAACLRMSA-N 0.000 description 1
- 208000026435 phlegm Diseases 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- KKVTYAVXTDIPAP-UHFFFAOYSA-M sodium;methanesulfonate Chemical compound [Na+].CS([O-])(=O)=O KKVTYAVXTDIPAP-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000956 solid--liquid extraction Methods 0.000 description 1
- 210000000952 spleen Anatomy 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000002137 ultrasound extraction Methods 0.000 description 1
Classifications
-
- 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
- C07H15/26—Acyclic or carbocyclic radicals, substituted by hetero rings
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- Genetics & Genomics (AREA)
- Molecular Biology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Medicines Containing Plant Substances (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Abstract
The invention discloses a method for extracting and separating liquiritin and glycyrrhizic acid, which comprises the following steps: s1, mixing the ionic liquid with the licorice powder, and extracting the liquiritin and the glycyrrhizic acid; s2, after extraction is completed, performing solid-liquid separation, taking supernate, adding NaOH solution, heating to 65-80 ℃ to obtain an ionic liquid phase containing liquiritin and a water phase containing glycyrrhizic acid, and separating the water phase and the ionic liquid phase; wherein the ionic liquid is a temperature response type ionic liquid. According to the invention, the temperature-responsive ionic liquid is used as an extracting agent, and the temperature of the system is changed after extraction is finished, so that the liquiritin and the glycyrrhizic acid can be separated.
Description
Technical Field
The invention relates to the field of extraction of liquiritin and glycyrrhizic acid, and particularly relates to a method for extracting and separating liquiritin and glycyrrhizic acid.
Background
The licorice is the dry root or rhizome of perennial herb, the plant of Leguminosae, is a tonifying Chinese herbal medicine, and has the effects of tonifying spleen and qi, clearing away heat and toxic materials, eliminating phlegm and stopping cough, relieving spasm and pain, and harmonizing the medicines.
Modern chemical research shows that liquorice mainly contains flavonoid glycoside components (liquiritin, isoliquiritin and the like) and glycyrrhizic acid components, wherein the content of the liquiritin and glycyrrhizic acid is the highest. Liquiritin belongs to flavonoid compounds and has the functions of neuroprotection, oxidation resistance and myocardial fibrosis resistance; glycyrrhizic acid belongs to triterpenoid saponin compounds, and has pharmacological effects of resisting inflammation, resisting virus, protecting liver and the like. The traditional method for extracting liquiritin and glycyrrhizic acid usually adopts organic solvent or water as an extracting agent, or combines ultrasonic extraction and microwave-assisted extraction. These methods consume large amounts of organic solvents, causing serious environmental impact. And the traditional solid-liquid extraction method can not effectively separate the liquiritin and the glycyrrhizic acid. There are related documents reporting new methods for simultaneously extracting and separating glycyrrhizin and glycyrrhizic acid by using an aqueous two-phase system and a three-phase extraction system, and these methods are effective, but use a large amount of organic solvents. The high-speed counter-current chromatography is used for separating and purifying the liquiritin and the glycyrrhizic acid, has complex equipment and high cost, and limits the application of the liquiritin and the glycyrrhizic acid.
The ionic liquid is a salt composed of anions and cations and in a molten state at or near room temperature. Compared with the traditional organic solvent, the ionic liquid has the characteristics of non-volatility, non-flammability, strong extraction capacity and the like, so the ionic liquid is considered to be a novel green solvent. The research on extracting and separating bioactive substances from natural plant resources by using ionic liquid as an extracting agent is increasing. However, these methods have a great problem. The target product is difficult to separate from the extractant due to the non-volatility of the ionic liquid. Therefore, back extraction and column chromatography separation methods using organic solvents are still widely used.
Disclosure of Invention
Based on the technical problems in the prior art, the invention aims to provide a method for extracting and separating liquiritin and glycyrrhizic acid, wherein the liquiritin and glycyrrhizic acid can be separated by using temperature-responsive ionic liquid as an extracting agent and changing the system temperature after extraction is finished, the method is simple, and the used ionic liquid can be recycled and reused, so that the method is green and environment-friendly.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for extracting and separating glycyrrhizin and glycyrrhizic acid comprises the following steps:
s1, mixing the ionic liquid with the licorice powder for extraction;
s2, after extraction is completed, performing solid-liquid separation, taking supernate, adding NaOH solution, heating to 65-80 ℃ to obtain an ionic liquid phase containing liquiritin and a water phase containing glycyrrhizic acid, and separating the water phase and the ionic liquid phase;
wherein the ionic liquid is a temperature response type ionic liquid.
The temperature response type ionic liquid is a special ionic liquid and has the characteristic of changing state or property by changing the temperature of the external environment. The temperature response type ionic liquid serving as a novel green solvent can replace the traditional volatile organic solvent to be applied to extraction and separation of active ingredients of natural products.
The invention utilizes the characteristic that temperature response type ionic liquid can change according to the temperature generation state or property as an extracting agent to extract the liquorice so as to realize the extraction and separation of liquiritin and glycyrrhizic acid in the liquorice.
In some embodiments, the ionic liquid is tetrabutylphosphonium p-toluenesulfonate.
In some embodiments, in step S1, the ionic liquid has a concentration of 20 to 80%.
In some embodiments, the extraction temperature in step S1 is 40-60 ℃.
In some embodiments, in step S1, the solid-to-liquid ratio is 1g: 20-100 mL.
In some embodiments, in step S1, the extraction time is 10-60 min.
In some embodiments, in step S2, a NaOH solution is added to form a mixed solution, wherein the concentration of NaOH is 0-2%.
In some embodiments, further comprising the steps of:
s3, adding a tannic acid aqueous solution into the ionic liquid phase, and then carrying out solid-liquid separation to obtain liquiritin and ionic liquid.
In some embodiments, the concentration of the aqueous tannic acid solution is 0.95-7.5%.
In some embodiments, the concentration of the aqueous tannic acid solution is 3.33 to 7.5%.
Compared with the prior art, the invention has the following beneficial effects:
the invention creatively takes the temperature response type ionic liquid as an extractant to extract the liquorice, then sodium hydroxide solution is added, and the temperature of the solution system is changed to realize the separation of the water phase and the ionic liquid, thereby realizing the extraction and the separation of the liquiritin and the glycyrrhizic acid.
The method can effectively separate the liquiritin and the glycyrrhizic acid, and the used ionic liquid can be recycled and recycled by a simple method, so that the cost is saved, and the method is green and environment-friendly.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The ionic liquid used in the following examples is tetrabutyl phosphonium p-toluenesulfonate sodium which is one of temperature response type ionic liquids, the ionic liquid can be homogeneous with water at low temperature, and the ionic liquid can be separated into two phases with water at elevated temperature. The ionic liquid is prepared by the following method:
mixing tetrabutyl phosphonium bromide and sodium p-toluenesulfonate in water at a molar ratio of 1:1, magnetically stirring, heating to 70 ℃ for reaction for 24 hours, and evaporating water to dryness to obtain ionic liquid, namely tetrabutyl phosphonium sodium p-toluenesulfonate.
The method for extracting and separating the liquiritin and the glycyrrhizic acid in the following embodiments comprises the following steps:
s1, mixing the ionic liquid with the licorice powder for extraction;
s2, after extraction is completed, performing solid-liquid separation, taking supernate, adding NaOH solution, heating to 65-80 ℃ to obtain an ionic liquid phase containing liquiritin and a water phase containing glycyrrhizic acid, and separating the water phase and the ionic liquid phase.
Examples 1 to 5
The method of the step S1 is adopted to extract the liquorice, and in the embodiments 1 to 5, other extraction conditions are the same, specifically: the solid-liquid ratio is 1g:40mL, the extraction temperature is 50 ℃, and the extraction time is 30min, which is different from the concentration of the ionic liquid. After the extraction, the extraction effects of glycyrrhizin and glycyrrhizic acid were measured, as shown in table 1.
TABLE 1 Effect of ionic liquids of different concentrations on the extraction yield of glycyrrhizin and glycyrrhizic acid
| Examples | Concentration of Ionic liquid (%) | Glycyrrhiza glycosides extraction rate (mg/g) | Glycyrrhetinic acid extraction yield (mg/g) |
| 1 | 20 | 5.52 | 15.00 |
| 2 | 40 | 5.71 | 15.30 |
| 3 | 50 | 5.79 | 19.82 |
| 4 | 60 | 6.61 | 25.04 |
| 5 | 80 | 6.22 | 18.79 |
Examples 6 to 10
The method of the step S1 is adopted to extract the liquorice, and in the embodiments 6 to 10, other extraction conditions are the same, specifically: the concentration of the ionic liquid is 60%, the extraction temperature is 50 ℃, and the extraction time is 30min, wherein the difference is that the solid-liquid ratio is different. After the extraction, the extraction effects of glycyrrhizin and glycyrrhizic acid were measured, as shown in table 2.
TABLE 2 influence of different solid-liquid ratios on the extraction rates of glycyrrhizin and glycyrrhizic acid
| Examples | Solid to liquid ratio (g/ml) | Glycyrrhiza glycosides extraction rate (mg/g) | Glycyrrhetinic acid extraction yield (mg/g) |
| 6 | 1:100 | 7.81 | 25.47 |
| 7 | 1:50 | 11.27 | 25.58 |
| 8 | 1:40 | 8.10 | 20.38 |
| 9 | 1:25 | 7.21 | 16.46 |
| 10 | 1:20 | 7.13 | 14.30 |
Examples 11 to 15
The method of step S1 is adopted to extract glycyrrhiza, and in examples 11 to 15, the other conditions are the same, specifically: the concentration of the ionic liquid is 60%, the solid-to-liquid ratio is 1g: 50mL, and 30min of extraction time, with the difference that the extraction temperature is different. After the extraction, the extraction effects of glycyrrhizin and glycyrrhizic acid were measured, as shown in table 3.
TABLE 3 Effect of different extraction temperatures on the extraction yield of Glycyrrhiza glycosides and Glycyrrhiza acids
| Examples | Temperature (. degree.C.) | Glycyrrhiza glycosides extraction rate (mg/g) | Glycyrrhetinic acid extraction yield (mg/g) |
| 11 | 40 | 9.41 | 23.33 |
| 12 | 45 | 10.78 | 23.94 |
| 13 | 50 | 11.22 | 24.89 |
| 14 | 55 | 9.65 | 28.29 |
| 15 | 60 | 8.61 | 26.78 |
Examples 16 to 20
The method of the step S1 is adopted to extract the liquorice, and in the embodiments 16 to 20, the other conditions are the same, specifically: the concentration of the ionic liquid is 60%, the solid-to-liquid ratio is 1g: 50mL, and an extraction time of 55 ℃ except that the extraction time was different. After the extraction, the extraction effects of glycyrrhizin and glycyrrhizic acid were measured, as shown in table 4.
TABLE 4 Effect of different extraction times on the extraction of Glycyrrhiza glycosides and glycyrrhizic acids
| Examples | Time (min) | Glycyrrhiza glycosides extraction rate (mg/g) | Glycyrrhetinic acid extraction yield (mg/g) |
| 16 | 10 | 9.65 | 22.41 |
| 17 | 20 | 9.72 | 24.32 |
| 18 | 30 | 9.63 | 28.51 |
| 19 | 40 | 9.13 | 25.75 |
| 20 | 60 | 9.20 | 25.59 |
From the above examples 1-20, it can be seen that, when tetrabutyl phosphonium is selected to use the sodium methanesulfonate as an ionic liquid as an extractant to extract glycyrrhizin and glycyrrhizic acid from licorice, the extraction effect is affected by the concentration of the ionic liquid, the solid-liquid ratio, and the weight ratio of ionic liquid is 1g: the extraction effect on the liquiritin and the glycyrrhizic acid is best when the volume is 40mL, the extraction temperature is 55 ℃ and the extraction time is 30 min.
Examples 21 to 24
The method of the step S2 is adopted to separate the liquiritin and the glycyrrhizic acid, and the specific operations are as follows: after extraction, performing solid-liquid separation by centrifugation, taking supernatant, adding NaOH solution, and heating to 70 deg.C to obtain liquiritin-containing ionic liquid phase and glycyrrhizic acid-containing water phase. Examples 21 to 24 differ in the NaOH solution added, as shown in Table 5.
TABLE 5 Effect of different NaOH concentrations on liquiritin and glycyrrhizic acid extraction and separation
| Examples | NaOH concentration (%) | Distribution coefficient of liquiritin | Distribution coefficient of glycyrrhizic acid | Coefficient of system selectivity |
| 21 | 0 | 11.17 | 0.09 | 0.96 |
| 22 | 0.5 | 4.22 | 2.36 | 9.95 |
| 23 | 1 | 3.19 | 4.16 | 13.27 |
| 24 | 2 | 2.09 | 3.56 | 7.45 |
Examples 25 to 29
The liquiritin and glycyrrhizic acid were extracted and separated by the method of the above step S2, and in examples 25 to 29, the concentrations of the NaOH solutions were all 1%, except that the extraction temperatures were different, as shown in table 6.
TABLE 6 influence of different extraction temperatures on the extraction and separation of glycyrrhizin and glycyrrhizic acid
From examples 21 to 29, it is understood that the effect of separating glycyrrhizin from glycyrrhizic acid was the best when the concentration of NaOH solution was 1% and the extraction time was 70 ℃.
Separating the ionic liquid phase and the water phase, adding tannic acid into the ionic liquid phase, allowing the tannic acid to complex with liquiritin in the ionic liquid phase to form precipitate, separating liquiritin from the ionic liquid, and performing solid-liquid separation to obtain liquiritin and the ionic liquid. The ionic liquid may be diluted 5-fold prior to the addition of tannic acid. The influence of different tannin concentrations on the liquiritin separation effect is examined, and is specifically shown in table 7.
TABLE 7 Effect of different tannin concentrations on liquiritin separation Effect
| Tannin concentration (%) | Distribution coefficient of liquiritin |
| 0.95 | 23.18 |
| 3.33 | 67.41 |
| 4.62 | 71.51 |
| 5.71 | 76.74 |
| 6.67 | 87.38 |
| 7.50 | 88.08 |
In summary, the most preferred embodiments of the method of the present invention are:
s1, mixing the ionic liquid with the concentration of 60% and the licorice powder according to the solid-to-liquid ratio of 1g: mixing 50mL of the extract, and extracting at 55 ℃ for 30 min;
s2, after extraction, performing solid-liquid separation, taking supernatant, adding 1% NaOH solution, heating to 70 ℃ to obtain an ionic liquid phase containing liquiritin and a water phase containing glycyrrhizic acid, and separating the ionic liquid phase and the water phase.
Adding tannic acid with concentration of 7.5% into the ionic liquid phase to separate out liquiritin from the ionic liquid phase to obtain liquiritin and ionic liquid. The separated ionic liquid can be circularly used for extracting liquiritin and glycyrrhizic acid.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A method for extracting and separating liquiritin and glycyrrhizic acid is characterized by comprising the following steps:
s1, mixing the ionic liquid with the licorice powder, and extracting the liquiritin and the glycyrrhizic acid;
s2, after extraction is completed, performing solid-liquid separation, taking supernate, adding NaOH solution, heating to 65-80 ℃ to obtain an ionic liquid phase containing liquiritin and a water phase containing glycyrrhizic acid, and separating the water phase and the ionic liquid phase;
wherein the ionic liquid is a temperature response type ionic liquid.
2. The method for extracting and separating glycyrrhizic acid from glycyrrhizic acid according to claim 1, wherein the ionic liquid is tetrabutyl phosphonium p-toluenesulfonate.
3. The method for extracting and separating glycyrrhizin and glycyrrhizic acid according to claim 1, wherein in step S1, the concentration of the ionic liquid is 20-80%.
4. The method for extracting and separating glycyrrhizin and glycyrrhizic acid according to claim 1, wherein in step S1, the extraction temperature is 40-60 ℃.
5. The method for extracting and separating glycyrrhizic acid from glycyrrhizic acid according to claim 1, wherein in step S1, the solid-to-liquid ratio is 1g: 20-100 mL.
6. The method for extracting and separating glycyrrhizin and glycyrrhizic acid according to claim 1, wherein in step S1, the extraction time is 10-60 min.
7. The method for extracting and separating glycyrrhizic acid from glycyrrhizin according to claim 1, wherein in step S2, NaOH solution is added to form a mixed solution, and the concentration of NaOH is 0-2%.
8. The method for extracting and separating glycyrrhizin and glycyrrhizic acid according to any one of claims 1 to 7, further comprising the steps of:
s3, adding a tannic acid aqueous solution into the ionic liquid phase, and then carrying out solid-liquid separation to obtain liquiritin and ionic liquid.
9. The method for extracting and separating glycyrrhizin and glycyrrhizic acid according to claim 8, wherein the concentration of the aqueous solution of tannic acid is 0.95-7.5%.
10. The method for extracting and separating glycyrrhizin and glycyrrhizic acid according to claim 9, wherein the concentration of the aqueous solution of tannic acid is 3.33-7.5%.
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