CN111635439A - Process method for improving yield of icariin - Google Patents
Process method for improving yield of icariin Download PDFInfo
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- CN111635439A CN111635439A CN202010523967.3A CN202010523967A CN111635439A CN 111635439 A CN111635439 A CN 111635439A CN 202010523967 A CN202010523967 A CN 202010523967A CN 111635439 A CN111635439 A CN 111635439A
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- epimedium
- ethanol
- acid
- icariin
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- TZJALUIVHRYQQB-XFDQAQKOSA-N Icariin Natural products O(C)c1ccc(C2=C(O[C@H]3[C@@H](O)[C@H](O)[C@@H](O)[C@H](C)O3)C(=O)c3c(O)cc(O[C@H]4[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O4)c(C/C=C(\C)/C)c3O2)cc1 TZJALUIVHRYQQB-XFDQAQKOSA-N 0.000 title claims abstract description 42
- TZJALUIVHRYQQB-XLRXWWTNSA-N icariin Chemical compound C1=CC(OC)=CC=C1C1=C(O[C@H]2[C@@H]([C@H](O)[C@@H](O)[C@H](C)O2)O)C(=O)C2=C(O)C=C(O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O3)O)C(CC=C(C)C)=C2O1 TZJALUIVHRYQQB-XLRXWWTNSA-N 0.000 title claims abstract description 42
- TZJALUIVHRYQQB-UHFFFAOYSA-N icariine Natural products C1=CC(OC)=CC=C1C1=C(OC2C(C(O)C(O)C(C)O2)O)C(=O)C2=C(O)C=C(OC3C(C(O)C(O)C(CO)O3)O)C(CC=C(C)C)=C2O1 TZJALUIVHRYQQB-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 39
- 230000008569 process Effects 0.000 title claims abstract description 24
- 241000893536 Epimedium Species 0.000 claims abstract description 44
- 235000018905 epimedium Nutrition 0.000 claims abstract description 44
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 15
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 12
- 235000020696 epimedium extract Nutrition 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 230000007062 hydrolysis Effects 0.000 claims abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 6
- 238000000746 purification Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 83
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000000284 extract Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- 239000012535 impurity Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- 239000003480 eluent Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 238000010828 elution Methods 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 230000009466 transformation Effects 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 241000893531 Epimedium koreanum Species 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 238000000605 extraction Methods 0.000 abstract description 8
- 239000008213 purified water Substances 0.000 description 9
- TUUXBSASAQJECY-UHFFFAOYSA-N 3,5,7-trihydroxy-2-(4-methoxyphenyl)-8-(3-methylbut-2-enyl)chromen-4-one Chemical compound C1=CC(OC)=CC=C1C1=C(O)C(=O)C2=C(O)C=C(O)C(CC=C(C)C)=C2O1 TUUXBSASAQJECY-UHFFFAOYSA-N 0.000 description 8
- 102000004190 Enzymes Human genes 0.000 description 8
- 108090000790 Enzymes Proteins 0.000 description 8
- 229940088598 enzyme Drugs 0.000 description 8
- 239000010419 fine particle Substances 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- CTGVBHDTGZUEJZ-UHFFFAOYSA-N Noricaritin Natural products CC(C)(O)CCC1=C(O)C=C(O)C(C(C=2O)=O)=C1OC=2C1=CC=C(O)C=C1 CTGVBHDTGZUEJZ-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000000498 cooling water Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000005325 percolation Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 235000015872 dietary supplement Nutrition 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000002207 metabolite Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- ULZLIYVOYYQJRO-JIYCBSMMSA-N Epimedin C Chemical compound C1=CC(OC)=CC=C1C1=C(O[C@H]2[C@@H]([C@H](O)[C@@H](O)[C@H](C)O2)O[C@H]2[C@@H]([C@H](O)[C@@H](O)[C@H](C)O2)O)C(=O)C2=C(O)C=C(O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O3)O)C(CC=C(C)C)=C2O1 ULZLIYVOYYQJRO-JIYCBSMMSA-N 0.000 description 1
- 208000010228 Erectile Dysfunction Diseases 0.000 description 1
- 208000001132 Osteoporosis Diseases 0.000 description 1
- 229940123333 Phosphodiesterase 5 inhibitor Drugs 0.000 description 1
- 240000004274 Sarcandra glabra Species 0.000 description 1
- 235000010842 Sarcandra glabra Nutrition 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079919 digestives enzyme preparation Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- YPFSXWUDSOVOGG-UHFFFAOYSA-N epimedin C Natural products COc1ccc(cc1)C2=C(OC3OC(C)C(O)C(OC(=O)C)C3OC4OC(CO)C(O)C(O)C4O)C(=O)c5c(O)cc(OC6OC(CO)C(O)C(O)C6O)c(CC=C(C)C)c5O2 YPFSXWUDSOVOGG-UHFFFAOYSA-N 0.000 description 1
- 229930003935 flavonoid Natural products 0.000 description 1
- 150000002215 flavonoids Chemical class 0.000 description 1
- 235000017173 flavonoids Nutrition 0.000 description 1
- HVQAJTFOCKOKIN-UHFFFAOYSA-N flavonol Natural products O1C2=CC=CC=C2C(=O)C(O)=C1C1=CC=CC=C1 HVQAJTFOCKOKIN-UHFFFAOYSA-N 0.000 description 1
- 150000002216 flavonol derivatives Chemical class 0.000 description 1
- 235000011957 flavonols Nutrition 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000003147 glycosyl group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 235000013402 health food Nutrition 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 201000001881 impotence Diseases 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 201000007270 liver cancer Diseases 0.000 description 1
- 208000014018 liver neoplasm Diseases 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 239000002590 phosphodiesterase V inhibitor Substances 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000036299 sexual function Effects 0.000 description 1
- 229960002639 sildenafil citrate Drugs 0.000 description 1
- DEIYFTQMQPDXOT-UHFFFAOYSA-N sildenafil citrate Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O.CCCC1=NN(C)C(C(N2)=O)=C1N=C2C(C(=CC=1)OCC)=CC=1S(=O)(=O)N1CCN(C)CC1 DEIYFTQMQPDXOT-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
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- 229940126680 traditional chinese medicines Drugs 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
- C07H1/06—Separation; Purification
- C07H1/08—Separation; Purification from natural products
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H17/00—Compounds containing heterocyclic radicals directly attached to hetero atoms of saccharide radicals
- C07H17/04—Heterocyclic radicals containing only oxygen as ring hetero atoms
- C07H17/06—Benzopyran radicals
- C07H17/065—Benzo[b]pyrans
- C07H17/07—Benzo[b]pyran-4-ones
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Molecular Biology (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Saccharide Compounds (AREA)
Abstract
The invention relates to a process method for improving the yield of icariin, which comprises the steps of extraction, solid-liquid separation, concentration, macroporous resin purification, concentration, hydrolysis, concentration, drying and the like, thus obtaining an epimedium extract. By optimizing the prior art, the yield of the icariin can be obviously improved, the quantity of epimedium medicinal materials required for producing the same equivalent icariin is greatly reduced, the production cost of an epimedium extract can be greatly reduced, the consumption of wild epimedium resources can be greatly relieved, and the exhaustion of the wild epimedium resources is avoided.
Description
Technical Field
The invention relates to the technical field of biological extraction, and particularly relates to a process method for improving the yield of icariin.
Background
Plants or plant extracts contain extremely complex chemical components, wherein a plurality of compounds have similar structures and are homologues or derivatives, and glycosyl, acetyl and other groups can be removed under certain specific conditions (such as an acid system, a basic system or a specific enzyme reaction system) and the compounds are converted into another compound with the same framework structure.
Herba epimedii, commonly known as herba epimedii, sarcandra glabra and the like, is one of the longest traditional Chinese medicines used in China, and has the effects of tonifying kidney yang, strengthening muscles and bones and dispelling wind and dampness. Modern studies have shown that its efficacy is related to the prenyl-containing flavonols (e.g. icariin). The epimedium extract which is produced by taking the epimedium as a raw material and carrying out the working procedures of extraction, purification and the like contains chemical components similar to those of the epimedium, has obvious effects of resisting fatigue and aging, improving the immunity of the organism and preventing osteoporosis, and is widely applied to the production of health-care food and dietary supplements at home and abroad.
With the deep research on the effective components and metabolites in epimedium, the application range of the epimedium series extract is further expanded. The hydrolysis and metabolite of epimedium flavonoids have strong biological activity, and researches show that icaritin has strong anti-tumor effect, and the Beijing shennogenyl is developing phase III clinical tests of icaritin (aiming at liver cancer, new medicine of class 1); meanwhile, the icaritin also has the function of a phosphodiesterase 5 inhibitor, the effect of treating male erectile dysfunction by the icaritin and the homologue is equivalent to that of treating sildenafil citrate, and the physical performance is obviously improved in addition to the improvement of the sexual function. Therefore, with the gradual definition of the action mechanism of the epimedium, the epimedium becomes a new hot point again, and the research and the declaration of the health care product taking the epimedium extract as the main functional raw material are carried out by a plurality of large health food enterprises at present. In domestic and international markets, the demand for epimedium extract is vigorous, and the demand for epimedium extract is in a state of short supply.
Because the epimedium planting technology is not popularized in a large range, compared with planting of other economic crops or medicinal materials, the benefit is not outstanding, the manual planting is still in a local small-scale test stage at present, and the epimedium medicinal materials basically all depend on wild resources at present. However, in recent years, the wild epimedium resource in the producing area is not retired and recovered because of the damage to the resource caused by the disorderly digging of farmers in the producing area, so that the epimedium resource is reduced year by year, and the price of the epimedium resource is high year by year.
Zhang Hai Yan is separated from Korean epimedium for the first time to obtain 3 '-carbonyl-2' -beta-L-quinosyl icariin (3 '-carbonyl-2' -0-L-quinovosylicarin, CQICA for short). The study of Mabaiping and the like finds that: CQICA is a precursor compound of icariin, and can be converted into icariin under specific conditions (e.g., heat treatment). The reported study on the content change of icariin in epimedium and wushanense medicinal materials subjected to heating treatment in Guobaulin and the like reports that the content of icariin in partial varieties of epimedium can be remarkably improved by heating the epimedium medicinal materials or powder at 150 ℃ for 30min, but the icariin precursor compound CQICA cannot be completely converted into the icariin under the condition, and the icariin is also partially degraded. The treatment method has high temperature requirement, is difficult to implement in a workshop on a large scale, and has the problems of incomplete conversion, icariin degradation and the like.
Disclosure of Invention
The invention aims to provide a process method for improving the yield of icariin, and aims to solve the problems of shortage of wild epimedium herb resources and high production cost of epimedium herb extracts at present. The method can obviously improve the yield of the icariin, greatly reduce the quantity of epimedium medicinal materials required for producing the same equivalent icariin, greatly reduce the production cost of the epimedium extract, greatly relieve the consumption of wild epimedium resources and avoid the exhaustion of the wild epimedium resources.
In order to achieve the above object, the present invention provides the following technical solutions:
a process method for improving the yield of icariin is characterized by comprising the following steps:
1) and (3) extracting: adding the epimedium raw material into a dissolving device, adding a solvent which is 3-50 times of the amount of the raw material, and extracting for 1-5 times to obtain an epimedium extracting solution.
2) And solid-liquid separation: mixing extractive solutions, and collecting supernatant of herba Epimedii.
3) And concentrating: and (3) concentrating the clear liquid obtained by solid-liquid separation by using a concentrator until the Brix value is 0.1-20% to obtain a clear concentrated liquid.
4) And purifying by macroporous resin: and adsorbing the epimedium clear liquid and/or clear concentrated liquid by using a macroporous adsorption resin column, washing the column with 1-15 times of pure water by volume to remove impurities, eluting with 20-95% ethanol by 2-10 times of volume by one step or multiple steps, and collecting epimedium ethanol eluate.
5) And concentrating: concentrating the ethanol eluent by a concentrator until the Brix value is 1-20 percent to obtain ethanol eluent concentrated solution.
6) And (3) hydrolysis: transferring the ethanol elution concentrated solution into a reaction container, adding a conversion reagent accounting for 0.01-5 wt% of the concentrated solution, reacting for at least 5 minutes, adding a neutralization reagent, adjusting the pH value to be neutral, and stopping the reaction to obtain the epimedium conversion solution.
7) And concentrating: and concentrating by using a concentrator until the relative density is 1.05-1.3 to obtain the epimedium conversion concentrated solution.
8) Drying and post-treatment: drying the concentrated solution by adopting proper drying equipment, and sieving to obtain the epimedium extract.
Further, the herba Epimedii comprises at least one of herba Epimedii, Korean herba Epimedii, herba Epimedii and its variant; the herba Epimedii raw material comprises herba Epimedii medicinal material, and non-transformed herba Epimedii extract and/or herba Epimedii extract.
Further, a centrifuge, a plate-and-frame filter press, a vacuum suction filter or a filter bag is adopted in the step 2) for solid-liquid separation.
Further, a macroporous resin purification step is also carried out before the step 7): adsorbing the conversion solution obtained in the step 6) by using a macroporous adsorption resin column, washing the column with 1-15 times of pure water by volume to remove impurities, eluting with 2-10 times of 20-95% ethanol by volume in one step or multiple steps, and collecting ethanol eluent.
Further, the epimedium extract or the concentrated solution thereof in the step 1), the epimedium clear solution in the step 2), the clear concentrated solution in the step 3) and/or the epimedium ethanol eluent in the step 4) are simultaneously sent to the step 6) for hydrolysis treatment.
Further, in the steps 1) to 5), 0.01 to 5 weight percent of conversion reagent is optionally added based on the total weight, and after reacting for at least 5 minutes, the neutralization reagent is added to adjust the pH value to be neutral.
Further, step 6) may be omitted after the optional addition of a conversion reagent in steps 1) to 5).
Further, the conversion reagent comprises at least one of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, concentrated ammonia water, triethylamine and a solution thereof; the transformation temperature is more than or equal to 10 ℃.
Further, the neutralizing agent in step 6) includes at least one of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, acetic acid, citric acid, oxalic acid, malic acid, maleic acid, fumaric acid, and a solution thereof.
The invention has the beneficial effects that:
firstly, the reaction system is simple: the existing patent relates to a process method for converting epimedin C into icariin by an enzyme method, which needs to be implemented in a specific reaction system (such as a pH buffer system with a specific range, a specific substrate concentration, a specific temperature and the like) in order to maintain the activity of the enzyme, and has higher requirements on the control of production process parameters. The invention has wide related process parameters, cheap and easily obtained reagents and is convenient for large-scale production and application.
Second, the cycle is short, high in efficiency: in the prior patent, compared with the reaction for at least 10 hours for enzyme conversion, the process method provided by the invention needs only about 5 minutes at the shortest time, so that the production period is greatly shortened, and the production efficiency is improved; in addition, the enzyme conversion reaction has strict requirements on the concentration of the substrate, the concentration of the substrate is generally several grams/liter, the conversion efficiency is low, the process method is suitable for conversion treatment of feed liquid with different substrate concentrations, and the production efficiency is far higher than that of an enzyme conversion process.
Thirdly, the production cost is greatly reduced: in the existing patent, the production cost of specific enzyme preparations required by enzyme conversion is high, the reaction volume is large, and a large amount of buffer solution is required for establishing an enzyme conversion system, so that the production cost is high. The invention relates to a process method which only uses a small amount of cheap reagents, has simple conversion process and high efficiency, and has far lower production cost than the enzyme conversion process.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described with reference to the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
300 kg of cut epimedium medicinal material (the icariin content is 0.55%) is put into a hot reflux extraction tank, and is refluxed and extracted for 3 times by 50% ethanol, the dosage of the solvent is 4200L, 3000L and 3000L respectively, and each extraction time is 1.5 h. Centrifuging to remove fine particles, mixing the three extractive solutions, cooling to 40 + -10 deg.C with circulating cooling water, adding 93L 1mol/L NaOH aqueous solution under stirring, standing at 40 + -10 deg.C for 2 hr, and adjusting pH to 6.5 with dilute hydrochloric acid. Concentrating under reduced pressure until the material liquid has no alcohol smell, and recovering ethanol to obtain 1000L concentrated solution. Adsorbing with 300 kg AB-8 macroporous adsorbent resin column at flow rate of 450L/h, washing with 600L purified water to remove impurities, eluting with 900L 70% ethanol, collecting 70% ethanol eluate, concentrating to relative density of 1.15, drying to obtain herba Epimedii extract 16.4 kg, and detecting icariin content of 15.5% by HPLC. The total yield of icariin was 154.1%.
Example 2
Adding 500 kg of cut herba Epimedii (icariin content of 0.55%) into a percolation tank, percolating with 7500L 50% ethanol at percolation rate of 40L/h. Collecting percolate at 6200L, concentrating under reduced pressure until the material liquid has no alcohol smell, recovering ethanol, centrifuging to remove fine particles, and collecting concentrated solution at 900L. Cooling to 60 +/-10 deg.c with circulating cooling water, and adding Na in 1mol/L while stirring2CO3Keeping the temperature at 60 + -10 deg.C for 12 hr, and adjusting pH to 7.0 with acetic acid. Adsorbing the trees by using 250 kg of D101 macroporousAdsorbing with lipid column at flow rate of 375L/h, washing with 750L purified water to remove impurities, eluting with 1000L 65% ethanol, collecting 65% ethanol eluate, concentrating to relative density of 1.09, drying to obtain herba Epimedii extract 25.8 kg, and detecting icariin content of 14.3% by HPLC. The total yield of icariin is 134.2%.
Example 3
Putting 3000 kg of cut herba Epimedii (icariin content is 0.25%) into 10 hot reflux extraction tanks, decocting with purified water for 3 times, wherein the solvent dosage in each tank is 4500L, 3600L and 3600L, and extracting for 1.5 hr each time. Centrifuging to remove fine particles, mixing extractive solutions of three times to obtain 105KL, cooling with circulating cooling water to below 80 deg.C, adsorbing with 4000 kg D101 macroporous adsorbent resin column at 16000L/h, washing with 6000L purified water to remove impurities, eluting with 12000L 80% ethanol, collecting 80% ethanol eluate, and concentrating under reduced pressure until the extractive solution has no alcohol smell to recover ethanol to obtain 2600L concentrated solution. Adding 100L of 5mol/L KOH aqueous solution while stirring, keeping the temperature at 50 +/-10 ℃, stirring for 30min, and adjusting the pH to 6.0 by using dilute sulfuric acid. Adsorbing with 2000 kg D101 macroporous adsorbent resin column at flow rate of 1000L/h, washing with 6000L purified water to remove impurities, eluting with 5000L 80% ethanol, collecting 80% ethanol eluate, concentrating under reduced pressure until the eluate has no alcohol smell, recovering ethanol, concentrating to relative density of 1.19, drying to obtain 75.9 kg herba Epimedii extract with icariin content of 14.9% by HPLC. The total yield of icariin is 150.8%.
Example 4
Adding 500 kg of cut herba Epimedii (icariin content of 0.55%) into a percolation tank, adding 300L of 2.5mol/L NaOH aqueous solution into 7500L 50% ethanol, and percolating at a speed of 50L/h. The colation is 6600L, and the pH is adjusted to 7.2 by oxalic acid. Concentrating under reduced pressure until the material liquid has no alcohol smell, recovering ethanol to obtain concentrated solution of about 1500L, and filtering with plate-and-frame filter to remove fine particles. Adsorbing by using a 300 kg D101 macroporous adsorption resin column, wherein the sample loading flow rate is 300L/h; washing with 3000L purified water to remove impurities; eluting with 900L 70% ethanol, collecting 70% ethanol eluate, concentrating to relative density of 1.09, drying to obtain herba Epimedii extract 28.5 kg, and detecting icariin content of 13.5% by HPLC. The total yield of icariin was 139.9%.
Example 5
Adding 750L of 20% ethanol into 1000L extraction tank, stirring, and adding 50 kg herba Epimedii extract (icariin content is 10.6%). Heating to 45 deg.C, stirring for 30 min. Adding 30L of 5mol/L NaOH aqueous solution, treating for 5min, and adjusting pH to 7.0 with dilute phosphoric acid. Fine particles were removed by filtration using a plate and frame filter. Adsorbing with 500 kg mixed D101/AB-8 macroporous adsorbent resin column at flow rate of 125L/h, washing with 4000L purified water to remove impurities, eluting with 1500L 80% ethanol, collecting 80% ethanol eluate, concentrating to relative density of 1.18, drying to obtain herba Epimedii extract 47.9 kg, and detecting icariin content of 15.1% by HPLC. The total yield of icariin was 136.5%.
Comparative example 1
Putting 3000 kg of cut herba Epimedii (icariin content is 0.25%) into 10 hot reflux extraction tanks, decocting with purified water for 3 times, wherein the solvent dosage in each tank is 4500L, 3600L and 3600L, and extracting for 1.5 hr each time. Centrifuging to remove fine particles, mixing the three extractive solutions to obtain 104KL, cooling with circulating cooling water to below 80 deg.C, adsorbing with 4000 kg D101 macroporous adsorbent resin column at sample flow rate of 15000L/h, washing with 4000L purified water to remove impurities, eluting with 16000L 70% ethanol, collecting 70% ethanol eluate, concentrating under reduced pressure to relative density of 1.14, drying to obtain 77.1 kg herba Epimedii extract, and detecting icariin content of 9.6% by HPLC. The total yield of icariin was 98.7%.
As can be seen from the above examples and comparative examples, the invention adds the transforming agent to carry out alkaline transformation treatment on the extracting solution, thereby greatly improving the icariin content and the total yield of the icariin.
The above-mentioned embodiments only express the embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. A process method for improving the yield of icariin is characterized by comprising the following steps:
1) and (3) extracting: adding the epimedium raw material into a dissolving device, adding a solvent which is 3-50 times of the amount of the raw material, and extracting for 1-5 times to obtain an epimedium extracting solution.
2) And solid-liquid separation: mixing extractive solutions, and collecting supernatant of herba Epimedii.
3) And concentrating: and (3) concentrating the clear liquid obtained by solid-liquid separation by using a concentrator until the Brix value is 0.1-20% to obtain a clear concentrated liquid.
4) And purifying by macroporous resin: and adsorbing the epimedium clear liquid and/or clear concentrated liquid by using a macroporous adsorption resin column, washing the column with 1-15 times of pure water by volume to remove impurities, eluting with 20-95% ethanol by 2-10 times of volume to perform one-step or multi-step elution, and collecting epimedium ethanol eluate.
5) And concentrating: concentrating the ethanol eluent by a concentrator until the Brix value is 1-20 percent to obtain ethanol eluent concentrated solution.
6) And (3) hydrolysis: transferring the ethanol elution concentrated solution into a reaction container, adding a conversion reagent accounting for 0.01-5 wt% of the concentrated solution, reacting for at least 5 minutes, adding a neutralization reagent, adjusting the pH value to be neutral, and stopping the reaction to obtain the epimedium conversion solution.
7) And concentrating: and concentrating by using a concentrator until the relative density is 1.05-1.3 to obtain the epimedium conversion concentrated solution.
8) Drying and post-treatment: drying the concentrated solution by adopting proper drying equipment, and sieving to obtain the epimedium extract.
2. The process of claim 1, wherein the epimedium comprises at least one of epimedium, epimedium koreanum, epimedium dauricum and its variants; the herba Epimedii raw material comprises herba Epimedii medicinal material, and non-transformed herba Epimedii extract and/or herba Epimedii extract.
3. The process of claim 1, wherein step 2) comprises performing solid-liquid separation using a centrifuge, a plate-and-frame filter press, a vacuum suction filter, or a filter bag.
4. The process according to claim 1, characterized in that step 7) is preceded by a macroporous resin purification step: adsorbing the conversion solution obtained in the step 6) by using a macroporous adsorption resin column, washing the column with 1-15 times of pure water by volume to remove impurities, eluting with 2-10 times of 20-95% ethanol by volume in one step or multiple steps, and collecting ethanol eluent.
5. The process of claim 1, wherein the epimedium extract or the concentrated solution thereof in the step 1), the epimedium clear solution in the step 2), the clear concentrated solution in the step 3) and/or the epimedium ethanol eluate in the step 4) are simultaneously fed into the step 6) for hydrolysis treatment.
6. The process of claim 1, wherein in steps 1) to 5) optionally 0.01 to 5 wt.% of a conversion reagent is added, and after at least 5 minutes of reaction a neutralising agent is added to adjust the pH to neutral.
7. The process of claim 6 wherein step 6) is omitted.
8. The process of claim 1 or 6, wherein the conversion reagent comprises at least one of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, concentrated ammonia, triethylamine, and solutions thereof; the transformation temperature is more than or equal to 10 ℃.
9. The process of claim 1 wherein the neutralizing agent in step 6) comprises at least one of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, acetic acid, citric acid, oxalic acid, malic acid, maleic acid, fumaric acid, and solutions thereof.
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| CN114249777A (en) * | 2021-11-19 | 2022-03-29 | 安徽金源药业有限公司 | Method for extracting icariin |
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| CN101416995A (en) * | 2007-10-24 | 2009-04-29 | 南京宇道科技开发有限公司 | Epimedium extract and preparation method, preparation and use thereof |
| CN108558812A (en) * | 2018-03-26 | 2018-09-21 | 北京珅奥基医药科技有限公司 | A kind of method that acidolysis prepares icariine |
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| CN101416995A (en) * | 2007-10-24 | 2009-04-29 | 南京宇道科技开发有限公司 | Epimedium extract and preparation method, preparation and use thereof |
| CN108558812A (en) * | 2018-03-26 | 2018-09-21 | 北京珅奥基医药科技有限公司 | A kind of method that acidolysis prepares icariine |
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| CN114249777A (en) * | 2021-11-19 | 2022-03-29 | 安徽金源药业有限公司 | Method for extracting icariin |
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