CN104861015A - Synergistic clean extraction method of effective components in licorice root - Google Patents

Synergistic clean extraction method of effective components in licorice root Download PDF

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CN104861015A
CN104861015A CN201510028975.XA CN201510028975A CN104861015A CN 104861015 A CN104861015 A CN 104861015A CN 201510028975 A CN201510028975 A CN 201510028975A CN 104861015 A CN104861015 A CN 104861015A
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radix glycyrrhizae
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potenlini
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李玉山
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Abstract

A synergistic clean extraction method of effective components in licorice root adopts a solvent to synchronously extract the effective components in licorice root in order to obtain a total extract product, and the total extract product is separated one by one according to physical and chemical properties of all the components. The method comprises the following steps: 1, preparing the total extract product of the licorice root; 2, separating water-soluble and fat-soluble components; 3, separating glycyrrhizic acid from licorice pigments, licorice glucose and licorice polysaccharides in the water-soluble components; 4, separating the licorice pigments from the licorice glucose and the licorice polysaccharides; 5, separating the licorice glucose from the licorice polysaccharides; 6, separating and purifying glabridin in the fat-soluble components; 7, separating and purifying liquiritin and isoliquiritin in the fat-soluble components; 8, separating and purifying isoliquiritigenin and liquiritigenin in the fat-soluble components; 9, separating and purifying licochalcone A in the fat-soluble components; 10, separating and purifying licorice lignin in the fat-soluble components; and 11, separating and purifying licorice cellulose in the fat-soluble components.

Description

In a kind of Radix Glycyrrhizae, the collaborative of effective constituent cleans extracting method
Technical field
The present invention relates to the collaborative of effective constituent in a kind of Radix Glycyrrhizae and clean extracting method.
Background technology
Radix Glycyrrhizae (Glycyrrhiza uralensis Fisch) is called: old, the sweet grass of state, Glycyrrhiza uralensis Fisch., sweet root.Medicinal part is root and rhizome, cylindrical, and there is bud trace on surface, has marrow in the middle part of section.Long 25-100cm, diameter 0.6-3.5cm.Crust degree of tightness differs, and the brown or taupe brown of surface red, the inside is faint yellow.Gas is micro-, and taste is sweet and special.The former plant of licorice medicinal materials of state-promulgated pharmacopoeia identification has three kinds, i.e. the dry root and rhizome of Radix Glycyrrhizae (Glycyrrhizauralensis Fisch.), glycyrrhiza inflate bat (Glycyrrhiza infiata Bat.) and glycyrrhiza glabra (Glycyrrhizaglabra L.).Radix Glycyrrhizae is China's traditional Chinese medicine material, and applicating history is long, is famous at home and abroad.As far back as the Warring States Period, just there is the record utilizing Radix Glycyrrhizae to cure the disease, apart from modern existing more than 2500 year.Eastern Han Dynasty's " legendary god of farming's book on Chinese herbal medicine " claims Radix Glycyrrhizae to be classified as top grade for " lantern " and " close sweet ".Chinese materia medica is thought: Radix Glycyrrhizae taste is sweet, flat, is invigorate the spleen and benefit qi, cough-relieving happiness disease, relieving spasm to stop pain, coordinating the actions of various ingredients in a prescription, the good medicine of removing toxic substances.Radix Glycyrrhizae extract is classified as safety non-toxic material by U.S. FDA.Scientific research proves, Radix Glycyrrhizae is mainly containing Potenlini and licoflavone class.Radix Glycyrrhizae is one of most popular herbal medicine in the world, and in ayurvedic medicine, it can assisting therapy eye illness, throat infection, stomach ulcer, sacroiliitis and hepatopathy.Reason is that it can reduce phlegm, moisturizing, anti-inflammatory, antipathogen, anti-hepatotoxin and antibacterial.The many growths of Radix Glycyrrhizae are at arid, semiarid sandy soil, and desert edge and loess hill area, be also easy to breeding in the field and flood land of irrigation areas.Its strong adaptability, strong stress resistance.Radix Glycyrrhizae happiness illumination is sufficient, and rainfall amount is less, and summer is extremely hot, winter severe cold, the ecotope that day and night temperature is large, has happiness light, drought-enduring, heat-resisting, Salt And Alkali Tolerance and cold-resistant characteristic.Be suitable for deep at soil layer, the soil is porous, grow in well-drained sandy soil.Radix Glycyrrhizae in Asia, there is distribution on Europe, Australia, the ground such as America.In China, Radix Glycyrrhizae is mainly distributed in Xinjiang, the Inner Mongol, Ningxia, Gansu, Shuozhou, shanxi Province is wild is main.Artificial growth Radix Glycyrrhizae main product in Xinjiang, the Inner Mongol, Gansu Hexi Corridor, the periphery in the west of Gansu Province, countries of Ningxia Hui Autonomous Region area.It is reported, often produce 300 tons of Radix Glycyrrhizae extractum and have the generation of 1000-1500 ton glycyrrhiza residue.Therefore, the disposal and utilization of glycyrrhiza residue causes the attention of people.The major ingredient of glycyrrhiza residue is: amino acid 7.57%, protamine 7.56%, crude protein 8.24%, moisture content 2.65%, ash 9.6%, Mierocrystalline cellulose 30.78%, calcium 2.17%, phosphorus 0.19%.
The chemical constitution of Radix Glycyrrhizae is very complicated, 1) Radix Glycyrrhizae root welding technology master is containing triterpenoid saponin, wherein main glycyrrhizin (glycyrrhizin) is the sweet ingredient of Radix Glycyrrhizae, is sylvite and calcium salt that the 18 β-glycyrrhetinic acid of 1 molecule and the glucuronic acid of 2 molecules combine the Potenlini (glycyrrhizic acid) generated.Other triterpenoid saponin has: Glycyrrhiza uralensis Fisch. saponin(e (uralsaponin) A, B and glycyrrhizin (licoricesaponin) A 3, B 2, C 2, D 3, E 2, F 3, G 2, H 2, J 2, K 2.Again containing flavonoid compound: 4',7-Dihydroxyflavanone (liquiritigenin), liquirtin (liquiritin), isoliquiritin unit (isoliquiritigenin), isoliquiritin (isoliquiritin), Neoliquiritin (neoliquiritin), parent's isoliquiritin (neoisoliquiritin), licoricidin (licoricidin), Licoricone (licoricone), Formononetin (formononetin), 5-O-methyl Radix Glycyrrhizae this fixed (5-O-methyllicoricidin), 4',7-Dihydroxyflavanone-4 '-celery sugar glycoside [liquiritigenin-4 '-qpiofur-anosyl (1 → 2) glucopyranoside, apioliquiritin], 4',7-Dihydroxyflavanone-7,4 '-diglucoside (liquiritigenin-7,4 '-diglucoside), puriri glycosides II (vicenin II), Isolicoflavonol (isolicoflanonol), Isoliquiritigenin-4 '-celery sugar heteroside [isoliquiritigenin-4 '-apiofuranosyl (1 →) glucopyranoside, licurazid, apioisoliquiritin].Also containing Coumarins compound: Radix Glycyrrhizae coumarin (glycycoum-arim), glycyol (glycyrol), isoglycyol (isoglycyrol), Radix Glycyrrhizae coumarin-7-methyl ether (glycyrin), neoglycyrol (neoglycyrol), Radix Glycyrrhizae pyrans coumarin (licopyranocoumarin), licocoumarone (licocoumarione) etc.Alkaloid: 5,6,7,8-tetrahydrochysene-4-toluquinoline (5,6,7,8-tetcmlibahydro-4-methylquinoline), 5,6,7,8-tetrahydrochysene-2,4-dimethyl quinoline (5,6,7,8-tetcmlibahydro-2,4-dimethylquinoline), 3-methyl-6,7,8-tri-hydrogen pyrrolo-[1,2-a] pyrimidine-3-ketone (3-methyl-6,7,8-tcmlibihydropyrrolo [1,2-] pyrimidin-3-one).Also containing licobenzofuran (licobenzofuran), have another name called liconeolignan (liconeolignan), β-sitosterol (β-sitosterol), n-tricosane (n-tcmlibicosane), n-hexacosane (n-hexacos-ane), heptacosane (n-heptacosane) etc.Another containing Radix Glycyrrhizae dextran GBW (glucan GBW), licorice polysaccharide (glycyrrigan) U a, U b, U c, polysaccharide (polysaccharide) GR-2a, GR-2II b, GR-2II C of tool panimmunity excitation and polysaccharide GPS etc.The leaf of Radix Glycyrrhizae is containing chromocor compound: puriri glycosides-II, narcissin (narcissi), Nicotifiorin (nicotiflorin), violaguercitrin (rutin), isoquercitrin (isoquercitcmlibin), astragalin (astcmlibagalin), uralenol (uralenol), Xin Wuer alcohol (uralenol), neouralenol (neouralenol), uralenin (uralenin), Quercetin-3, 3 '-dme (quercetin-3, 3 '-dimethyl ether), Uralenol-3-methylether (uralenol-3-methylether), uralene (uralene), Quercetin (quercetin) etc.Also containing the new glycosides in Ural (uralenneoside).Radix Glycyrrhizae over-ground part contains Scopoletin (scopoletin), Formononetin, lupinus luteus Wei Te ketone (lupiwighteone), second shape thorn ketone element (sigmoidin) B and peaceful (gancaonin) A, B, C, D, E, L, M, N, O, P, Q, R, S, T, U, the V of Radix Glycyrrhizae, 2) glycyrrhiza glabra root welding technology is containing Potenlini, 18-β glycyrrhetinic acid, namely biosone (uralenic acid) outward, also has triterpene compound: 18 Alpha-hydroxy glycyrrhetinic acids (18 α-hydroxyglycyrrhetic acid), 24-hydroxyl glycyrrhetinic acid (24-hydroxyglycyrrheticacid), 24-hydroxyl-11-deoxyglycyrrhetinic acid (24-hydroxy-11-deoxyglycyrrhetic acid), 11-deoxyglycyrrhetinic acid (11-deoxyglycyrrhetic acid), 3 beta-hydroxy oleas-11, 13 (18)-diene-30-acid [3 β-hydroxyolean-11, 13 (18)-dien-30-oic acid] glycyrrhetol (glycyrrhetol), glycyrrhiza glabra ester (glabrolide), different glycyrrhiza glabra inspection ester (isoglabrolide), deoxidation glycyrrhiza glabra lactone (deoxyglabrolide), the different glycyrrhiza glabra lactone of 21 Alpha-hydroxy (21 α-hydroxyisoglabrolide), liquoric acid (liquoric acid) etc.Again containing flavone component: glycyrrhiza glabra glycosides (liquiritoside) is namely liquirtin, glycyrrhiza glabra aglycon (liquiritogenin) is namely 4',7-Dihydroxyflavanone, different glycyrrhiza glabra glycosides (isoliquiritoside) is namely isoliquiritin, different glycyrrhiza glabra aglycon (isoliquiritogenin) is namely 4',7-Dihydroxyflavanone, Neoliquiritin, parent's isoliquiritin, isoliquiritin unit-4 '-celery sugar glucoside (licuraside, licurazid), isoliquiritin unit-4-celery sugar glucoside [neolicuraside, isoliquiritigenin-4-apiofuranosyl (1 → 2) glucopyranoside], glabranin (glabranin), glycyrrhiza glabra alcohol (glabrol), glycyrrhiza glabra fixed (glabridin), glycyrrhiza glabra ketone (glabrone), glycyrrhiza glabra element (glabreene), 7,2 '-dihydroxyl-3 ', 4 '-methylene-dioxy isoflavones (glyzaglabrin), 7-acetoxyl group-2-methyl isoflavones (glazarin), 7-methoxyl group-2-methyl isoflavones (7-methyoxy-2-methylisoflavone), prunusetin (prunetin), 7-hydroxy-2-methyl isoflavones (7-hydroxy-2-methylisoflavone), raw loose flavanone (pinocembrin), Formononetin etc.Again containing glycyrrhiza glabra coumarin (liqcoumarin) and water-soluble polysaccharide and pectin (pectin).Multiple flavonoid compound: Quercetin, isoquercitrin (isoquercitcmlibin), Quercetin-3-two glucoside (quercetin-3-glucobioside), trifolitin (kaempferol), astragalin, saponaretin (saponaretin), 4',7-Dihydroxyflavanone, isoliquiritin unit, genkwanin (genkwanin), Kaempferol-bis-heterosides (kaempferol-3-glucoboside) etc.Another containing polysaccharide 9.7%, wherein water-soluble polysaccharide 1.6%; 3) glycyrrhiza inflate bat root is containing triterpenes glucin, glycyrrhetinic acid-3-celery sugar glucuronide (apioglycyrrhizin), glycyrrhetinic acid-3-pectinose glucuronide (araboglycyrrhizin), 18 β-glycyrrhetinic acid, 11-deoxyglycyrrhetinic acid, Glycyrrhiza uralensis Fisch. saponin A 3, G 2, H 2deng.Flavones ingredient: 4',7-Dihydroxyflavanone, liquirtin, isoliquiritin unit, isoliquiritin, ononin, 4 ', 7-dihydroxyflavone (4 ', 7-dihydroxyflavone), licoflavone (licoflavone) A, 4',7-Dihydroxyflavanone-4 '-celery sugar glucoside, isoliquiritin unit-4 '-celery sugar glucoside, Radix Glycyrrhizae distant and out of sight ear ketone (licochalcone) A, B, C, D, seta licochalcone (echinatin), glycyrrhiza glabra ketone.Arylprop diketone: peaceful (glyinflanin) A, B, C, the D of 5 '-isopentene group glycyrdione (5 '-prenyllicodione), glycyrrhiza inflate bat diketone (glycyrdione) A, B and glycyrrhiza inflate bat, again containing β-paddy alcohol (β-sitosterol); 4). Glycyrrhiza Aspera Root root is containing triterpenes components: Potenlini, glycyrrhiza glabra lactone etc.Flavones ingredient: liquirtin, isoliquiritin, Glycyrrhiza Aspera Root element (glyasperin) A, B, C, D, kumatakenin (kumata kenin), oriental topaz feather fan legumin (topazolin), Glycyrrhisoflavone (licoisoflavone) B, half Glycyrrhisoflavone (semilicoisoflavone) B, licoisoflavanone (licoisoflavanone), 3 '-(γ, γ-dimethyl-allyl) very tie up ketone [3 ' (γ, γ-dimethylallyl)-kievitone], licoricidin, Radix Glycyrrhizae isoflavan (licoriisoflavan) A, 1-methoxyl group Fei Xifoli alcohol (1-methyoxyficifolinol).Coumarins composition: Radix Glycyrrhizae coumarin, different Radix Glycyrrhizae coumarin (isoglycycoumarin), glycyol, licocoumarone, another containing water-soluble polysaccharide, pectin; 5). yellow Radix Glycyrrhizae root welding technology is containing triterpenes components: Potenlini, penta La Er glycyrrhizin A and B, glyeurysaponin (glyeurysaponin).Flavones ingredient: yellow liquirtin (glycyroside), ononin, liquirtin, isoliquiritin, 4',7-Dihydroxyflavanone-4 '-celery sugar glucoside, different Radix Glycyrrhizae unit-4 '-celery sugar glucoside, Fructus Choerospondiatis glycosides (choerospondin), root of subprostrate sophora flavonoid glycoside (sophoraflavone) B, Xia Futa basket glycosides (schaftoside), wild pansy flavonoid glycoside (isovi-osanthin), clover red sandalwood phenol-3-O-glucoside (medicarpin-3-O-glucoside), puriri glycosides II, β-sitosterol (β-sitosterol), daucosterol (daucosterol), phloretic acid (phloretic acid), 6) root of Yunnan Licorice root is containing triterpenes components: root of Yunnan Licorice prosapogenin D (glyyyunnanpro-sapogenin D), root of Yunnan Licorice sapogenin (glyyunnansapogenin) A, B, C, E, F, G, H and Macedonia's Potenlini (macedonic acid), again containing B-Sitosterol.Flavones ingredient: isoliquiritin unit, 4 ', 7-dihydroxyflavone, 7-methoxyl group-4 '-flavonol (7-methoxy-4 '-hydroxyflavone), 7-methoxyl group-4 '-flavonol alcohol (7-methoxy-4 '-hydroxyflavonol).Root is containing triterpenoid saponin: the sweet glycosides of cloud (yunganoside) A 1, B 1, C 1, D 1, E 2and F 2, add containing alkaloid: Hypaphorine (hypaphorine); 7) the commercially available sweet wax commodity of China, except raising variety, the species indeterminata of running after fame with area in addition, quite a few to their research.Hereby select its important person to be summarized as follows: the root welding technology of (1) northwest Radix Glycyrrhizae is containing Potenlini, liquirtin, isoliquiritin, 4',7-Dihydroxyflavanone, isoliquiritin unit, Radix Glycyrrhizae coumarin, Radix Glycyrrhizae pyrans coumarin, licocoumarone, Licochalcone A, Isolicoflavonol, northwest Glycyrrhisoflavone (glycyrrhisoflavone), northwest licoisoflavanone (glycrrhisoflvanone), Licoflavonol, Radix Glycyrrhizae beans essence-7-methyl ether, licoricidin, Licoricone, the peaceful F of Radix Glycyrrhizae, G, H, I, sweet phenol, 5-O-cresols (5-O-methylglycyrol), kumatakenin etc.(2) root welding technology of Xinjiang Radix Glycyrrhizae is determined containing Potenlini, liquirtin, isoliquiritin, isoliquiritin unit, the sweet fruit phenyl styryl ketone of 4 ', 7-dihydroxyflavone, Formononetin, glycyrrhiza glabra alcohol, seta, Licochalcone A, B, Glycyrrhisoflavone B, licoisoflavanone (licoisoflavanone), glycyrrhiza glabra element, glycyrrhiza glabra.(3) root welding technology of northeast Radix Glycyrrhizae is containing Potenlini, liquirtin, isoliquiritin, 4',7-Dihydroxyflavanone, isoliquiritin unit, Radix Glycyrrhizae coumarin, Radix Glycyrrhizae pyrans coumarin, licocoumarone, licocoumarone, licoricidin, Licoricone, glycyol, 5-O-methyl glycyol etc.These compositions and quantity usually can be different with the difference of the factors such as the kind of Radix Glycyrrhizae, planting area, collecting time; large quantifier elimination shows; Potenlini and licoflavone class material are most important physiologically active substances in Radix Glycyrrhizae; mainly be present in the part within licorice epidermis, in Radix Glycyrrhizae, flavonoids has kind more than 150.
The main pharmacological function of Radix Glycyrrhizae: 1) for insufficiency of heart-QI, deficiency of spleen-QI and stomach-QI, fatigue and weakness etc.Often there is ball etc. in Ramuli Cinnamomi and Glycyrrhizae Decoction, zhigancao decoction, decoction of four noble drugs, reason; 2) for ulcer sores, swelling and pain in the throat etc.Often there are Xian fang Huoming Yin, Radix Platycodonis decoction etc.; 3) for asthma and cough.Often there are erchen tang, Linggan Wuwei Jiangxin Tang, sangxing decoction, Radix Platycodonis decoction, Gancao Ganjiang soup etc.; 4) for stomachache, stomachache and the anxious pain of gastrocnemius muscle contraction etc., peony and licorice decoction is often had; 5) for being in harmonious proportion the strong of some drugs.As relax rheum officinale, saltcake discharge function and to GI stimulation; 6) similar adrenocortical hormone sample effect.There is gastric acid secretion inhibiting too much, alleviate the effect of gastrointestinal smooth myospasm; 7) licoflavone, Radix Glycyrrhizae extractum and glycyrrhetinic acid all have obvious Antitussive and Expectorant Effect; 8) there is anti-inflammatory, anti-allergic effects, throat and the tunica mucosa tracheae of inflammation can be protected, have detoxification; 9) Liquiritigenin is a kind of compound of similar hormone, can balance the hormone-content in women's body, the symptom that treatment Menopause occurs; 10) glycyrrhetinic acid can block carcinogens and tumor growth.
5.1 ten thousand tons, Xinjiang in 2013 port import Radix Glycyrrhizae, comparatively increases by 98.3% in 2012; Be worth 6,820 ten thousand dollars, increase by 1.4 times; Beautiful yuan/ton of import average price 1342.5, goes up 19.1%.Import in December 5455 tons, increases by 71.3%; Be worth 7,580,000 dollars, increase by 81.3%; Beautiful yuan/ton of import average price 1388.8, goes up 5.8%, chain rate drop 7.2%.Within 2013, Radix Glycyrrhizae import volume significantly increases, and especially increases the second half year obviously, comparatively all increases substantially the second half year in 2012.Average price has fluctuated at about 1200 dollars per ton all the time since the fourth quarter in 2012, and the second half year in 2013 presents the situation risen in fluctuation gradually.Processing trade share progressively expands, and ordinary trade and frontier trade in small amount all have growth.Port, Xinjiang in 2013, with processing trade mode import 2,392 ten thousand dollars, increases by 88.4% on a year-on-year basis, accounts for 35.1% of port, Xinjiang same period Radix Glycyrrhizae total import value; With way of general trade import 2,436 ten thousand dollars, increase by 1.1 times, account for 35.7%; With border small amount mode import 1,992 ten thousand dollars, increase by 3.6 times, account for 29.2%.Private enterprise increases very fast, and stateowned enterprise increases substantially.Private enterprise's import in 2013 3910 ten thousand dollars, increases by 1.6 times, accounts for 57.4%; 2,438 ten thousand dollars, stateowned enterprise import Radix Glycyrrhizae, increases by 1.9 times, accounts for 35.7%; The same period, foreign capital affiliate's import 4,720,000 dollars, declines 12.4%, accounts for 6.9%.Kazakhstan is Radix Glycyrrhizae main body entrance state, and each trading partner all has growth.Port, Xinjiang in 2013, from 3,979 ten thousand dollars, Kazakhstan import Radix Glycyrrhizae, increases by 1.6 times, accounts for 58.3%; White Uzbekistan import 1,381 ten thousand dollars, increases by 39%, accounts for 20.2%; From 7,970,000 dollars, Azerbaijan import Radix Glycyrrhizae, increase by 2.5 times on a year-on-year basis, account for 11.7%.The same period, also there is a small amount of import at port, Xinjiang from Afghanistan, Tajikistan, Kirghizstan.Fresh or dry Radix Glycyrrhizae presents the import rising tendency that falls in export.Because international Radix Glycyrrhizae market is more active on the one hand, because the import tariff of Radix Glycyrrhizae and Radix Glycyrrhizae juice and medicinal extract is reduced to 0 from 6% in 2008 by Customs tariff Commission of the State Council on the other hand, excite the enthusiasm of enterprise import Radix Glycyrrhizae, and this measure is also one of effective measure solving China's Licorice shortage.
1. liquorice pigment, different name glycyrrhizic flavochrome is morin, No. CAS: 480-16-0, No. EINECS: 207-542-9, molecular formula is C 15h 10o 72H 2o is that oxygen containing heterocycle connects two aromatic nucleus, is generally yellow or lark needle crystal, and be long placed in air oxidizable for brown, fusing point 285 DEG C-290 DEG C (decomposition), is slightly soluble in water.
Derive from pulse family draft liquorice root (Glycyrrhiza uralensis for many years; G.glabra and congeneric species thereof) rhizome be raw material, the yellow colorants obtained with water or carbon dioxide upercritical fluid extraction, is usually used in the basic food yellow colorants such as the noodles of more than pH8.1) developer effect, is commonly used to the iron, zinc, cobalt etc. that detect trace in chemical analysis; 2) can inhibitory enzyme activity, there is anti-oxidant, anti-pain, antibacterial, anti-inflammatory, atherosclerosis, the effect such as reduction blood sugar and anti-stress; 3) antitumous effect, by inducing apoptosis of tumour cell, promotion anti-tumour cell proliferative, intervention tumour cell intracellular signaling, promote to press down pain genetic expression, promote tumour necrosis factor, suppress carcinogen and the approach such as anti-oxidant to realize antitumous effect, to ascites hepatoma cells kill and wound have permanent; 4) anti-inflammatory, immunization, plays antiinflammatory immunity function mainly through affecting the secretion of cell, mitotic division and intercellular interaction; 5) antioxygenation, in most flavonoid compound structure 2,3 double bonds and 4 carbonyls and 3 or 5 hydroxyls have scavenging free radicals and oxidation resistant ability, energy is scavenging free radicals directly, also be combined by some oxydase in body, affect its configuration, conformation, the activity of inhibitory enzyme, thus suppress the generation of free radical.The existence of 4 carbonyls extends π-conjugated systems, is conducive to forming more stable free radical intermediate, is conducive to anti-oxidant activity, can be used for anti-virus infection, treatment headache, stomach trouble, chronic inflammatory diseases and coronary heart disease.There is stronger anti-microbial effect to streptococcus aureus, dysentery bacterium and Corynebacterium diphtheriae, have obvious mutagenesis.
Extraction bibliographical information about liquorice pigment is less, about the extraction of liquorice pigment, Liao Shenghua, Tian Qiulin, Wu soldier's report morin (morin) in " carbon paste electrode Anodic stripping measures morin in glycyrrhiza uralensis fisch " (physical and chemical inspection-chemical fascicle 40 (3): 140-14) is Flavonoid substances, is one of main component of many natural drugs, as Radix Glycyrrhizae, Ginkgo Leaf, all contains in the sophora bud.
2. Radix Glycyrrhizae dextran (glucan) is α-D-pyrans dextran, and molecular weight 4000, is dissolved in water and dimethyl alum, is insoluble to the organic solvent such as alcohol, ketone.Structural formula is as follows:
α-D-Glc p-(1-[-4-α-D-Glc p-l-] 23-4)-α-D-Glc p
This polysaccharide white powder, without branch, and molecular weight, be a kind of new dextran, ultimate analysis proves nonnitrogenous.Liu Bingcan, Fang Jinian is at " separation and purification of Radix Glycyrrhizae dextran and chemical structure " (Acta Pharmaceutica Sinica 1991, report the Radix Glycyrrhizae obtained from the diluted alkaline extracting solution of Radix Glycyrrhizae (Glycyrrhiza uralensis Fisch) in 26 (9:672-675) and have poly-smart GBW, be through deproteinated, dialysis and precipitation, again through homogeneous components that column chromatography obtains.It is made up of single grape box residue, and molecular weight 4000, have passed through separation and purification, purity and molecule, measures, sugar component analysis, methylation reaction, Partial acid hydrolysis, and periodates is oxidized, Smith DeR, and CNMR measures, KI-I 2reaction etc.
Radix Glycyrrhizae dextran (glucan GBW) is the Radix Glycyrrhizae U of three kinds of neutral tool RE activity a, U b, U c, tool immunological stimulation, Radix Glycyrrhizae dextran energy enhancing body immunologic function, has activationa and proliferation effect to mouse spleen lymphocyte, shows and cause mitogen characteristic, have synergy with ConA.
3. licorice polysaccharide (GPS) is the one of extraction purification vegetable polysaccharides out from Radix Glycyrrhizae.Relative molecular weight is for being greater than 2000kDa, and not containing seminose, Sun Runguang etc. are shown by AFM Analysis, and licorice polysaccharide has 3 kinds of essential core structures at least: take glucose as main chain, the single glucose structure connected by α-(Isosorbide-5-Nitrae) key; Or form a main chain with 1,3-D-semi-lactosi, at the side chain that 6 bit strips of all galactose units of main chain have a L-arabinose residue connected by α-1,5-to form; Or form a main chain with 1,3-D-semi-lactosi, there is a side chain branch be made up of 1,6-galactose residue at 6 bit strips of main chain semi-lactosi unit.Therefore, this polysaccharide structures positively charged in acid condition, its hydroxyl there is stronger chemical reactivity.Licorice polysaccharide is primarily of glucose, pectinose and semi-lactosi composition, and the core texture feature of licorice polysaccharide is a main chain containing being made up of β-1,3-D-semi-lactosi.At the side chain that 6 bit strips of all galactose units of main chain have a L-arabinose-β-1,6-connected by α-1,5-or 1,3-galactose residue to form.Licorice polysaccharide has many biological activitys: have antitumor, radioprotective, antiviral, antiulcer agent, hypoglycemic, anti-ageing, immunomodulatory, anti-inflammatory and the effect such as antibacterial.Licorice polysaccharide, by strengthening immune cell function, impels the defense mechanism of body secretes immunoglobulin (Ig), cytokine, enhancing body immune defense, activating complement activity participation host, regulates the phagolysis of scavenger cell.Its immunoregulation effect, the entirety that antitumor, antivirus action is organic connections.Although start late to the research of licorice polysaccharide, the research of licorice polysaccharide is more and more subject to people's attention.
Extraction document about licorice polysaccharide is as follows: Huang Shen, Li Ping Qi, Li Hong etc. " research of macroporous resin adsorption desorb licorice polysaccharide effect " (time precious traditional Chinese medical science traditional Chinese medicines, 2007,18 (11): 2620-2621) water extraction is reported in, alcohol precipitation, then uses Saveg method isolating protein, then uses the best results of LSA-5B type macroporous resin; Wang Yuewu, Zhang Haibo, remaining water equality is at " in Glycyrrhiza uralensisFisch residue the separation and purification of polysaccharide and property analysis " (Nankai University's journal (natural science), 1999,32 (4): 36-38) report Glycyrrhiza uralensisFisch residue in and obtain pure polysaccharide through flooding, the element that discolors, removing protein, dialysis, DEAE-Cellulose (DE-32) and Sephadex G-75 gel filtration chromatography; Chen Fengqing, Cong Jianmin report licorice polysaccharide supersound extraction in " licorice polysaccharide ultrasonic extraction process optimizing research " (China brewages, 2009,1:138-140), and licorice polysaccharide content reaches 4.818%; Draw cutting edge of a knife or a sword in morning, Jiang Wei, Wang Xiaojing report solvent extraction, microwave extraction in " chemistry of licorice polysaccharide and pharmacological research " (Harbin University of Commerce's journal (natural science edition), 2004,20 (5): 515-518); Ma Wen, Xie Yinjun, Zhang Wansi report licorice polysaccharide decoloration process in " licorice polysaccharide activated carbon decolorizing technique " (spectrographic laboratory 2013,30 (4): 2965-2968); Wang Zhenqiang, Shen Sen, Fan Xin report licorice polysaccharide water extraction, alcohol precipitation flocculation process in " research of licorice polysaccharide extraction and purification process " (food research and development, 2012,33 (5): 41-44); Zhao Yunsheng, Yao Haihua, Wang Qilin etc. add water report Radix Glycyrrhizae ultrasonic degreasing in " Glycyrrhiza uralensis Fisch. polysaccharide extracting process optimizing research " (Liaoning Journal of Traditional Chinese Medicine, 2013,40 (3): 526-529) after supersound extraction, alcohol precipitation; Re Nakasi wood, Cong Yuanyuan, Tu Pengfei are in " separation and purification of glycyrrhiza inflate bat polysaccharide and physico-chemical property thereof " (West China pharmaceutical journal, 2008,23 (4): 448-450) water extraction is used after reporting Radix Glycyrrhizae alcohol degreasing in, alcohol precipitation, with Sevag method removing protein, obtains Crude polysaccharides, through dialysis, freeze-drying, dissolving, through DEAE-52 cellulose chromatography, then through SepharoseCL-6B and SephedexG-50 column chromatography, obtain single holosaccharide.Summary is got up, and is exactly degreasing, water extraction, alcohol precipitation, column chromatography, decolouring, the traditional technologys such as deproteinated.
4. Potenlini (Glycyrrhizic Acid), another name: glycyrrhizin, CAS No.1405-86-3, No. EINECS: 215-785-7, standard No. WS-10001-(HD-0506)-2002, molecular formula: C 42h 62o 16, molecular weight: 822.92, boiling point: 1050.9 DEG C of at 760mmHg, white crystalline powder, odorless, has special sweet taste.Structural formula is as follows:
Potenlini is pentacyclic triterpene oleanane type compound, is a kind of saponin(e, and natural Potenlini exists with α-GL and β-GL two kinds of configurations.The Potenlini preparation that market is applied mainly contains 18 alpha-liquorice acid two ammoniums and 8 β-monoammonium glycyrrhizinate.Structural difference is only at C 18h configuration on position is different, is respectively trans and cis.18 α-H and C 30on carboxyl not at same plane, and 18 β-H are in same plane with it.Due to steric effect, the former lipotropy is greater than the latter, and in α-GL structure, D/E ring is transconfiguration, therefore it is antiviral, anti-inflammatory action is much larger than β-GL.Be no matter α-GL or β is-GL, its aglycon glycyrrhetinic acid (GA) is more much better than than the activity of Potenlini, and di-ammonium salts can make GL under the effect of glycuronidase, generate GA, thus improves the ratio that GL is converted into GA.β-GL polarity is large, and at digestive tube absorption difference, α-GL does not form polymer, is easily absorbed.Potenlini is topmost activeconstituents in Radix Glycyrrhizae.Often be used as sweeting agent and make an addition to food, beverage, candy industry, can also natural pigment be made, for makeup and cigarette industry.Potenlini has following functions: antibechic of 1) reducing phlegm, anti-inflammatory, antiviral, and anti-respiratory system infection, for the treatment of the diseases such as pharyngitis, laryngitis, trachitis, bronchitis, conjunctivitis, asthma, cough; 2) anticancer, antiviral activity, inhibited to hiv virus, papilloma virus, be used for the treatment of cancer; 3) non-specific immunity regulating effect, for the treatment of eczema, skin pruritus; 4) protecting liver and detoxication, treatment chronic hepatitis, invigorating the spleen and regulating the stomach, alleviation stomach ulcer, modern study proves, the dominant mechanism of Potenlini removing toxic substances is its adsorption; 5) reducing blood-fat, atherosclerosis, can generate double salt or compound preparation with multiple alkaloid, microbiotic, amino acid etc., improves effect of drug bioavailability and reduction toxic side effect.Often be used as sweeting agent and make an addition to food, beverage, candy industry, can also natural pigment be made, for makeup and cigarette industry.1. apply in makeup: be a kind of natural surface active agent, there is very strong foaming power, there is emulsification, disperse, be incubated, moisten and send out, softening skin, crease-resistant, anti-sebum, go effect of freckle, anti-inflammatory anti-itch and washing decontamination, and there is scavenger cell oxyradical, delaying senility function.Existing domestic other factory have be widely used in shampoo, hair jelly, vanishing cream, facial mask, perfume (or spice) washes one's hair in the product such as liquid and toothpaste.2. the application in food: 1) be pure natural sweetener; 2) replace sucrose to use, not only can increase sugariness but also available it overcome the shortcoming such as fermentation, corruption caused because of multiplex sugar; 3) this product is to thermoae stable, the change such as nondiscoloration, decomposition.
Extraction document about Potenlini is as follows: Fu Boqiang, Liu Bo, Wang little Ru etc. " X D A-macroporous adsorbent resin is to the fractionation by adsorption of Potenlini and Radix Glycyrrhizae total flavones " (R&D of modern TCM with put into practice 2004,81 (supplementary issue): 45-49) in report absorption with macroporous adsorbent resin be separated, methanol wash column deviates from Potenlini, Potenlini yield 52%, content 65.5%; Wang Baijun, Xu Qingjuan report the ethanolic soln refluxing extraction containing ammonia in " ammonia ethanolic soln extracts Potenlini technical study from Radix Glycyrrhizae " (Liaoning chemical industry, 2009,38 (9): 620-622), and acid is heavy, obtains Potenlini; Zhang Hui, Tingting ZHAO, wear Liujiang etc. at " technical study of half bionical-Enzymatic Extraction Radix Glycyrrhizae acid " (Chinese Journal of Modern Applied Pharmacy, 2013,30 (9): 969-972) report Radix Glycyrrhizae in and add cellulase, extract as extracting solution using citrate-phosphate disodium hydrogen damping fluid respectively; State Rong, Li Jianjun, the bright grade of state " adopting Response Surface Method to optimize the ultrasonic extraction process of Potenlini in licorice piece " (Journal of Northwest Sci Tech University of Agriculture and Forestry (natural science edition), 2006,34 (9): 187-192) report Potenlini supersound extraction in, Potenlini extraction yield is 21.06%; Guo Wenjing, Zhang Shouqin, Wang Changzheng is in " superelevation platen press extracts the technical study of Potenlini from Radix Glycyrrhizae " (foodstuffs industry section, 2007, report 3:194-195) with water is Extraction solvent, ultra high pressure extraction, glycyrrhizic acid inclusion compound yield can reach 11.71%, and in crude product, glycyrrhizic acid content reaches 73.09%; Zhang Junsong, Zhang Changji, Pan Cunkuan report ethanol ultra high pressure extraction in " technical study of ultra high pressure extraction Potenlini " (Food science, 2009,30, (18): 75-79), and the extraction yield of Potenlini is respectively 14.61%; Wang Ying, Sun Jing, Zhang Dongjie are at " supercritical CO 2the technical study of extraction Potenlini " report supercritical CO in (food and machinery, 2006,22 (3): 34-36) 2extraction Potenlini; Li Ping Qi, Wang Hebin, Li Xueyu report the supersound extraction of Potenlini in " research of ultrasonic method combined extracting licoflavone and Potenlini " (Shandong journal of traditional Chinese medicine, 2005,24 (1): 38-40); Zhang Zesheng, Cui Cuicui, Sun Yu etc. " alcohol ammonia process extracts Potenlini technical study " (food research and development, 2009,30 (4): 101-103) microwave extraction Potenlini is reported in, the yield 12.9% of crude product, purity 31.3%, extraction yield 90.3%; Zeng Qihua " extracting the technical study of Potenlini and glycyrrhetinic acid from Radix Glycyrrhizae " (Zunyi Mormal college journal 2006,8 (1): 62-64) water extraction is reported in, acidifying, precipitation, D-101 type macroporous resin is best to Potenlini absorption property; Wu Qunying, Jiang Baiquan, white orchid jasmine " macroporous resin is to the adsorption and purification of Potenlini " (Jiangxi chemical industry, 2006, report D-101 resin absorption purified glycyrrhizic acid 3:99-101), adopt ethanol elution, the Potenlini purity of eluted product reaches 82.38%; Carry out heptan, Zhang Junliang, Yang Laishun etc. report and select D101 type macroporous resin, with 10% ethanol elution in " Amberlyst process refines Potenlini " (application chemical industry, 2006,35 (4): 316-317); Wang Yang, Wang Yuesheng, Yan Han " macroporous adsorbent resin is to the adsorption and desorption performance study of Potenlini " (CHINA JOURNAL OF CHINESE MATERIA MEDICA, 2006,31 (4): 295-297) report AB-8 in, D-101 is large to Potenlini adsorptive capacity, desorption efficiency is higher; Guo Yongyi, Jia Yanyan, Chen Hua is at " research of macroporous adsorbent resin separation and purification Potenlini " (Asia-Pacific traditional medicine, 2011,7 (11): 15-17) HPD-600 type macroporous resin is reported in the absorption of Potenlini, with 60% ethanolic soln wash-out, product purity can reach more than 95%; Wang Yahong, Zhou Duanwen is at " technical study of absorption with macroporous adsorbent resin purified glycyrrhizic acid " (Chinese patent medicine, 2006,28 (9): 1268-1271) report D-101 type macroporous adsorbent resin in the absorption of Potenlini, product purity can reach 95.109; Sun Chen, Liu Wenju, Zhang Bin is at " research of nonionogenic tenside aqueous two-phase extraction Potenlini " (food science and technology, 2014,39 (7): 237-241) Potenlini is reported in AEO-7/ sodium phosphate double-aqueous phase system aqueous two-phase extraction, percentage extraction can reach 99.30%, and its partition ratio reaches 317.90.Fu Yujie, Zhao Wenhao, Hou Chunlian are in " Vacuum-Cavitated Technology for Glycyrrhizic Acid Extraction " (applied chemistry, 2005,22 (12): 1369-1371) report negative pressure cavitation in and extract Potenlini, extract yield is 1.2 times of ultrasonic extraction, 1.7 times of soxhlet extraction; Li Ping Qi, Wang Hebin, Li Hong etc. are in " screening of licoflavone and Potenlini combined extracting solvent systems " (modern food science and technology, 2005,21 (1): 6-8) report in and select lime slurry, alkali aqueous solution, mixed alkali liquor, BWE mixed solvent to be Extraction solvent, best with BWE mixed solvent; Pan Guoshi, leaf literary talent is at " Potenlini (GA) production technique " (basic unit's J Chinese, 2000,14 (5): 8-9) solvent method (decocting method, infusion method, percolation) solvent-extraction process is reported in, Amberlyst process; Cui Yongming, remaining Longjiang, Ao Mingzhang etc. report supersound extraction Potenlini in " extraction of Potenlini and bacteriostatic activity research thereof " (research and development of natural products, 2006,18:428-431); Li Jianjun, state Rong, Mo Xiaoyan reports supersound extraction Potenlini in " optimizing research of Technology for Extracting Glycyrrhizic Acid from Liquorice " (Food science, 2006,27 (12): 326-330); Ling Xiuju, multifarious pole, Wu Zhengqi " Technology for Extracting Glycyrrhizic Acid from Liquorice research " (Hubei University Of Technology's journal, 2006,21 (2): 12-13) report weak ammonia extraction Potenlini in, improve 15.44%, 15.90% than traditional alkali extraction and acid precipitation technique; Xu Jianjun, horse Qinghe, Li Haiqi etc. report the factor affecting glycyrrhizic acid inclusion compound and prepare in " Technology for Extracting Glycyrrhizic Acid from Liquorice research " (Xinjiang Chinese materia medica, 2013,31 (1): 40-43); She Jinming, Liu has gesture, Xie Xianzhen etc. " Potenlini Extractive technology process optimization " (Hunan Technology College's journal (natural science edition), 2010,23 (3): 55-59) report ammoniacal liquor extraction using alcohol in, extraction efficiency can reach 9.86%, and treating process selects D-101 type macroporous resin, ethanol is as elutriant, and stripping liquid concentrates Potenlini high purity 89.6% after decolouring; History peak, Zhou Baohua, Chen Xuefu report the best decoloration process of Potenlini in " research of Potenlini decoloration process " (foodstuffs industry and science and technology, 2011,32 (9): 319-321); Cui Xingyu, Cui Jian, Chen Shuwei is at " research of Potenlini new preparation process " (Institutes Of Technology Of Taiyuan's journal, 2001,32 (3): 271-273) report the extraction using alcohol containing ammonia in, AB-8 macroporous resin adsorption, gac decolours in Glacial acetic acid, recrystallization, obtains the colourless Potenlini product that purity is high; You Xinyong, Wang Lei, Sun Yanwei etc. report extraction using alcohol in " the extracting factor optimization of glycyrrhizin " (foodstuffs industry, 2014,35 (5): 85-97), and the extraction yield of glycyrrhizin is 27.2%; Wang Qiaoe, Ren Hong, Cao Xueli reports multi-stage countercurrent and extracts Potenlini in " the counterflow extraction technique research of Radix Glycyrrhizae acid " (Beijing Technology and Business University's journal (natural science edition), 2011,29 (1): 33-36); Du Wenbin, Zhang Hong report with the extraction using alcohol containing ammonia in " Study on extraction of Radix Glycyrrhizae acid " (Agriculture of Anhui science, 2008,36 (25): 10945-10946), the extraction yield 10.85% of Potenlini; Cao Liping, Pu little Hong, Liu Meiyou etc. report ammoniacal liquor microwave extraction Potenlini in " the optimal extraction technology research of Radix Glycyrrhizae acid " (Chemical Industry in Guangzhou, 2009,37 (7): 94-96), and extraction yield is 12.80%; Wang Shan, Huang Yi, Cao Lei etc. report ammoniacal liquor dilute alcohol solution and extract in " extraction of Radix Glycyrrhizae acid and measuring method summary " (chemical science and technology, 2010,18 (1): 76-80); Wang Qiaoe, Shen Jincan, Yu Wenjia etc. report microwave extraction Potenlini in " microwave extracting of Radix Glycyrrhizae acid " (herbal medicine, 2003,34 (5): 407-409); Report the alcohol reflux Potenlini containing ammonia in Zhang Juan, Yang Zhonglin, Li Ping " Study on Preparation of Radix Glycyrrhizae acid " (Chinese patent medicine, 2007,29 (5): 686-689), the rate of transform is 92.55; Report ammonia second in Zhao Lei, Shi Qingzhi, Tang Xing " the extraction and purification process research of Radix Glycyrrhizae acid and liquirtin " (China Dispensary, 2009,20 (6): 426-428) to extract, the Potenlini purity after purifying is higher than 85%; Li Shanjia, Wang Yuli, Yang Mingjun etc. are in " extracting the novel process research of Potenlini in Radix Glycyrrhizae " (Gansu science journal, 2010,22 (2): 53-57) reporting ultrasound-enhanced extraction yield in is 12.20%, and microwave radiation exaraction yield is 10.77%; Zhu Zhongjia, Xiong Fuliang, Zhang Xueqiong etc. report Radix Glycyrrhizae total saponins boiling, HPD-300 type resin absorption, wash-out in " the extraction and purification process research of Radix Glycyrrhizae total saponins " (Chinese patent medicine, 2011,33 (2): 341-343); Sun Xiaotao, Lee's a kind of apple, Wang Changtao is in " high performance liquid chromatography evaluates macroporous resin purification Potenlini technique " (Food science, 2013,34 (6): 93-97) report by the comparison to DA201-C and AB-8 two profiles macroporous resin Static Adsorption and desorb in, select AB-8 type macroporous resin to carry out purifying to Potenlini, eluant ethanol, Potenlini purity 52.3% after purifying, after recrystallization, purity is 76.0%; Su Yantao, Han Li, " technical study of intermittent foam separation and Extraction Radix Glycyrrhizae the acid " (herbal medicine such as horse swan goose, 2007,38 (3): 365-368) optimum process condition that intermittent foam is separated glycyrrhizin is reported in, the rate of recovery of Potenlini is 91.9%, Potenlini massfraction 32.3%; Yang Fu, Min Zhiling, Chen Weichu etc. report supersound extraction Potenlini in " electrostatic field works in coordination with the research of supersound extraction Radix Glycyrrhizae acid " (applied acoustics, 2014,33 (2): 160-166), and extraction yield is 11.02%.Qiao Wuzhong, Wang Yanhui, Li Mei powder etc. are at " utilizing the research of Macroporous Adsorption Resin Potenlini " (Chinese patent medicine, 2006,28 (6): 794-796) report the technique of refining Potenlini with X-5 in, with ethanol elution, Potenlini purity can reach 95%; Fu Boqiang, Li Huan, Liu Bo etc. are in " purifying of Glycyrrhizin by Foam Fractionation and enrichment " (R&D of modern TCM and practice, 2004,18 (supplementary issue): 57-61) in report foam separation Potenlini, investigated concentration and pH value thereof, nitrogen flow, column dimensions to the HP LC spectral purity of concentration ratio, mass recovery, foam solution and the impact of foam separation time.Li Yuhui, Xu Deping, Zhang Lianfu is at " extracting the technical study of glabridin and Potenlini in glycyrrhiza glabra " (research and development of natural products simultaneously, 2011,23 (3): 547-550) report in and extract Potenlini with containing ethanol containing ammonia, the yield of Potenlini is 5.08% ± 0.03%; Zhang Qiang, Yang Zhenhua reports microwave radiation exaraction Potenlini in " technique of microwave radiation exaraction Potenlini " (food research and development, 2010,31 (4): 38-40), and Potenlini yield is 12.59%; Feng Fusheng, Xuan Chunsheng, Chen Shuwei etc. report with AB-8 resin absorption in " polymeric adsorbent AB-8 is to the absorption property of Potenlini and the application in extraction purification thereof " (research and development of natural products, 10 (1): 60-64), 10% ethanol elution; Li Chunying, Li Xiaojuan, Yang Leis etc. are at " Responds Surface Methodology optimizes Potenlini and licoflavone combined extraction technology " (Heilongjiang University's natural science journal, 2009,26 (3): 390-395) the alcohol concn refluxing extraction Potenlini containing sodium hydroxide is reported in, Potenlini yield 5.73%; Chen Shuanhua reports orthogonal experiment and optimizes Potenlini extraction in " orthogonal experiment optimizes the extraction process of Potenlini " (the bright traditional Chinese medical science, 2010,25 (6): 954-9560), and extraction yield is up to 3.13%; Long Jiapeng, Chen Zhenbin, Liu Xiaojiao etc. are at " the combined-enzyme method extraction process of the preferred Potenlini of orthogonal test " (China Dispensary, 2014,25 (7): 626-629) report licorice powder in and carry out enzymolysis, ammoniacal liquor alcohol steep, Potenlini extraction yield can reach 85.02%; Tao Weiwei, the golden storehouse for grain, etc. of section, Yang Nianyun etc. are at " research of Glycyrrhiza uralensis Fisch. saponin component " (herbal medicine, 2013,44 (12): 1552-1557) Radix Glycyrrhizae is reported in extraction using alcohol, by D-101 macroporous resin adsorption wash-out, 50% ethanol elution, obtains Radix Glycyrrhizae total saponins extract; You Xinyong, Wang Lei, Sun Yanwei etc. report extraction using alcohol in " the extracting factor optimization of glycyrrhizin " (foodstuffs industry, 2014,35 (5): 95-97), and the extraction yield of glycyrrhizin is 27.2%.
5. licoflavone (Glycyrrhizic Flavone) is the general name of 150 kinds of compounds such as liquirtin, 4',7-Dihydroxyflavanone and Liquiritigenin, isoliquiritigenin, glabridin, licoflavone is red-brown, water insoluble and various grease, is dissolved in ethanol, propylene glycol, glycerine and part organic solvent.Have and have multiple efficacies: 1) it has the effect of anti-inflammatory, anti-allergic, left cicatrical or non-cicatrical pigmentation after can alleviating skin damage, also have restraint of tyrosinase activity, remove oxygen order by base, suppression dopachrome change and the oxidasic activity of DHICA, licoflavone takes off in spot liquid at compound skin-whitening, tetter such as treatment " dark spot ", contact dermatitis, ordinary base sore, dermatitis, freckle, pigmentation etc. is a kind of quick, efficient, green whitening cosmetics additive; 2) adrenocortical hormone sample effect, has the sample effect of salt hydrocortisone and the effect of glucocorticosteroid sterol sample; 3) anti-experiment peptide ulceration, spasmolysis, strengthens the antagonistic action effect of HIV (human immunodeficiency virus) (HIV); Japanese scholars TaKagi reports, a kind of flavones ingredient is obtained by after China's northeast Radix Glycyrrhizae removing glycyrrhizin, called after FM100 (commodity are called Aspallon) has the effect of anti-experiment peptide ulceration, anti-inflammatory, strengthens the antagonistic action effect of HIV (human immunodeficiency virus) (HIV).Japanese's professor's Tian Tuonan report difficult to understand, in Radix Glycyrrhizae, the propagation of three kinds of flavones to hiv virus (HIV) has rejection ability; 4) suppress capillary permeability, have stronger restraining effect to platelet aggregation, arrhythmia, anti-inflammatory, antibechic, to eliminate the phlegm, the functions such as delaying human body caducity; 5) licoflavone has treatment diabetes, depression.
Extraction document about Radix Glycyrrhizae total flavones is as follows: Han Bo, Chen Wen, Jing Wenjuan etc. are at " AB-8 macroporous adsorbent resin is to the absorption of Radix Glycyrrhizae total flavones " (Nanfang Medical Univ's journal, 2007,27 (3): 265-267) absorption behavior of AB-8 resin to licoflavone is reported in, the ethanol of 60%; Xu Qingping, Zhu Guang existence " XAD-16 macroporous resin is separated the research of licoflavone " (He'nan University of Technology's journal (natural science edition), 2010,31 (1): 49-52) report the technical study that macroporous resin XAD-16 is separated licoflavone in, determine best separation condition; Li Hong, Li Ping Qi, Liu Hong etc. report XDA-1 type macroporous adsorbent resin in " XDA-1 type resin is to the research of licoflavone absorption-desorption effect " (Chinese patent medicine, 2007,29 (6): 830-833) all can reach more than 90% to licoflavone adsorption rate and desorption efficiency." macroporous resin adsorption desorb licoflavone Effect disquisition " (Chinese Chinese materia medica information magazine, 2013,20 (9): 49-51) condition that HPD300 resin absorption is separated licoflavone is reported in, with ethanol elution, elution rate 1.5BV/h, eluting agent is 3BV; Yang Fei, Li Shuhong is at " macroporous resin column is separated the research of total flavones in Radix Glycyrrhizae " (food and pharmaceutical, 2013,15 (6): 427-428) report the leaching of Radix Glycyrrhizae ethanol in filter, concentrated evaporate to dryness, heating water dissolves, pH is adjusted with milk of lime, filtrate merged, AB-8 type macroporous resin is 68.0% to the adsorption rate of Radix Glycyrrhizae total flavones, and desorption efficiency is 83.5%; Yi Yunhong, Wu Gongqing, Zeng Fulan etc. are in " research of purification with macroreticular resin liquorice flavonoids compound " (Agriculture of Anhui science, 2011,39 (14): 8364-8366) optimised process of ADS-7 type purification with macroreticular resin licoflavone is reported in, flavones powder flavones content after purifying is 47.1%, and refining rate is 211.2%; Report the optimised process of microwave extraction licoflavone in " comparative studies of combined-enzyme method and multistage microwave amplifier licoflavone " (Hubei Journal of Traditional Chinese Medicine, 2004,26 (6): 52-53), extraction yield can reach 16.6%; Wang Yunyun, Li Li, Li Xiangyu etc. report the optimised process that combined-enzyme method extracts free total flavones in glycyrrhiza residue in " combined-enzyme method extracts total flavones in glycyrrhiza residue " (chemistry and biotechnology, 2008,25 (8): 49-51); Xu Ying, Liu Jia etc. report licoflavone optimum extraction condition in " in licorice slag licoflavone Study on extraction " (Chinese experimental pharmacology of traditional Chinese medical formulae magazine, 2010,16 (15): 15-19); Liu Xiaofeng, Xiang Yanhong, Zhang Baigang etc. report licoflavone optimum extraction condition in " Study on extraction of licoflavone " (Agriculture of Anhui science, 2009,37 (6): 2542-2543); Liu Jia, Ji Fang, Sun Taoli etc. are at " licoflavone separation purifying technique " (Chinese experimental pharmacology of traditional Chinese medical formulae magazine, 2012,18 (10): 49-51) report the optimal separation purifying process of licoflavone in, the content of licoflavone is respectively 5.177,4.998,5.012g/L; Wang Hebin, Zhou Zhongbo, Luo Feng etc. " licoflavone extracting method and anti-oxidant activity research " (time precious traditional Chinese medical science traditional Chinese medicines, 2008,19 (9): 2106-212107) report in and adopt conventional method, ultrasonic wave, microwave, microwave and ultrasonic wave synergic extraction 4 kinds of Different Extraction Method to extract licoflavone, the licoflavone content of 4 kinds of method extractions is respectively 1.78%, 1.85%, 1.92%, 2.04%; Zhang Zhi east, Tang Qiyong, cogongrass armies etc. are at " licoflavone Study on Extraction Method progress " (Xinjiang Agricultural Sciences, 2006,43 (6): 517-519) report licoflavone in and mainly comprise water extraction, organic solvent extraction, microwave method, supersonic method, supercritical extraction, macroreticular resin absorbing method and enzymolysis process; Li Hong, Li Ping Qi, Liu Hong etc. report the top condition of glycyrrhiza residue ethanol ultrasonic extraction in " in glycyrrhiza residue the extraction of flavones and polysaccharide and assay " (Food Additives Used in China, 2006,193-196), and the content of licoflavone is 2.69%; Lv Ziming, Chen Kai, Yu Xianghong etc. are at " the purification with macroreticular resin optimal process of Radix Glycyrrhizae total flavones " (Chinese experimental pharmacology of traditional Chinese medical formulae magazine, 2012,18 (11): 24-27) report the purification effect of AB-8 type macroporous adsorbent resin to Radix Glycyrrhizae total flavones in best, Radix Glycyrrhizae total flavones purity is 38%; Chang Jing, Zhou Yajing, rock-block field swallow etc. reports the optimum extraction process of Radix Glycyrrhizae total flavones in " Radix Glycyrrhizae total flavones optimal extraction technology " (Asia-Pacific traditional medicine, 2014,10 (8): 24-25); " research of Radix Glycyrrhizae total flavones material composition extraction and purification process " (Chinese Medicine Leader, 2010,7 (26): 54-56) report in and adopt refluxing extraction licoflavone, by resin purification technique, the pure Radix Glycyrrhizae total flavones of the preparation such as organic reagent extraction, purity is 90.12%; Yang Shaojuan, Zhao Haiyan, horse Yongping etc. are at " research of polyamide resin chromatography purifying liquorice flavones " (guangdong agricultural science, 2011, the top condition of polyamide resin chromatography purifying liquorice flavones is reported 16:85-87), flavones content can be made after twice upper prop to be elevated to 49.75% by 6.42% of crude product, and purity improves 6.75 times; Field celebrating comes, Xie Yuchun, Zhang Bo etc. are at " Separation of Hydrophilic Licorice Flavonoid by Solvent Extraction Method " (process engineering journal, 2007,7 (3): 496-500) report in trialkyl phosphine petroleum ether solution for extracted organic phase, by extraction water dissolubility licoflavone in licorice extract; Yang Hui, Jiang Baiquan, white orchid jasmine reports the optimum extraction process of Radix Glycyrrhizae total flavones in " Extracting Flavonoids from Waste Residue of Licorice by Solvent Method " (Jiangxi chemical industry, 2006,3:90-92); Li Yanbin, Zhang Qin, Tao Chengyu etc. are at " food research and development " (2010,31 (9): 156-158) yield that all effectively can improve licoflavone through fermentable process is reported in, wherein flavones yield difference 0.89%, 0.87% after whiterot fungi, cellulose-decomposing bacterium fermentation, whiterot fungi and cellulose-decomposing bacterium mixed fermentation process, flavones yield reaches 1.32%; Deng Yinmei, Cui Yongming, Li Wei etc. are at " response phase method optimizes homogenate extraction total Flavonoids from Glycyrrhiza Leaves technical study " (chemistry and biotechnology, 2008,25 (9): 44-47) total Flavonoids from Glycyrrhiza Leaves optimum extraction process is reported in, the extraction rate reached 2.91% of total flavones under these processing condition; Ma Shuyan, it is diligent that wood closes Bu Liabuli, Ji Xiaojuan is at " Hydrolysis kinetics of Xinjiang Radix Glycyrrhizae total flavones and assay " (northwest pharmaceutical journal, 2008,23 (5): 276-278) total flavones in ultrasonic method extraction glycyrrhiza inflate bat and glycyrrhiza glabra is reported in, refine with macroporous resin, in glycyrrhiza inflate bat and glycyrrhiza glabra crude extract, general flavone content is respectively 3.8% and 3.5%, and after refining, general flavone content reaches 35.4% and 33.2% respectively; Report total flavones extraction conditions in Radix Glycyrrhizae in Guo Yanru, Lin Jie the technical study of total flavones " in the alcohol steep Radix Glycyrrhizae " (herbal medicine, 2013, (24): 158-161), yield is 1.279%.After response surface optimization, yield improves 0.049%, and the best yield of flavones is 1.328% under this condition; Wang Qing, Miao Wenjuan, Xiang Cheng etc. are at the research of flavonoids " in the Glycyrrhiza uralensis Fisch. " (herbal medicine, 2014,45 (1): 31-35) report Glycyrrhiza uralensis Fisch. in extract with alcohol heating reflux respectively, concentrating under reduced pressure, obtains medicinal extract, extraction, is separated through silica gel column chromatography; Han Yanan, Cheng Xinyu, Hou Junling etc. are " technique of macroporous resin purification Radix Glycyrrhizae over-ground part total flavones " (Jilin old docter of TCM, 2014,34 (1): 82-85) report HPD-BJQH macroporous resin purification Radix Glycyrrhizae total flavones optimum process in, after purifying, the purity of total flavones rises to 36.11% from original 9.68%; The flavones reported in Radix Glycyrrhizae in the research of flavones ingredient " in the Radix Glycyrrhizae " (northern pharmacy, 2013,10 (7): 6-10) such as Duan Zhitao, Gao Ying, Li Weimin is broadly divided into water-soluble flavone and fat-soluble flavones.The people such as Xing Guoxiu provide structure and the title of more than 150 liquorice flavonoids compound in article.Radix Glycyrrhizae rhizome is used extraction using alcohol by Shen Liming respectively, through organic solvent extraction after extract reclaims, utilizes silicagel column, ODS, preparative HPLC to be separated, obtains flavonoid compound.Xinjiang licorice slag is added extraction using alcohol by Yang Lin etc., concentrated, extraction, and concentrated, obtain medicinal extract, medicinal extract is through silica gel column chromatography.The extraction using alcohol such as Yang Li, concentrated, organic solvent extraction thing used respectively by medicinal extract, after silica gel isochromatic spectrum post is separated, obtain flavonoid compound.Jia Shishan etc. are by Glycyrrhiza uralensis Fisch. leaf methanol leakage, and extraction, silica gel on aqueous fraction, wash-out, extraction after elutriant is concentrated, through polymeric amide chromatographic separation.Ma Hongyan etc. determine the liquorice dregs total flavone extracting process condition optimized.Jiang Honghong etc. study the optimal extract process of Radix Glycyrrhizae total flavones.Yu Pengfei etc. have inquired into optimum extraction process, optimised process.Huang Mingjin etc. study optimum extraction process.The bright ultrasonic technique that adopts such as strange of Lee carries out combined extracting to flavones in Radix Glycyrrhizae and Potenlini.Under Liu Hong etc. have studied ultrasound condition, difference extraction time is on the impact of licoflavone extraction yield.King Ying Qiang etc. compares water extraction, alcohol reflux and supersound extraction three kinds of extracting method.The research such as Shi Zhongfeng shows, after adopting extraction using alcohol, directly cross AB-8 macroporous resin resin column, collect alcohol elution, concentrating under reduced pressure, vacuum-drying obtain Radix Glycyrrhizae total flavones extract, and Radix Glycyrrhizae total flavones yield is more than 3.4%.Lv Ziming etc. are with total flavones adsorptive capacity and desorption efficiency for inspection target, and screen 12 kinds of dissimilar resins, the purification effect of AB-8 type macroporous adsorbent resin to Radix Glycyrrhizae total flavones is best, and Radix Glycyrrhizae total flavones purity is 38%.
6. glabridin (Glabridin) another name: light Radix Glycyrrhizae pyridine, reputation name: whitening gold, CASNo.59870-68-7, code: 18251924383.Molecular formula: C 20h 20o 4, molecular weight: 324.3704, density: 1.257g/cm 3, fusing point: 156-158 DEG C, structural formula is as follows:
Derive from Glycyrrhiza glandulifera Waldst, this product low levels is brown ceramic powder, and high-content is colorless plate crystal.Water insoluble, be dissolved in the organic solvents such as 1,3 butylene glycol, propylene glycol, ethanol completely.Glabridin is one of Main Flavonoids constituents in glycyrrhiza glabra.1) glabridin demonstrates very strong Green Tea Extract oxygenizement, obviously can suppress interior free yl, with from by Free radicals injury, prevent and treat the atherosclerosis relevant with free-radical oxidn, cell aging etc.; 2) glabridin has certain reducing blood-fat and hypotensive effect; 3) effect that glabridin has outstanding anti-inflammatory, antibacterial, anti-oxidant and anti-melanochrome is formed, prevents pachylosis, is one of the whitening composition of current good effect, complete function.It is skin-lightening cosmetic additive that the cosmetics company of MARUZEN, Lancome, Dior, SoniaRykiel, Chanel and Korea S releases glabridin, whitening cream can be made, China scientific worker prepares glabridin liposome, improve skin-whitening and speckle eliminating effect, in the world, makeup circle are described as " whitening gold ".Sell 40% the most general glabridin in the market, main component is licoflavone, is brown or white powder.U.S. Sabinsa is one of manufacturer of comparatively early production glabridin in the world, is extract from Glycyrrhiza glandulifera Waldst.Can by chemosynthesis, but main employing is extracted from the root of Glycyrrhiza glabra L. (syn.Liquiritae officinalis Moench., Fani.Fabaccae) at present; 4) Italy's research also confirms that Glabridin has the effect of depress appetite, but it can reduce fat and does not lose weight; 5) there is bibliographical information Radix Glycyrrhizae to can be used for reducing the cortin of infectious dermatosis, the effect of steroid can be strengthened.
Extraction bibliographical information about glabridin is as follows: Fan Li, Duan Wenjuan, Wang Xiao etc. are at " ultra-high voltage extracts the research of Potenlini and glabridin in glycyrrhiza glabra " (food science and technology simultaneously, 2013,38 (12): 214-218) ultra-high voltage extraction using alcohol is reported in, the extraction yield 1.05mg/g of glabridin; Chen Junming, Wang Ping, Wang Xuefeng etc. are at the research of glabridin extraction process " in the glycyrrhiza residue " (Xinjiang Chinese materia medica, 2014,32 (4): 63-66) report glycyrrhiza residue extracting in water in, be concentrated into syrupy shape, dissolve with methanol, suction filtration, collects filtrate.Filtrate charcoal absorption flavones, washing, collects washings, Celite resin absorption, glabridin content more than 50%; It is diligent that wood closes Bu Liabuli, Re Nakasi wood, and Ma Shuyan etc. report glycyrrhiza glabra acetone extraction in " in Radix Glycyrrhizae the extraction of glabridin and anti-oxidant activity research " (research and development of natural products, 2007,19:675-677), use Al 2o 3column chromatography for separation, adopts E-test to carry out wash-out, obtains Glabridin sterling; Fan Yuhan, Wang Yinjun, Zhang Aijuns etc. are at " optimization of glabridin extraction process and separation " (Ningxia Medical University's journal, 2014,36 (1): 111-114) report glycyrrhiza glabra alcohol reflux in, utilize silica gel column chromatography, purity reaches 81.24%; Ma Shuyan, it is diligent that wood closes Bu Liabuli, Bahaerguli Ka Haer etc. are at " preparation technology of glycyrrhiza glabra osajin composition glabridin " (Xinjiang Medicine University's journal, 2007,30 (7): 692-694) glycyrrhiza glabra acetone extraction is reported in, with alumina column chromatography; Guo Ruili, Li Xueqin, Zhang Xiaopeng the microwave radiation exaraction of glabridin " in the glycyrrhiza glabra research " (time precious traditional Chinese medical science traditional Chinese medicines, 2011,22 (8): 1817-1819) report microwave extraction glabridin in, glabridin yield is 0.256%; Li Xueqin, Guo Ruili reports ionic liquid and makes extraction agent in " hydrophobic ionic liquid extraction glabridin " (chemical research and application, 2013,35 (2): 169-172), extract glabridin extracting solution, the percentage extraction of glabridin reaches 85.49%; It is that solvent supersonic extracts that Xu Yan, Zhang Qingxi, Yuan Qipeng etc. report with ethyl acetate in " technical study of glabridin " (food science and technology, 2009,34 (12): 235-239), and extraction yield is 0.269%; Fan Jinling, Zhang Lin, red legends etc. report methanol extraction in " research of glabridin technique is extracted in response phase method optimization " (Chinese food journal, 2012,12 (4): 72-76), and glabridin yield predictor is 0.52%; Sai Limanha get Er, Li Hongzhi, wood closes the diligent grade of Bu Liabuli at " preparation process amelioration of Xinjiang licoflavone constituents glabridin " (Asia-Pacific traditional medicine, 2008,4 (9): 27-28) report licorice powder extraction using alcohol in, extract obtains Glabridin sterling with silica gel column chromatography column chromatography; Fan Yuhan, Wang Yinjun, Zhang Aijun etc. report extraction using alcohol, filtering with microporous membrane in " optimization of glabridin extraction process and separation " (Ningxia Medical University's journal, 2014,36 (1): 111-114), are concentrated into paste.Add water in medicinal extract, hold over night, centrifugal, collecting precipitation thing is dry.Utilize silica gel column chromatography; Chen Junming, Wang Ping, Wang Xuefeng etc. are at the research of glabridin extraction process " in the glycyrrhiza residue " (Xinjiang Chinese materia medica, 2014,32 (4): 63-66) report licorice slag in extract, concentrated, charcoal absorption, wash-out, obtains licoricidin content more than 50%.
7. liquirtin (Liquiritin liquiritin), molecular formula C 21h 22o 9, molecular weight 418.39, chemical name: (S)-7-Hydroxy-2-[4-((2S, 3R, 4S, 5S, 6R)-3,4,5-trihydroxy-6-hydroxymethyltetrahydropyran-2-yloxy) phenyl] chroman-4-one.CAS No.551-15-5, fusing point: 212 ~ 213.Structural formula is as follows:
Liquirtin belongs to triterpene compound, is activeconstituents important in liquorice flavonoids compound, and the height Chang Zuowei of its content evaluates the important indicator of Radix Glycyrrhizae quality, and in Radix Glycyrrhizae, content can reach 6-14%.The sugariness of liquirtin is about 177 times of sucrose, and its sweet taste is slowly lasting, and arranging in pairs or groups with sucrose and citric acid uses sweet taste better, has again very strong flavouring usefulness.Therefore, liquirtin, as important foodstuff additive, is widely used in milk-product, chocolate, jam product, pickled food, egg-products and beverage.In addition, liquirtin has well anti-oxidant, anti-inflammatory, removing toxic substances, adjustment body immunity, antiulcer agent, invigorate the spleen and benefit qi, detoxify protect the liver, moisten the lung and relieve the cough, the pharmacologically active such as coordinating the actions of various ingredients in a prescription, receive the extensive concern of domestic and international investigator.Liquirtin in Radix Glycyrrhizae is generally present in Radix Glycyrrhizae with the form of the inorganic salt such as liquirtin monopotassium salt.
Document about liquirtin and isoliquiritin is as follows: Zheng Yunfeng, Yang Jinqiang, Wei Juanhua etc. are in " multi objective measures and optimizes the technique that polyamide resin is separated liquirtin " (CHINA JOURNAL OF CHINESE MATERIA MEDICA will, 2013,38 (22): 3902-3906) report Radix Glycyrrhizae in and add alcohol reflux, recycling design, lyophilize extract, adsorbs with polyamide resin; Supersound extraction is reported in " technical study of ultrasonic-assisted extraction Radix Glycyrrhizae glycosides " (food science and technology industry, 2009,8:256-258); Su Guolin, Liu Gang, Liu Yuchen etc. report the technique that Ma Wen etc. have studied ultrasonic method and multistage microwave amplifier liquirtin in " extracting and purifying method of liquirtin and Advance on Pharmacological Activities " (contemporary Chinese Chinese medicine, 2011,13 (10): 48-51).He Mingzhen etc. have studied the preparation technology of liquirtin and isoliquiritin, and Radix Glycyrrhizae is added alcohol reflux, reclaim ethanol and obtain medicinal extract.Medicinal extract is through macroporous resin AB-8 column chromatography, and gradient elution, gel filtration chromatography is separated, and obtains isoliquiritin, through the preparation of preparation liquid phase, obtains liquirtin.Liang Xinmiao etc. have invented a kind of method preparing liquirtin, Radix Glycyrrhizae soak by water reconcentration are obtained medicinal extract, alcohol precipitation, and membrane sepn instrument is separated, and are separated through X-5 macroporous adsorbent resin, collect elutriant concentrated frozen and are drying to obtain liquirtin.Wang Zhenhui, Li Chaosheng, Wang Haisen etc. are at " liquirtin extraction process optimization of orthogonal test " (Chinese experimental pharmacology of traditional Chinese medical formulae magazine, 2011,17 (10): 30-31) liquirtin optimum extraction condition; He Mingzhen, Huang little Ping, Feng Yulin etc. report Radix Glycyrrhizae and add alcohol reflux in " preparation of Radix Glycyrrhizae glycosides, isoliquiritin reference substance and qualification " (Jiangxi College of Traditional Chinese Medicine journal, 2009,21 (5): 29-30), reclaim ethanol and obtain medicinal extract, medicinal extract, through macroporous resin AB-8 column chromatography, takes off, through polyamide column chromatography with ethanol-water system gradient Xian, gel filtration chromatography is separated, and is prepared into liquirtin and isoliquiritin through preparative liquid phase; The preparation technology of liquirtin extracting solution is reported in Zhao Lei, Shi Qingzhi, Tang Xing " the extraction and purification process research of Radix Glycyrrhizae acid and liquirtin " (China Dispensary, 2009,20 (6): 426-428); Zhao Haijiao, Ren Quanxia, Fan Yuhan etc. are at " character utilizing flavanone and cinnamophenone mutually to transform prepares isoliquiritin " (food science and technology, 2011,36 (10): 210-213) report liquirtin in and be converted into isoliquiritin technique, utilize flavanone can be converted into the character of cinnamophenone in the basic conditions, liquirtin is converted into isoliquiritin; The red sudden strain of a muscle of fish, Wu Shaojie, the mediate grade of Jin Feng is at " resin method extracts the research of Radix Glycyrrhizae glycosides " (food and fermentation industries, 25 (1): 40-43) Radix Glycyrrhizae water logging is reported in, filter, distillation, the step yield such as precipitation are more than 9%, crude product obtains liquirtin sterling through D 101 resin and HP20 plastic resin treatment again, and yield is respectively 60% and 86%; Cong Jingxiang, Wang Shaoyan, Zhu Lei etc. report the extraction of liquirtin and isoliquiritigenin in the optimization of liquirtin and isoliquiritigenin extraction process " under the acidic conditions " (Agriculture of Anhui science, 2011,39 (16): 9582-9584); " extraction and isolation of glycyrrhizin and liquirtin and Structural Identification " (foodstuffs industry science and technology, 2010,31 (9): 127-130) Glycyrrhiza uralensis Fisch. ethanol room temperature immersion, filtrate merges, underpressure distillation obtains concentrated solution, crosses post AB-8 resin, ethanol gradient elution, through TLC (thin layer chromatography) qualification, the elutriant that Rf is identical merges; Su Guolin, Liu Gang, the extracting and purifying method that Liu Yuchen etc. report liquirtin in " extracting and purifying method of liquirtin and Advance on Pharmacological Activities " (contemporary Chinese Chinese medicine, 2011,13 (10): 48-50) is a lot, organic solvent extraction, column chromatography purification, microwave, supersound extraction, macroporous resin, simulated moving bed chromatography method purifying etc., Cong Jingxiang etc. adopt simulated moving bed chromatography technology purification liquirtin first.
8. isoliquiritin (Isoliquiritoside), CAS No.5041-81-6, molecular formula: C 21h 22o 9, molecular weight: 418.3.This product is dicotyledons pulse family Leguminosae Radix Glycyrrhizae Glycyrrhiza uralensisFisch., glycyrrhiza inflate bat G.infiata Bat., or the root and rhizome of glycyrrhiza glabra G.glabra L. extracts, yellow powder, fusing point: 187-189.Structural formula is as follows:
Isoliquiritin is an important flavonoid compound in Radix Glycyrrhizae, correlative study shows, isoliquiritin has the pharmacological action such as activity, the active inhibition tumor cell propagation of change topoisomerase II of antiulcer agent, anti-inflammatory, antioxygenation, anti-lipid peroxidation, suppression TYR list phenolase.But because the content of isoliquiritin in Radix Glycyrrhizae is not high, make the difficulty extracting isoliquiritin comparatively large, therefore its market value exceed about 10 times than liquirtin.
9. Liquiritigenin (4',7-Dihydroxyflavanone) (Liquiritigenin), chemical name: 7,4 '-dihydroxyl flavanone, molecular formula: C 15h 12o 4, molecular weight: 256.25338, CAS No.578-86-9.For white crystalline powder, structural formula is as follows:
Liquiritigenin derives from glycyrrhizic legume Glycyrrhiza uralensis Fisch., has spasmolysis, antiulcer agent, antibacterial, and the effect of liver cell oxidase inhibitor is similar to dioxy cinnamophenone character.With sucrose in water ratio, its sweet stimulation is slowly lasting, and its sugariness is 200-500 times of sucrose.Have flavour, have lasting unhappy sensation, coordinate with sucrose, asccharin, citric acid, then sweet taste is better.Liquiritigenin itself is not with fragrance matter, but has flavouring effect.Can not fermentation be caused, in curing food, replace sucrose, the phenomenons such as fermentation, variable color, sclerosis can be avoided.Liquiritigenin and glycosides thereof are a kind of flavones, have effect of spasmolysis, antiulcer agent, restraint of tyrosinase activity, scavenging activated oxygen, suppress the effects such as intestinal bacteria, streptococcus aureus, Bacillus subtilus in addition, in makeup, have the multiple efficacies such as whitening.Chinese scholars has obtained abundant achievement to the pharmacology activity research of Radix Glycyrrhizae, is worth carrying out more deep research to its effective constituent
Extraction document about Liquiritigenin and isoliquiritigenin is as follows: Li Guozhong, Li Nan, and guarantor's space etc. are at " supercritical CO 2the extraction process of extraction isoliquiritigenin " report Radix Glycyrrhizae pulverizing alcohol immersion in (applied chemistry, 2007,24 (1): 67-70), load in extraction kettle, in entrainment agent heap, add the liquor-saturated solution of people's second.Regulate certain temperature, pressure, CO 2flow velocity, filling CO in pump 2after, start overcritical equipment, collect extraction liquid, Fu Yujie, Liu Xiaona, Hou Chunlian etc. are in " research of On Separation And Purification of Isoliquiritigenin By Macroporous Adsorption Resin " (ion-exchange and absorption, 2006,22 (4): 315-322) the adsorption and desorption ability of HPD-600, D4020, D101, AB-8, NKA-II, AL-2 and NKA-9 resin to isoliquiritigenin is reported in, screening optimum resin is AB-8, determine optimal processing parameter, isoliquiritigenin sample solution rate of recovery after AB-8 resin absorption and desorption is 76.7%, purity brings up to 29.1% by 2.02%, improves 14.4 times, Wang Jianguo, Liu little Feng, Huang Zhijun etc. are at " research that Liquiritigenin and isoliquiritigenin extract " (Chemical Industry in Guangzhou, 2010, 38 (1): 111-113) extracting of Glycyrrhiza uralensis Fisch. methyl alcohol is reported in, boil off methyl alcohol, obtain red-brown paste, with hot water dissolving, aqueous phase solvent extracts, henna paste is obtained except after desolventizing, dissolve with methanol, add polymeric amide mixing to mix thoroughly, polyamide chromatography, gradient elution is made with methanol-chloroform mixed solvent, be separated with silicagel column respectively again, TLC detects, collect, merge and flow out part, obtain colourless long needle crystal Liquiritigenin and the lobate crystallization isoliquiritigenin of golden yellow, Yang Li, Shen Fengjia is at " synthesis of Liquiritigenin and isoliquiritigenin " (Acta Pharmaceutica Sinica, 1994,29 (11): 877-880) synthesis reporting Liquiritigenin and isoliquiritigenin in belongs to the synthesis of classical flavonoid compound, reaction in polyphosphoric acid, Friedel-crafts reaction, aldehyde condensation, isoliquiritigenin is converted into Liquiritigenin, Niu Mei, Hu Xianwang, Gao Jun report Radix Glycyrrhizae ethanol extraction heat in " Liquiritigenin and isoliquiritigenin Separation Research ", concentrate to obtain dark-brown mashed prod, use distilled water heat of solution, use organic solvent extraction respectively.Be concentrated into concentrating under reduced pressure after pasty state to do, obtain yellowish brown meal, upper silica gel H post wash-out, silica gel H post go up again by elutriant, wash-out, treated must colorless needle crystals body Liquiritigenin and isoliquiritigenin.Fu Yujie, Liu Xiaona, Wang Wei etc. are at " acid-hydrolysis method extracts isoliquiritigenin technical study in Radix Glycyrrhizae " (Chinese Pharmaceutical Journal, 2007,42 (11): 818-821) optimised process that acid-hydrolysis method extracts isoliquiritigenin is reported in, the extraction yield that acid-hydrolysis method extracts isoliquiritigenin is 2.47 ‰, and in medicinal extract, isoliquiritigenin content is 3.01%; Ma Yongting; Luo Hao; Li Shuanming etc. are at " synthesising process research of isoliquiritigenin " (plant research; 2009; 29 (5): 637-640) report in 2; 4-resacetophenone and p-Hydroxybenzaldehyde are raw material, and by hydroxyl protection, aldol condensation and deprotection synthesis obtain isoliquiritigenin.And to committed step aldol reaction condition wherein as the kind of catalyzer, the mol ratio of substrate, temperature of reaction, solvent and reaction times are optimized; Huang Jiwei, Ling Xinlong, vast stretch of wooded country great waves " the easy study on the synthesis of isoliquiritigenin " (time precious traditional Chinese medical science traditional Chinese medicines, 2012,23 (10): 2454-2456) report current in, the synthesis of isoliquiritigenin is normally reacted with classical cinnamophenone synthetic method-Claisen-Schmidt, namely makees catalyzer in ethanolic soln with alkali, is obtained by condensation.The synthesis of isoliquiritigenin is first by 1,3-dihydroxy-benzene synthesis 2,4-resacetophenone, then itself and the homemade chloromethyl methyl ether of 4-hydroxy benzaldehyde are protected, prepare corresponding protected ketone and aldehyde, then there is aldol reaction and prepare cinnamophenone containing protecting group, finally deprotection base in acid condition, obtain isoliquiritigenin; It is diligent that wood closes Bu Liabuli, Ayniwiaer is bought and is carried, Re Nakasi wood is at " preparation method of isoliquiritigenin and Advance on Pharmacological Activities " (Chinese Journal of Modern Applied Pharmacy magazine, 2009,26 (4): 277-280) the sequence of operations methods such as Niu Lin etc. extracts with Glycyrrhiza uralensis Fisch. ethanol heat, concentrated evaporate to dryness, hot water extraction, organic solvent extraction, silica gel H column chromatography for separation are reported in.He Yujie etc. study processing condition and the relevant parameters of On Separation And Purification of Isoliquiritigenin By Macroporous Adsorption Resin, by comparing the adsorption and desorption ability of different resins to isoliquiritigenin, filtering out optimum resin is AB-8, and have studied its adsorption and desorption performance to isoliquiritigenin, determine best adsorption and de-adsorption processing parameter, the rate of recovery is 76.7%, purity brings up to 29.1% by 2.02%, the domestic existing patent of invention about isoliquiritigenin synthetic method, namely with 2, 4-resacetophenone and p-Hydroxybenzaldehyde are raw material, take lewis' base as catalyzer, through condensation reaction synthesizing isoliquiritigenin crude product, again through decolouring and recrystallization process, its fine work obtained, Li Hongzhi, Ayniwiaer is bought and is carried, wood closes the diligent grade of Bu Liabuli and report p-Hydroxybenzaldehyde and 2 in " synthesis of isoliquiritigenin derivant and structural characterization " (Chinese Journal of New Drugs, 2009,18 (19): 1882-1885), 4-resacetophenone, boric acid, glycol ether is Material synthesis, and crude product is through silica gel column chromatography, wash-out, recrystallization obtains yellow needle-like crystals isoliquiritigenin.Fu Yujie etc. are by screening 7 kinds of macroporous resins, and determine that AB-8 is the optimum resin of purifying isoliquiritigenin, isoliquiritigenin sample solution rate of recovery after AB-8 resin absorption and desorption is 76.7%, and purity brings up to 29.1% by 2.02%, improves 14.4 times.
10. isoliquiritigenin (isoliquiritin unit) (Isoliquiritigenin) molecular formula: C 15h 12o 4, molecular weight 256.25, CAS No.961-29-5.Chemical name: 4,2 ', 4 '-trihydroxy-phenyl styryl ketone, structural formula is as follows:
(E)-1-(2,4-dihydroxy phenyl)-3-(4-hydroxy phenyl)-2-propylene-1-ketone, yellow powder.Isoliquiritigenin belongs to hydroxy-benzalacetophenone compounds, and its content in Radix Glycyrrhizae accounts for about 7/50000 to ten thousand/10000ths.1) antitumor action, has the activity significantly promoting cancer cell-apoptosis and inhibition tumor cell propagation, to the restraining effect luring cancer agent and carcinogenic promoting agent, induced tumor reverse effect, suppress the increment of liver cancer cell, suppress human cervical carcinoma cell propagation, suppress prostate cancer cell active.Research display, isoliquiritigenin can be used as new type anticancer lead compound, has important value; 2) antioxygenation, isoliquiritigenin significantly can suppress the generation of HL-60 reactive oxygen species, and the change of reactive oxygen species may be the major reason causing cytodifferentiation; 3) anti-inflammatory action, isoliquiritigenin is a kind of aldose reductase inhibitor, by suppressing cyclooxygenase, lipoxygenase, Peroxidase activity to carry out anti-platelet aggregation, plays anti-inflammatory action; 4) to effect that is cardiovascular and tracheae, isoliquiritigenin can alleviate the damage of ischemia-reperfusion to heart, can alleviate heart disorder and myocardial infarction that Reperfu-sion causes, by noncompetitive Ca2+ overloading, lax tracheal smooth muscle, the tracheal strip that can significantly suppress High K+ depolarization to cause shrinks.In addition, isoliquiritigenin has anti-AIDS, anti-diabetic complication isoreactivity, thus one of study hotspot becoming pharmacy circle.
11. licochalcone As (Licochalcone A), molecular formula: C 21h 22o 4, molecular weight: 338.39698, CAS No.58749-22-, pale yellow powder.Structural formula is as follows:
Licochalcone A is a kind of phenols chalcone compound be present in Radix Glycyrrhizae, be regarded as the species specificity composition of glycyrrhiza inflate bat, in Radix Glycyrrhizae, in chalcone compounds, the content of licochalcone A is the highest, therefore has more actual application value to the research of licochalcone A.1975, Saitoh T etc. were separated first and obtain licochalcone A from Radix Glycyrrhizae, and demonstrate its structure.Licochalcone A has anti-oxidant, anti-inflammatory, antibacterial, anti-leishmaniasis, antitumor, the multiple pharmacological effect such as immunological enhancement and estrogen-like, has been widely used in food and medicine industry.Antineoplastic action mechanism is inducing tumor cell early apoptosis, and licochalcone A is expected to the important sources becoming natural antitumor medicine.
Document about liquorice chalcone is as follows: Yang Linwei, Song Xinbo, Zhang Lijuans etc. are at " licochalcone A preparation method and Advance on Pharmacological Activities " (Liaoning University of TCM's journal, 2013,15 (11): 85-86) preparation method of licochalcone A is reported in: the method extraction separation and purification cinnamophenone of column chromatography, macroporous resin, high-speed counter-current method, preparative chromatography, polyamide column chromatography and silica gel column chromatography.Li Hongzhi etc. adopt in chloroform immersion, Sonication assisted treatment glycyrrhiza inflate bat root meal to extract and obtain total flavones crude product, adopt the method for polyamide column chromatography to refine total flavones crude product, be separated from refining total ketone finally by twice silica gel column chromatography and obtain the higher licochalcone A of purity.Cui Yongming etc. adopt the method for EtOH Sonicate auxiliary treatment to obtain extract from the glycyrrhiza inflate bat meal of Xinjiang, secondly extract is passed through silica gel column chromatography, again through secondary silica gel column chromatography after the elutriant of collection principal constituent, after collecting target compound, obtain licochalcone A through recrystallization.The leaching such as Wang Shujie, macroporous resin are separated and obtain total flavones crude product, then adopt the method extraction separation and purification cinnamophenone of polyamide column chromatography and silica gel column chromatography, then obtain sterling through recrystallization.A Dila tells Er Xuntayi etc. and adopts the water extracted immersing paste and extraction using alcohol medicinal extract to carry out abstraction and purification by polyamide chromatography post, finally obtains licochalcone A.Zhang Juan etc., by glycyrrhiza residue alcohol extract hot water ultrasonic dissolution, filter, upper AV-8 macroporous resin, ethanol elution, preparation liquid phase separation, then obtain sterling through Sephdex LH-20 purifying.Wang Qiaoe etc. adopt the upper phase that fixes mutually of solvent systems normal hexane-chloroform-methanol-water, do moving phase mutually down, and after purifying, the purity of licochalcone A and inflacoumarin A is respectively 99.1% and 99.6%; Han Longzhe, Zhang Juan, Ni Hui etc. is at " preparation of glycyrrhiza inflate bat dregs of a decoction total flavones and licochalcone A and anti tumor activity in vitro research " thereof (modern medicines and clinical, 2013,28 (5): 668-672) liquorice dregs is reported in through alcohol reflux, recycling design.Liquid after concentrated through HPD100 macroporous resin purification, ethanol elution, through polyamide column chromatography separation and purification, wash-out, obtain liquorice dregs total flavones, total flavones is separated through silica gel column chromatography, wash-out, and eluted fraction is separated through polyamide column chromatography, wash-out, recrystallization, obtains licochalcone A.
12. Radix Glycyrrhizae xylogen xylogen are the aromaticity superpolymer containing oxo phenylpropyl alcohol or derivatives thereof structural unit in a kind of unbodied, molecular structure be extensively present in plant materials.Xylogen is the complicated phenol polymer of one formed by four kinds of alcohol monomers (to tonquinol, lubanol, 5-hydroxyl lubanol, sinapyl alcohol).
At occurring in nature, xylogen is only second to cellulosic second largest renewable resources, and according to estimates, the annual whole world can produce 1,500 hundred million tons of xylogen by plant-growth.There is aromatic base, phenolic hydroxyl group, alcoholic extract hydroxyl group, carbon back conjugated double bond isoreactivity group in lignin structure, therefore can carry out being oxidized, reduce, be hydrolyzed, alcoholysis, acidolysis methoxyl group, Suo Ji, photodissociation, phthalein, sulfonation, alkylation, halogenation, nitrated, many chemical reactions such as polycondensation or graft copolymerization.Different according to monomer, xylogen can be divided into 3 types: the syringyl lignin (S-xylogen) be polymerized by Syringa oblata Lindl. base propane structures alone, the guaiacyl xylogen be polymerized by guaiacyl propane structures alone (G-xylogen) and the p-hydroxy phenyl xylogen (H-xylogen) by p-hydroxyphenylpropane structure monomer polymerization.The principal character absorption peak of Radix Glycyrrhizae lignin function group has: 3400cm -1, 2930cm -1, 1665cm -1, 1600cm -1, 1508cm -1, 1446cm -1, 1411cm -1, 1325cm -1, 1020cm -1there is vibration peak.Be respectively-OH stretching vibration, the stretching vibration peak of C-H in methyl, methylene radical and methyne, conjugation carbonyl, aromatic nucleus skeleton, the C-H flexural vibration peak of methyl and methylene radical, the stretching vibration peak of phenolic hydroxyl group, Syringa oblata Lindl. core absorption band, aromatic proton C-O vibration peak, the flexural vibration peak of ehter bond.Xylogen is nontoxic, inexpensive, and at present, the lignin product developed both at home and abroad reaches more than 200 and plants, and therefore, xylogen has important using value in Chemical Manufacture: 1) rubber reinforcing filler; 2) adhesive made of synthetic resin; 3) building materials auxiliary agent, cement water reducing agent; 4) scale inhibitor and inhibiter; 5) coal water slurry dispersing agent; 6) water conditioner; 7) oil field chemical.Also be widely used in pesticide processing, moulded coal make, the filler of tanning, pelletizing of carbon black and soil, sand dune, powder outstanding person control etc.
Document about Radix Glycyrrhizae xylogen is as follows: Zhao Jianbo, Chen Xinping, Jiang Jianhui is at the Study on extraction of alkali lignin " in the glycyrrhiza residue " (Tarim University's journal, 2011, 23 (3): 42-45) raw material degreasing dewaxing is reported in, get dewaxing sample and add sodium hydroxide solution extraction, filtrate acid adjustment, concentrated, concentrated solution alcohol settling, filter, acidifying after filtrate is concentrated, leave standstill, supernatant liquid centrifugation, washing, obtain xylogen, lignin extraction rate is 4.88%, in xylogen, total hydroxy radical content is 5.43%, content of phenolic hydroxyl groups is 3.28%, alcoholic extract hydroxyl group content is 2.15%.Zhao Jianbo, Chen Xinping is in " utilizing alkaline process and organic solvent method to extract glycyrrhiza residue xylogen " (Jiangsu's agriculture science, 2014,42 (2): 223-225) report glycyrrhiza residue in and adopt alkaline process and organic solvent method, with sodium hydroxide, ammoniacal liquor, acetone and ethylene glycol for solvent extracts xylogen from glycyrrhiza residue, measure the content of lignin function group, molecular weight and molecular weight distribution further.
The macromolecular polysaccharide that 13. Radix Glycyrrhizae cellulosic fibre elements are made up of glucose, water insoluble and common organic solvents is the main component of plant cell wall.Mierocrystalline cellulose is a kind of polysaccharide that occurring in nature distribution is the widest, content is maximum, accounts for more than 50% of vegitabilia's carbon content.In general timber, Mierocrystalline cellulose accounts for 40 ~ 50%, also has the hemicellulose of 10 ~ 30% and the xylogen of 20 ~ 30%.Structure is as follows:
Physiological action: 1) treat diabetes, food fibre can improve susceptibility and the utilization ratio of insulin receptor, the sugar of parcel food, balance postprandial blood sugar, regulating blood glucose levels, treatment diabetes; 2) prevention and therapy coronary heart disease, food fibre can be combined with cholic acid and excrete, and cholesterol can be impelled to transform to cholic acid, thus reduce cholesterol levels, and the rising of serum cholesterol content can cause coronary heart disease; 3) hypotensive effect, food fibre can adsorb sodium ion, potassium ion in enteron aisle, reduces the natrium/kalium in blood, reduces blood pressure; 4) antitumous effect, food fibre can produce short chain fatty acid can suppress saprophytic microorganism growth, food fibre can fetter the materials such as cholic acid and be excreted, and prevents carcinogenic generation, and food fibre can promote intestines peristalsis, increase faecal volume, shorten emptying time, reduce the chance that carcinogens contacts with colon, food fibre produces the growing multiplication of butyric acid energy inhibition tumor cell, induce it to normal cell turnover, and control the expression of oncogene; 5) banting obesity, food fibre makes the total intake of food reduce, and food fibre serves filling effect to stomach, produces satiety and depress appetite.Food fibre is combined with partial fatty acid, decreases the specific absorption to fat; 6) treat constipation, food fibre has very strong water-absorbent, and intestinal contents volume is increased, and the deliquescing that fluffs of defecating, can stimulate contraction and the wriggling of enteron aisle, accelerates stool excretion, plays the effect for the treatment of constipation.
Mierocrystalline cellulose is natural polymer ancient, the abundantest on the earth, is inexhaustible, the natural reproducible resource that the mankind are the most valuable.Before cellulose chemistry and industry start from more than 160 year, be that polymer chemistry is born and the main study subject of developing period, the achievement in research of cellulose and its derivates be the foundation of Polymer Physics and chemistry subject, development and abundantly made major contribution.
As follows about the cellulosic document of Radix Glycyrrhizae: Ji Yuanyuan is at " utilizing glycyrrhiza residue to prepare carboxymethyl cellulose " (Shanxi chemical industry, 1997, report 2:43-44) and add dilute nitric acid solution boiling 0.5-1.5h by thick glycyrrhiza residue pressure kettle, after cooling, be washed till neutrality with clear water.By the slag charge after washing and sodium hydroxide solution boiling in pressure kettle, after naturally cooling, be washed till neutrality with clear water, dry, content of cellulose can reach 80%.
In a kind of Radix Glycyrrhizae, the collaborative of effective constituent cleans extracting method, the present invention adopts a kind of solvent, by saponin(e in glycyrrhiza inflate bat and flavones simultaneous extraction, obtain general extractive, then general extractive is separated with fat-soluble according to water-soluble, then according to the physico-chemical property of each composition, is separated one by one, advance layer by layer, obtain each single component.The present invention considers from the integrated separation of all prods, has invented the collaborative of effective constituent in Radix Glycyrrhizae on the whole and has cleaned extracting method, does not just focus on the extraction and isolation of single product." eat dry bleeding " and be the value orientation of comprehensive utilization of resources.But, recycling economy is never " eating dry bleeding ", in Radix Glycyrrhizae, the collaborative of effective constituent cleans extracting method, while pursuit resource " eats dry bleeding ", to the waste produced in production process, turn waste into wealth, turn harm into good, to reach the object of comprehensive utilization, impel the development of recycling economy, realize resources conservation, eco-friendly economic model.
It is all the independent extraction to composition a certain in Radix Glycyrrhizae in background technology, for overcoming the deficiency in background technology, the present invention aims to provide the collaborative of effective constituent in a kind of Radix Glycyrrhizae and cleans extracting method, with glycyrrhiza inflate bat (Glycyrrhiza infiata Batalin) for raw material is through the preparation of general extractive, be separated one by one respectively again and obtain liquorice pigment, Radix Glycyrrhizae dextran, licorice polysaccharide, Potenlini, licoflavone, anacidity licoflavone, glabridin, liquirtin, isoliquiritin, isoliquiritigenin, Liquiritigenin, licochalcone A, Radix Glycyrrhizae xylogen and Radix Glycyrrhizae Mierocrystalline cellulose.
Technical solution of the present invention is:
In Radix Glycyrrhizae, the collaborative of effective constituent cleans an extracting method, comprises the steps:
(1) preparation of the general extractive of glycyrrhiza inflate bat.
(2) to be water-solublely separated with fat-soluble component.
(3) Potenlini and liquorice pigment in water soluble component, Radix Glycyrrhizae dextran, being separated of licorice polysaccharide.
(4) liquorice pigment and Radix Glycyrrhizae dextran, being separated of licorice polysaccharide.
(5) being separated of Radix Glycyrrhizae dextran and licorice polysaccharide.
(6) separation and purification of glabridin in fat-soluble component.
(7) separation and purification of liquirtin, isoliquiritin in fat-soluble component.
(8) separation and purification of isoliquiritigenin, Liquiritigenin in fat-soluble component.
(9) separation and purification of licochalcone A in fat-soluble component.
(10) separation and purification of Radix Glycyrrhizae xylogen in fat-soluble component.
(11) the cellulosic separation and purification of Radix Glycyrrhizae in fat-soluble component.
Summary of the invention
Embodiment
Glycyrrhiza inflate bat rhizome meal adds in multi-function extractor, adverse current pump circulation, mouth is set out in the middle of tank body, bottom pump suction cover, mineralization pressure formula upwardly, existing circulating effect, can better loosen medicinal material in tank again, and it is that top at the bottom of tank body increases a deceleration agitator that benefit is greater than dynamic extraction, medicinal material decocts in tank, and centre is stirred.Decoct end to need to carry out vacuum fluid, so not only can shorten the fluid time, and more importantly raffinate effective in slag can be taken out to the greatest extent, avoid waste.Equipment in working order time, the valve of fastening system gas circuit of rising to the bait is also in running order, relief cylinder must be used during work, so as not to pressure release break off relations and have an accident.Close good multi-function extractor mouth, by the dimethyl formamide of accurate measurement vacuum suction reactor, open reactor mouth, start stirring, ethanol pH11-13 is adjusted with saturated sodium hydroxide, sealing extractor mouth, open the heating of extractor heat-carrying steam valve, close heat-carrying steam valve when tank upward pressure table indicator pressure to be extracted reaches 0.25MPa, keep extractor internal pressure at 0.20-0.40Mpa, Extracting temperature is at 80-90 DEG C, extract 2.0h, extract completely and start step-down, tapping after being cooled to 60-70 DEG C, obtain first time licorice extract.Filter residue adds dimethyl formamide again, start stirring, adjust ethanol pH11-12 with saturated sodium hydroxide, sealing extractor mouth, open the heating of extractor heat-carrying steam valve, close heat-carrying steam valve when tank upward pressure table indicator pressure to be extracted reaches 0.20MPa, keep extractor internal pressure at 0.20-0.40Mpa, Extracting temperature is at 80-90 DEG C, extract 1.Sh, extract completely and start step-down, tapping after being cooled to 60-70 DEG C, obtain second time licorice extract.Filter residue adds dimethyl formamide again, start stirring, ethanol pH10-11 is adjusted with saturated sodium hydroxide, sealing extractor mouth, opens the heating of extractor heat-carrying steam valve, closes heat-carrying steam valve when tank upward pressure table indicator pressure to be extracted reaches 0.20MPa, keep extractor internal pressure at 0.20-0.40Mpa, start step-down, tapping after being cooled to 60-70 DEG C after getting 1.0h extraction completely at 80-90 DEG C, obtain third time licorice extract.Front extracted twice liquid merging is neutralized to neutrality, concentrated, applies mechanically, so circulate during extraction next time of third time extracting solution.
At vacuum tightness-(0.090-0.094) Mpa, concentrated at temperature 70-80 DEG C, enriched material proportion 1.18, obtains Potenlini general extractive.Add Radix Glycyrrhizae general extractive 10,8, the purified water of 6 times amount (W/W) is dissolved three times at 60-80 DEG C respectively, and filter, water liquid and precipitate and separate, obtain water-soluble and fat-soluble component.In D101 resin column more than 95% alcohol dipping 4h, then use purified water drip washing, until effluent liquid is not muddy at dilute with water.Finally use water repetitive scrubbing, without obvious ethanol smell.The above-mentioned aqueous solution being passed through resin column with the flow velocity of 1-4BV/h, can not have bubble in resin layer, detect the spillage of object product in effluent liquid, when spillage reaches 10% of inlet concentration, is absorption terminal.First elute glucose and polysaccharide by the purified water of 1-2BV, more again with 10-20% ethanol elution, collect elutriant, obtain Potenlini ethanolic soln, then with 50-80% ethanol elution, obtain liquorice pigment ethanolic soln.Liquorice pigment solution be concentrated into proportion 1.05-1.15, add appropriate sherwood oil, 6 #solvent oil, one of in ethyl acetate, stirs, crystallization, crystallisate again with normal hexane, sherwood oil, 6 #solvent oil, washing, obtains white liquorice pigment one of in ethyl acetate.The Potenlini ethanolic soln of gained is evaporated to proportion 1.05-1.20, places crystallization, obtain crude product Potenlini, add normal hexane after crude product drying, sherwood oil, 6 #one of solvent oil, in ethyl acetate, then drip a small amount of dehydrated alcohol, stir, till washing away pigment, vacuum-drying, obtains white Potenlini.Resin after wash-out to without alcohol taste with purified water drip washing resin layer, is then used 4%NaOH solution with 1-2BV/h drip washing resin layer 2-3h, is washed till neutrality with distilled water.
Sephadex LH-20 dextrane gel adding distil water is stirred, at the swelling 6h of room temperature.Removing gel upper water and fine particle, with purified water repetitive scrubbing several times, then with buffered soln washing 2-3 time, pump solution and gel particle air entrapment.Avoid undue agitation, avoid using magnetic stirring apparatus.Before dress post, used water flotation process removes monomer, powder and impurity in gel, the bubble of discharging in gel and vacuum available pump is bled.Whole packed column must be made very even, otherwise must refill.Post is vertically fixed, adds a small amount of moving phase to get rid of the bubble of bottom in post, add some moving phases in post about 1/4 height.Column top connects a funnel, neck diameter is about the half of necking, then degassed gel suspension is added under agitation, slowly, equably, continuously, open the capillary outlet of chromatographic column simultaneously, maintain suitable flow velocity, gel particle will successively horizontal rise, and deposit equably, until desired height position in post.Finally remove funnel, cover the surface of gel bed with less filter paper gently, then use a large amount of eluent by gel bed scrubber for some time.Before loading, with elutriant balance chromatography column at least two column volumes until baseline becomes steady, the swelling property of gel in novel solvent should be noted as changed solvent, and according to the position of character determination post height setter, as used identical solvent, in chromatography afterwards, column equilibration can omit.Before sample is separated, must whether check uniformly chromatographic column.Put one as the parallel fluorescent lamp of post post is other, in the post that detects by an unaided eye, whether have " lines " or bubble.Also can add coloured macromole etc. in chromatographic column, namely the molecular weight adding material in the separating ranges of gel column, if it is narrow, even, smooth to observe bands of a spectrum in post, should illustrate that column performance is good.Otherwise, again must load gel column.Add the biased sample containing glucose and licorice polysaccharide, and start to collect effluent liquid, regulate eluent flow rate to be that every 1mL/min carries out wash-out, obtain licorice polysaccharide, washing, to licorice polysaccharide elutriant, concentrated, add the H of 3-5% (W/W) 2o 2at 60 DEG C, heat 30min, add acetone precipitation, collecting precipitation, dry, obtain licorice polysaccharide.Use 10-20% sodium chloride solution wash-out again, obtain Radix Glycyrrhizae dextran, add the H of 3-5% (W/W) 2o 2at 60 DEG C, heat 30min, be concentrated into dry, add pyridine, dimethyl formamide, dissolve one of in dimethyl sulfoxide (DMSO), filter, collect filtrate, add methyl alcohol or alcohol settling after being concentrated into 1/5 volume, collecting precipitation, dry, obtain Radix Glycyrrhizae dextran.Elutriant is used respectively 721 its optical density(OD) of type spectrophotometric determination.
By fat-soluble precipitation vacuum-drying, obtain dry thing, use normal hexane respectively, sherwood oil, No. 6 solvent oils, extract 3 times one of in ether, first time 5 times amount (V/W) extracts degreasing, and second time 4 times amount (V/W) extracts degreasing, and third time 3 times amount (V/W) extracts degreasing, collect the liquid after degreasing, degreasing solvent reclaims.Licoflavone mixture after degreasing is with trichloromethane, toluene or dichloromethane extraction 3 times, first time 5 times amount (V/W) extracts degreasing, second time 4 times amount (V/W) extracts degreasing, third time 3 times amount (V/W), united extraction liquid, obtains glabridin extracting solution, is evaporated to proportion 1.05-1.20.With neutral alumina wet method upper prop, the device of alumina chromatographic column, the ratio of its internal diameter and column length is between 1: 10-1: 20.The trichloromethane first measuring certain volume adds chromatography column, opens piston, and added at leisure by aluminum oxide simultaneously and make its one side sedimentation, one side is added, until add.Aluminum oxide can not have bubble and " destruction " chromatography column.After aluminium to be oxidized adds, still make trichloromethane rinse certain hour, sample solution is injected above alumina column gently, does not make aluminum oxide cylinder be disturbed, otherwise will chromatographic effect be affected.First with pure trichloromethane wash-out, then with trichloromethane: ethyl acetate=40: 10-40: 15 (v/v) are eluting solvent, flow velocity is 1.2mL/min, and sample introduction concentration is 2mg/mL, and type of elution is with linear terraced wash-out, and post bed body selects 25, and column temperature is room temperature.TLC checks and merges same stream part, and concentrated, crystallization, obtains white light licoricidin.
By said extracted, the residuum of glabridin is with ethyl acetate or butylacetate, extract 3 times, first time 5 times amount (V/W) extracts degreasing, and second time 4 times amount (V/W) extracts degreasing, third time 3 times amount (V/W), united extraction liquid, obtain liquirtin, isoliquiritin, isoliquiritigenin, Liquiritigenin extracting solution, be evaporated to proportion 1.05-1.10, with silica gel wet method upper prop, 200-300 order silica gel, claims 30-70 doubly to applied sample amount.Add the trichloromethane of dry silica gel volume one times, fully stir with glass stick, chromatography column is cleaned, be vertically fixed on retort stand, select there is film end as chromatography column end opening, end opening is connected emulsion tube and clamps with screw clip.Add trichloromethane in chromatography column, open end opening screw clip, allow solution flow out, get rid of residual bubble, finally retain the elutriant of about 2 cm heights, tighten screw clip.Silica gel is stirred gently evenly, slowly inject post with glass stick along chromatography column inwall, when silica gel to deposit under post bed more than 1cm, open end opening screw clip, continue dress post and reach 8cm to post bed height, close outlet.Forbid to produce bubble in dress post process, avoid occurring layering.Balance 1-2BV with elutriant again, silica gel face remains certain Shen takes off liquid.After balance, tighten lower end screw clip.Filling needs the post bed of a formation stable uniform.After sedimentation completes, add more trichloromethane, with duplex ball or air pump pressurization, until constant flow rate.Post bed is about compressed into 9/10 volume.By the solution loading containing liquirtin, isoliquiritin, isoliquiritigenin, Liquiritigenin, add some trichloromethanes, then by a degreasing tampon extremely close to Silica Surface.Then just can add a large amount of trichloromethane relievedly, and can not Silica Surface be washed out.First with pure trichloromethane wash-out, then with trichloromethane: methyl alcohol=1: 100-5: 100 (V/V) are eluent, TLC checks, merge same stream part, flow velocity is 2mL/min, and sample introduction concentration is 2.5mg/mL, type of elution is with linear gradient wash-out, and post bed body selects 25, and column temperature is room temperature.TLC checks and merges same stream part, and concentrated, crystallization, obtains Liquiritigenin and isoliquiritigenin respectively.
The silica gel chromatographic column of Liquiritigenin and isoliquiritigenin by above-mentioned wash-out, again respectively with trichloromethane: methyl alcohol=6: 100-10: 100 (V/V) for eluent gradient Shen take off, flow velocity is 2mL/min, sample introduction concentration is 2.5mg/mL, chromatography under room temperature, and TLC checks, merge same stream part, concentrated, crystallization, obtains liquirtin and isoliquiritin respectively.
Liquirtin will be extracted, isoliquiritin, isoliquiritigenin, methyl alcohol or alcohol extraction 3 times is added in Liquiritigenin residuum, first time 5 times amount (V/W) extracts degreasing, second time 4 times amount (V/W) extracts degreasing, third time 3 times amount (V/W), merge liquorice chalcone extracting solution, be concentrated into proportion 1.05-1.10, admix neutral alumina, dry method upper prop, liquorice chalcone extract and a small amount of neutral alumina are mixed into semi-solid, after adding chromatography column, E-test is adopted to carry out wash-out, first with eluent ethyl acetate, again with ethyl acetate: methyl alcohol=1: 100-5: 100 (V/V) gradient elution, TLC checks, merge same stream part, concentrated, crystallization, obtain liquorice chalcone.
Sodium carbonate or the sodium hydrogen carbonate solution 1-2 times amount (W/W) of pH9-10 will be added in the residuum being extracted liquirtin, isoliquiritin, isoliquiritigenin, Liquiritigenin and liquorice chalcone, heated and boiled 30-80min, press filtration, it is limpid that filter cake is washed to effluent liquid, merges with sub-filtrate above, be evaporated to proportion 1.10-1.20, pH1-3 is regulated, precipitation, press filtration with one of in hydrochloric acid, sulfuric acid or phosphoric acid, filter cake is dried, and obtains Radix Glycyrrhizae xylogen.
To liquirtin, isoliquiritin, isoliquiritigenin, Liquiritigenin, liquorice chalcone and Radix Glycyrrhizae xylogen residuum be extracted add the aqua calcis 4-8 times amount (W/W) of pH11-13,3-10% (W/V) hydrogen peroxide or chlorine bleach liquor is added under stirring, pH11-12 is adjusted with one of in hydrochloric acid, sulfuric acid or phosphoric acid, press filtration, be washed to effluent liquid neutrality, dry, obtain Radix Glycyrrhizae Mierocrystalline cellulose.

Claims (12)

1. in Radix Glycyrrhizae, the collaborative of effective constituent cleans an extracting method, it is characterized in that, with glycyrrhiza inflate bat (Glycyrrhiza inflata Batalin), for raw material, the method is successively through following steps:
(1) preparation of the general extractive of glycyrrhiza inflate bat.
(2) to be water-solublely separated with fat-soluble component.
(3) Potenlini and liquorice pigment and Radix Glycyrrhizae dextran in water soluble component, being separated of licorice polysaccharide.
(4) purifying of Potenlini and liquorice pigment.
(5) being separated of Radix Glycyrrhizae dextran and licorice polysaccharide.
(6) separation and purification of glabridin in fat-soluble component.
(7) separation and purification of Liquiritigenin, isoliquiritigenin in fat-soluble component.
(8) separation and purification of liquirtin, isoliquiritin in fat-soluble component.
(9) separation and purification of liquorice chalcone in fat-soluble component.
(10) separation and purification of Radix Glycyrrhizae xylogen in fat-soluble component.
(11) the cellulosic separation and purification of Radix Glycyrrhizae in fat-soluble component.
2. in a kind of Radix Glycyrrhizae according to right 1, the collaborative of effective constituent cleans extracting method, it is characterized in that, in step (1), extraction agent is pyridine, morpholine, dimethyl sulfoxide (DMSO), one of in dimethyl formamide or mixing and liquid, regulates pH10-13 with sodium hydroxide or potassium hydroxide, adverse current pump circulation extracts three times, extracts 2.0h under first time 10 times amount (V/W) backflow; 1.5h is extracted under second time 8 times amount (V/W) backflow; 1.0h is extracted under third time 6 times amount (V/W) backflow.With neutral with regulating one of in hydrochloric acid, sulfuric acid or phosphoric acid, being evaporated to proportion 1.15-1.20, obtaining Radix Glycyrrhizae general extractive.
3. in a kind of Radix Glycyrrhizae according to right 1, the collaborative of effective constituent cleans extracting method, it is characterized in that, step adds Radix Glycyrrhizae general extractive 10 in (2), 8, the purified water of 6 times amount (W/W) is dissolved three times at 60-80 DEG C respectively, filter, water liquid and precipitate and separate, obtain water-soluble and fat-soluble component.
4. in a kind of Radix Glycyrrhizae according to right 1, the collaborative of effective constituent cleans extracting method, it is characterized in that, in step (3), the aqueous solution water liquid of gained is by D-101 macroporous resin adsorption, first wash, obtain Radix Glycyrrhizae dextran and licorice polysaccharide mixed aqueous solution, again with 10-20% ethanol elution, collect elutriant, obtain Potenlini ethanolic soln., then with 50-80% ethanol elution, obtain liquorice pigment ethanolic soln, be concentrated into proportion 1.05-1.15, obtain liquorice pigment enriched material.
5. in a kind of Radix Glycyrrhizae according to right 1, the collaborative of effective constituent cleans extracting method, it is characterized in that, in step (4), the Potenlini ethanolic soln of gained in (3) is evaporated to proportion 1.05-1.20, place crystallization, obtain crude product Potenlini, normal hexane is added, sherwood oil, 6 after crude product drying #one of solvent oil, in ethyl acetate, then drip a small amount of dehydrated alcohol, stir, till washing away pigment, vacuum-drying, obtains white Potenlini.Liquorice pigment ethanolic soln in (3) is evaporated to proportion 1.05-1.20, adds appropriate sherwood oil, 6 #solvent oil, one of in ethyl acetate, stirs, crystallization, crystallisate again with normal hexane, sherwood oil, 6 #solvent oil, washing, obtains white liquorice pigment one of in ethyl acetate.
6. in a kind of Radix Glycyrrhizae according to right 1, the collaborative of effective constituent cleans extracting method, it is characterized in that, in step (5), the water liquid of gained in (4) is passed through Sephadex LH20 gel column chromatography, washing, obtain licorice polysaccharide elutriant, concentrated, add the H of 3-5% (W/W) 2o 2at 60 DEG C, heat 30min, add acetone precipitation, collecting precipitation, dry, obtain licorice polysaccharide.Use 10-20% sodium chloride solution wash-out again, obtain Radix Glycyrrhizae dextran, add the H of 3-5% (W/W) 2o 2at 60 DEG C, heat 30min, be concentrated into dry, add pyridine, dimethyl formamide, dissolve one of in dimethyl sulfoxide (DMSO), filter, collect filtrate, add methyl alcohol or alcohol settling after being concentrated into 1/5 volume, collecting precipitation, dry, obtain Radix Glycyrrhizae dextran.
7. in a kind of Radix Glycyrrhizae according to right 1, the collaborative of effective constituent cleans extracting method, it is characterized in that, by fat-soluble precipitation vacuum-drying in step (6), obtains dry thing, uses normal hexane respectively, sherwood oil, 6 #solvent oil, extracts 3 times one of in ether, and first time 5 times amount (V/W) extracts degreasing, and second time 4 times amount (V/W) extracts degreasing, and third time 3 times amount (V/W) extracts degreasing, collects the liquid after degreasing, and degreasing solvent reclaims.Licoflavone mixture after degreasing is with trichloromethane, toluene or dichloromethane extraction 3 times, first time 5 times amount (V/W) extracts degreasing, second time 4 times amount (V/W) extracts degreasing, third time 3 times amount (V/W), united extraction liquid, obtain glabridin extracting solution, be evaporated to proportion 1.05-1.20 with neutral alumina wet method upper prop, first with pure trichloromethane wash-out, again with trichloromethane: ethyl acetate=40: 10-40: 15 (v/v) are eluting solvent, flow velocity is 1.2mL/min, sample introduction concentration is 2mg/mL, type of elution is with linear terraced wash-out, post bed body selects 25, column temperature is room temperature.TLC checks and merges same stream part, and concentrated, crystallization, obtains white light licoricidin.
8. in a kind of Radix Glycyrrhizae according to right 1, the collaborative of effective constituent cleans extracting method, it is characterized in that, the residuum of glabridin will be extracted in (6) with ethyl acetate or butylacetate in step (7), extract 3 times, first time 5 times amount (V/W) extracts degreasing, second time 4 times amount (V/W) extracts degreasing, third time 3 times amount (V/W), united extraction liquid, obtain liquirtin, isoliquiritin, isoliquiritigenin, Liquiritigenin extracting solution, be evaporated to proportion 1.05-1.10, admix silica gel, adsorb with silicagel column, first with pure chloroform wash-out, again with trichloromethane: methyl alcohol=1: 100-5: 100 (V/V) are eluent, TLC checks, merge same stream part, flow velocity is 2mL/min, sample introduction concentration is 2.5mg/mL, type of elution is with linear gradient wash-out, post bed body selects 25, column temperature is room temperature.TLC checks and merges same stream part, and concentrated, crystallization, obtains Liquiritigenin and isoliquiritigenin respectively.
9. in a kind of Radix Glycyrrhizae according to right 1, the collaborative of effective constituent cleans extracting method, it is characterized in that, in step (8) by middle to (7) wash-out the silica gel chromatographic column of Liquiritigenin and isoliquiritigenin, then with trichloromethane: methyl alcohol=6: 100-10: 100 (V/V) are for eluting solvent, flow velocity is 2mL/min, sample introduction concentration is 2.5mg/mL, chromatography under room temperature, and TLC checks, merge same stream part, concentrated, crystallization, obtains liquirtin and isoliquiritin respectively.
10. in a kind of Radix Glycyrrhizae according to right 1, the collaborative of effective constituent cleans extracting method, it is characterized in that, methyl alcohol or extraction using alcohol 3 times is added in residuum in step (9) in (8), first time 5 times amount (V/W) extracts degreasing, second time 4 times amount (V/W) extracts degreasing, third time 3 times amount (V/W), merge liquorice chalcone extracting solution, be concentrated into proportion 1.05-1.10, admix neutral alumina, dry method upper prop, first with eluent ethyl acetate, again with ethyl acetate: methyl alcohol=1: 100-5: 100 (V/V) gradient elution, TLC checks, merge same stream part, concentrated, crystallization, obtain liquorice chalcone respectively.
In 11. a kind of Radix Glycyrrhizaes according to right 1, the collaborative of effective constituent cleans extracting method, it is characterized in that, sodium carbonate or the sodium hydrogen carbonate solution 1-2 times amount (W/W) of pH9-10 will be added in residuum in (9) in step (10), heated and boiled 30-80min, press filtration, it is limpid that filter cake is washed to effluent liquid, merge with pressing filtering liquid above, be evaporated to proportion 1.10-1.20, pH1-3 is regulated, precipitation, press filtration with one of in hydrochloric acid, sulfuric acid or phosphoric acid, filter cake is dried, and obtains Radix Glycyrrhizae xylogen.
In 12. a kind of Radix Glycyrrhizaes according to right 1, the collaborative of effective constituent cleans extracting method, it is characterized in that, residuum in step (10) adds the aqua calcis 4-8 times amount (W/W) of pH11-13,3-10% (W/V) hydrogen peroxide or chlorine bleach liquor is added under stirring, adjust pH11-12 with one of in hydrochloric acid, sulfuric acid or phosphoric acid, press filtration, is washed to effluent liquid neutrality, dry, obtain Radix Glycyrrhizae Mierocrystalline cellulose.
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