CN101348488A - Separation and extraction method for camptothecine - Google Patents
Separation and extraction method for camptothecine Download PDFInfo
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- CN101348488A CN101348488A CNA2008100737811A CN200810073781A CN101348488A CN 101348488 A CN101348488 A CN 101348488A CN A2008100737811 A CNA2008100737811 A CN A2008100737811A CN 200810073781 A CN200810073781 A CN 200810073781A CN 101348488 A CN101348488 A CN 101348488A
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- camptothecine
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- ethyl acetate
- extracting method
- filtration
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Abstract
The invention relates to the natural active ingredient extraction field from plants, in particular to a method for separating and extracting camptothecin. The technological line of the invention is as follows: common camptotheca fruits and common camptotheca leaves are taken as materials, and the technological steps are as follows: crushing, leaching of dilute sodium hydroxide solution, acid precipitation and impurity removal of the leaching solution, micro-filtration, ultrafiltration, nanofiltration, column chromatography by macropore adsorbent resins, desorption by ethanol and condensation of a stripping liquid to an extractive, extraction by ethyl acetate and crystallization of a extraction liquid to obtain a coarse product of camptothecin,recrystallization of a mixing liquid of the ethyl acetate and the acetone to obtain refined products of camptothecin. The method for separating and extracting camptothecin of the invention can fully leach out active ingredients of materials by multiple leaching, and after the processes of micro-filtration, ultrafiltration, nanofiltration concentration, column chromatography by macropore adsorbent resins and multiple crystallization, the extraction rate of the invention is 70 to 80 percent against the content of active ingredient camptothecin of the materials, and the purity of products extracted is more than 98 percent.
Description
(1) technical field:
The present invention relates to extract natural effective ingredient field from plant, relating in particular to a kind of is raw material with fruit of camptotheca acuminata, leaf of Common Camptotheca, produces the separating and extracting method of camptothecine.
(2) background technology:
(Camptothecin CPT), is faint yellow plate crystal to camptothecine, and molecular formula is C
20H
16N
2O
4, molecular weight is 348.3, molecular structural formula is:
Camplotheca acuminata (Camptothecaacuminata Demce) is the distinctive a kind of tall and big deciduous tree of China, belongs to the Cornales Nyssaceae, is distributed widely in the Yangtze valley and each provinces and regions, south, and Guangxi is important main product ground.1966, the Monroe E.Wall of the U.S. isolated camptothecine first from the camplotheca acuminata extract, had antitumour activity through this tryptophane one terpenes alkaloid of tumour evidence, had caused people's extensive concern.The camptothecine of discovering of the seventies in 20th century all has unique curative effect to multiple malignant tumours such as cancer of the stomach, colorectal carcinoma, liver cancer, bladder cancer, leukemia, chronic granulocytic hemophilia.Can block the synthetic of topoisomerase I (Topo I) to Y.H.Hsiang discovery camptothecine in 1985, Topo I is a kind of and the closely-related a kind of enzyme of cell fission, the generation of blocking-up this kind of enzyme can stop the growth of cancer cells, this is the anticancer mechanism of camptothecine uniqueness just, and this discovery has started the new upsurge of camptothecine and derivative research thereof again.
At present, camptothecine is generally extracted from camplotheca acuminata and is obtained.State Intellectual Property Office discloses the patents of several relevant camptothecine extraction processes respectively at the following time: are extracting method of disclosed a kind of camptothecine technology 1:1996 Mays 8, patent publication No. is CN1121920, this patent of invention is a raw material with fruit of camptotheca acuminata or root skin, adopt abrasive dust → poach → boil liquid to concentrate → paste → ethanol to separate gummy impurity → separate out crude product → chloroform mixed solution repeatedly to obtain the operational path of product behind the recrystallization, and in abrasive dust → poach operation, add oxidation inhibitor.Present method facility investment is few, the purity 92% of drying products, and output capacity is about 2/10000; Technology 2:1999 December disclosed a kind of camptothecine on the 22nd production method, patent publication No. is CN1239096, this invention is main raw material with the leaf of Common Camptotheca, fruit is an auxiliary material, leftover materials after pulverizing → ethanol percolation → supercritical carbon dioxide extraction diacolation extracts → concentrated percolate and extraction liquid → macroporous adsorbent resin column chromatography → recrystallization obtain the operational path of product, product purity is 97.5%, productive rate 2/10000～3/10000; Technology 3:2000 April disclosed a kind of camptothecine on the 26th production method, patent publication No. is CN1251366, this invention is a raw material with leaf of Common Camptotheca and seed, behind pulverizing → ethanol and water diacolation → concentrated percolate → macroporous adsorbent resin column chromatography → recrystallization, obtain the operational path of product, product purity is 97.5%, productive rate 2/10000～3/10000; Technology 4:2003 April disclosed camptothecine on the 16th production technique, patent publication No. is CN1410426, this invention is raw material with the leaf of Common Camptotheca, be concentrated into the operational path that obtains product after medicinal extract → solvent extraction and crystallization get crude product → recrystallization through pulverizing → ethanol or buck extraction → extraction liquid, product purity is 97.5%, productive rate 2/10000; Technology 5:2005 June disclosed camptothecine on the 1st production technique, patent publication No. is CN1621406, this invention is that 8/10000～10/10000 fruit of camptotheca acuminata is a raw material with camptothecine content, through pulverizing → ethanol percolation → concentrate percolate → filter filtrate → solvent extraction → mixed solvent 1 recrystallization purifying → mixed solvent 2 recrystallization purifyings get coarse-grain → mixed solvent 3 refining purifying and get elaboration, product purity 94%, product yield 4.0/10000.
The applicant finds that after deliberation the product yield of technology 1 and technology 4 is all lower, is about 2/10000; The product yield of technology 2 and technology 3 all is no more than 3/10000, has wherein also adopted supercritical carbon dioxide extraction in the technology 2, and production technique is comparatively complicated, and investment of production equipment is bigger, and cost is higher; Though the yield of the product of technology 5 can reach 4/10000, its precondition is that the content of the camptothecine in the raw material of selecting for use must reach 8/10000～10/10000 fruit of camptotheca acuminata, and owing to be raw material with the fruit of camptotheca acuminata only, also is subjected to seasonal restriction.
(3) summary of the invention:
It is raw material with fruit of camptotheca acuminata, leaf of Common Camptotheca that the technical problem to be solved in the present invention provides a kind of, and the effective constituent in the raw material (camptothecine) is extracted the separating and extracting method of the camptothecine of yield height, good product purity.
Can realize the separating and extracting method of the camptothecine of above-mentioned purpose, with Fructus Camptothecae Acuminatae, leaf of Common Camptotheca is raw material, through the pulverizing → diluted sodium hydroxide solution lixiviate → heavy removal of impurities → micro-filtration of vat liquor acid → ultrafiltration → nanofiltration → macroporous adsorbent resin column chromatography → alcohol desorption, the ethanolysis imbibition is concentrated into medicinal extract → ethyl acetate extraction, the extraction liquid crystallization, the mixing solutions that obtains camptothecine crude product → ethyl acetate-acetone carries out recrystallization and obtains the camptothecine elaboration.
The content of camptothecine is bigger in fruit of camptotheca acuminata, the leaf of Common Camptotheca, and between 2/10000～14/10000, the present invention is that 7/10000～8/10000 fruit of camptotheca acuminata, leaf of Common Camptotheca are raw material with camptothecine content preferably; Having overcome single is the seasonal restricted problem that raw material is subjected to the fruit of camptotheca acuminata, has fully guaranteed the source of raw material.The degree of grinding of described raw material can be determined as required, generally carries out meal and gets final product, and the granularity of the raw material after promptly pulverizing is not less than 20 orders.
In order fully to leach the active ingredient camptothecin in the raw material, raw material can be carried out extracted many times with diluted sodium hydroxide solution, generally be advisable for 3 times with lixiviate, the time of each lixiviate and the consumption of diluted sodium hydroxide solution can be determined as required, be generally each lixiviate 2～3 hours, the consumption of each lixiviate diluted sodium hydroxide solution is 15～20ml/ (a g raw material); After lixiviate was finished, the vat liquor that merges 3 lixiviates entered next procedure again.Lixiviate is generally carried out at normal temperatures, and described diluted sodium hydroxide solution is that mass concentration is 0.5%～1.5% sodium hydroxide solution.
The heavy removal of impurities of described vat liquor acid is that the pH value with vat liquor transfers to neutrality, again the process of carrying out coarse filtration through 120～300 purpose filter clothes.Because vat liquor is when diluted sodium hydroxide solution soaks, brought a certain amount of impurity inevitably into, in order to remove the large particulate matter in these impurity and the vat liquor, can be earlier the pH value of vat liquor be transferred to neutrality, carry out coarse filtration to achieve the above object through 120～300 purpose filter clothes again.Wherein, can use hydrochloric acid during the pH value of transferring vat liquor, or sulfuric acid, or acetic acid etc. other vat liquor pH value can be transferred to neutral acid.
In order further to remove particulate and macromole impurity such as suspended solids in the vat liquor, bacterium, colloid, solid protein, also the vat liquor after the coarse filtration can be carried out micro-filtration with microfiltration membrane; Described microfiltration membrane can be ceramic membrane or metallic membrane, preferably adopts the ceramic membrane of 30nm to carry out micro-filtration.
To the vat liquor molecular weight cut-off behind the micro-filtration is that 10000 film carries out ultrafiltration, to remove molecular weight in the vat liquor greater than 10000 material.
To the vat liquor molecular weight cut-off after the ultrafiltration is that 200 film carries out nanofiltration and concentrates.In this nanofiltration process, inorganic salt and water can pass through, and make that solvent and solute separately reach spissated purpose, and do not have phase transformation in concentration process in the vat liquor.
Described macroporous adsorbent resin can be polar macroporous adsorption resin, also can be nonpolar macroporous adsorption resin, preferred AB-8, or HPD100, or HPD300, or D101 macroporous adsorbent resin; Wherein be best with AB-8.Vat liquor after nanofiltration concentrates is directly gone up macroporous adsorptive resins and is adsorbed, and the flow velocity of last sample is with 3～8 times of column volumes/hour be advisable, until macroporous adsorptive resins saturated (passing through high-performance liquid chromatogram determination); Wash with water to washings colourlessly then,, use alcohol desorption again to remove the non-adsorbable impurity of resin such as inorganic salt; It is 50%～90% aqueous ethanolic solution that the used ethanol of described desorb can be volumetric concentration, and its consumption is generally 2.5～3.5 times of column volumes; Described ethanolysis imbibition is condensed into the medicinal extract shape, and its proportion is generally 30～35 Baumes.
For active ingredient camptothecin contained in the medicinal extract is extracted more completely, available ethyl acetate is carried out 3 extractions to medicinal extract; Wherein, when extracting for the first time, the consumption of ethyl acetate is 8～10ml/ (a g medicinal extract); When extracting for the second time, the consumption of ethyl acetate is 4～6ml/ (a g medicinal extract); When extracting for the third time, the consumption of ethyl acetate is 2～4ml/ (a g medicinal extract).Combining extraction liquid concentrates the back with it and places crystallization, and the crystal of separating out is the camptothecine crude product.For the better crystallization of camptothecine in the extraction liquid is come out, the extraction liquid after merging can be concentrated into 0.02～0.03 times of the total consumption of ethyl acetate.
Ethyl acetate and acetone volume ratio are 1: 4～4: 1 in the mixing solutions of described ethyl acetate-acetone, and its consumption is 5～10ml/ (a g camptothecine crude product); The number of times of described recrystallization is 2～3 times.
Also can carry out conventional drying, pulverizing, packing to the camptothecine elaboration that recrystallization obtains, obtain the camptothecine product.
The invention has the advantages that:
1, be the raw material production camptothecine with fruit of camptotheca acuminata, leaf of Common Camptotheca, raw material is gathered conveniently, and the camplotheca acuminata resource is not had destruction, has realized Sustainable utilization of resources, has solved raw material supply and has been subjected to the seasonal problem that limits;
2, the big organic solvents of toxicity such as chloroform are not used in this invention in whole process of production, have reduced the harm to the production operation personnel health;
3, technology of the present invention is simple, and processing ease is easy to suitability for industrialized production;
4, adopt membrane separation technique, the separation efficiency height, equipment volume is little, and the processing power of membrane sepn is easy to amplify, and easy and other extraction processes couplings;
5, the present invention fully leaches effective constituent in the raw material by extracted many times, again through micro-filtration, ultrafiltration, nanofiltration concentrate, macroporous adsorbent resin column chromatography and crystalline technology repeatedly, make extraction yield of the present invention can reach 70%～80% of active ingredient camptothecin content in the raw material, extract the product purity that obtains and to reach more than 98%; When selecting camptothecine content for use is 7/10000～8/10000 raw material when carrying out separation and Extraction, and its product yield can reach 5/10000～6/10000, and product purity is 98.5%.
(4) embodiment:
Embodiment 1
Get 10 kilograms of camptothecine contents and be 7/10000～8/10000 fruit of camptotheca acuminata dry product, be crushed to 20 orders; Be 0.5% sodium hydroxide solution lixiviate at normal temperatures 2 hours earlier, isolate fruit of camptotheca acuminata with 150 mass per liter concentration; Add 200 mass per liter concentration again and be 0.5% sodium hydroxide solution lixiviate at normal temperatures 2 hours, and isolated fruit of camptotheca acuminata; The mass concentration that adds 150 liters again is 0.5% sodium hydroxide solution lixiviate at normal temperatures 2 hours, isolates fruit of camptotheca acuminata, merges the vat liquor of three lixiviates; With hydrochloric acid its pH value is transferred to neutrality, carry out coarse filtration through 120 purpose filter clothes again; Vat liquor after the coarse filtration is carried out micro-filtration with the ceramic membrane of 30nm; It is 10000 ultrafiltration that vat liquor behind the micro-filtration is carried out molecular weight cut-off; It is that 200 nanofiltration concentrates that vat liquor after the ultrafiltration is carried out molecular weight cut-off; The gained concentrated solution is with the flow velocity of 5 times of column volume/h, last AB-8 macroporous adsorptive resins adsorbs, absorption back with deionized water be washed till washings colourless after, be that 80% aqueous ethanolic solution carries out desorb with 2.5 times of column volumes, volumetric concentration again, collect stripping liquid, with its concentrating under reduced pressure under 70～80 ℃ of conditions medicinal extract that to obtain 1 kilogram of proportion be 35 Baumes; Respectively with 8 liters, 5 liters, 3 liters ethyl acetate extraction 3 times, combining extraction liquid, and be concentrated into 0.32 liter is placed and is separated out camptothecine crude product 15 grams after 12 hours with medicinal extract; Use ethyl acetate-acetone mixing solutions (1: 1) of 75 milliliters, 100 milliliters that the camptothecine crude product is carried out recrystallization more respectively, obtain 5.10 gram camptothecine products; Its purity is 98.53%, and yield is 5.1/10000.
Embodiment 2
Get the double centner camptothecine content and be 3/10000～4/10000 leaf of Common Camptotheca dry product, be crushed to 10～20 orders; Be 1.0% sodium hydroxide solution lixiviate at normal temperatures 3 hours earlier, isolate leaf of Common Camptotheca with 2000 mass per liter concentration; Add 2000 mass per liter concentration again and be 1.0% sodium hydroxide solution lixiviate at normal temperatures 2 hours, and isolated leaf of Common Camptotheca; The mass concentration that adds 2000 liters again is 1.0% sodium hydroxide solution lixiviate at normal temperatures 2 hours, isolates leaf of Common Camptotheca, merges the vat liquor of three lixiviates; With sulfuric acid its pH value is transferred to neutrality, carry out coarse filtration through 300 purpose filter clothes again; Vat liquor after the coarse filtration is carried out micro-filtration with the metallic membrane of 30nm; It is 10000 ultrafiltration that vat liquor behind the micro-filtration is carried out molecular weight cut-off; It is that 200 nanofiltration concentrates that vat liquor after the ultrafiltration is carried out molecular weight cut-off; The gained concentrated solution is with the flow velocity of 8 times of column volume/h, last D101 macroporous adsorptive resins adsorbs, absorption back with distilled water be washed till washings colourless after, be that 50% aqueous ethanolic solution carries out desorb with 3.5 times of column volumes, volumetric concentration again, collect stripping liquid, it is concentrated the medicinal extract that to obtain 13 kilograms of proportions be 30 Baumes; Respectively with 130 liters, 52 liters, 52 liters ethyl acetate extraction 3 times, combining extraction liquid, and be concentrated into 7 liters is placed and is separated out camptothecine crude product 50 grams after 14 hours with medicinal extract; Use the mixing solutions (1: 4) of 500 milliliters, 400 milliliters, 300 milliliters ethyl acetate-acetone that the camptothecine crude product is carried out recrystallization more respectively, obtain 25.2 gram camptothecine products; Its purity is 98.12%, and yield is 2.52/10000.
Embodiment 3
Getting 500 kilograms of camptothecine contents and be 6/10000 leaf of Common Camptotheca dry product, is 1.0% sodium hydroxide solution lixiviate at normal temperatures 3 hours with 8000 mass per liter concentration earlier behind the meal, isolates leaf of Common Camptotheca; Add 10000 mass per liter concentration again and be 1.5% sodium hydroxide solution lixiviate at normal temperatures 2 hours, and isolated leaf of Common Camptotheca; The mass concentration that adds 7500 liters again is 0.5% sodium hydroxide solution lixiviate at normal temperatures 3 hours, isolates leaf of Common Camptotheca, merges the vat liquor of three lixiviates; With acetic acid its pH value is transferred to neutrality, carry out coarse filtration through 200 purpose filter clothes again; Vat liquor after the coarse filtration is carried out micro-filtration with the ceramic membrane of 30nm; It is 10000 ultrafiltration that vat liquor behind the micro-filtration is carried out molecular weight cut-off; It is that 200 nanofiltration concentrates that vat liquor after the ultrafiltration is carried out molecular weight cut-off; The gained concentrated solution is with the flow velocity of 3 times of column volume/h, last HPD300 macroporous adsorptive resins adsorbs, absorption back with deionized water be washed till washings colourless after, be that 90% aqueous ethanolic solution carries out desorb with 3 times of column volumes, volumetric concentration again, collect stripping liquid, it is concentrated the medicinal extract that to obtain 60 kilograms of proportions be 32 Baumes; Respectively with 540 liters, 300 liters, 120 liters ethyl acetate extraction 3 times, combining extraction liquid, and be concentrated into 24 liters is placed and is separated out camptothecine crude product 450 grams after 12 hours with medicinal extract; Use ethyl acetate-acetone mixing solutions (2: 3) of 4500 milliliters, 2700 milliliters that the camptothecine crude product is carried out recrystallization more respectively, obtain 238 gram camptothecine products; Its purity is 98.08%, and yield is 4.76/10000.
Claims (10)
1, the separating and extracting method of camptothecine, it is characterized in that: with Fructus Camptothecae Acuminatae, leaf of Common Camptotheca is raw material, through the pulverizing → diluted sodium hydroxide solution lixiviate → heavy removal of impurities → micro-filtration of vat liquor acid → ultrafiltration → nanofiltration → macroporous adsorbent resin column chromatography → alcohol desorption, the ethanolysis imbibition is concentrated into medicinal extract → ethyl acetate extraction, the extraction liquid crystallization, the mixing solutions that obtains camptothecine crude product → ethyl acetate-acetone carries out recrystallization and obtains the camptothecine elaboration.
2, the separating and extracting method of camptothecine according to claim 1 is characterized in that: the number of times of described diluted sodium hydroxide solution lixiviate is 3 times, each lixiviate 2～3 hours; During each lixiviate, the consumption of diluted sodium hydroxide solution is 15～20ml/ (a g raw material).
3, the separating and extracting method of camptothecine according to claim 1 is characterized in that: described micro-filtration is that the vat liquor after the coarse filtration is filtered with microfiltration membrane.
4, the separating and extracting method of camptothecine according to claim 3 is characterized in that: described microfiltration membrane is the ceramic membrane of 30nm.
5, the separating and extracting method of camptothecine according to claim 1 is characterized in that: described ultrafiltration is to be 10000 membrane filtration with the vat liquor molecular weight cut-off behind the micro-filtration.
6, the separating and extracting method of camptothecine according to claim 1 is characterized in that: described nanofiltration is to be 200 membrane filtration with the vat liquor molecular weight cut-off after the ultrafiltration.
7, according to the separating and extracting method of any one described camptothecine in the claim 1～6, it is characterized in that: the used ethanol of described desorb is that volumetric concentration is 50%～90% aqueous ethanolic solution, and its consumption is 2.5～3.5 times of column volumes.
8, according to the separating and extracting method of any one described camptothecine in the claim 1～6, it is characterized in that: ethyl acetate extraction 3 times of described medicinal extract, when extracting for the first time, the consumption of ethyl acetate is 8～10ml/ (a g medicinal extract); When extracting for the second time, the consumption of ethyl acetate is 4～6ml/ (a g medicinal extract); When extracting for the third time, the consumption of ethyl acetate is 2～4ml/ (a g medicinal extract).
9, according to the separating and extracting method of any one described camptothecine in the claim 1～6, it is characterized in that: the volume ratio of ethyl acetate and acetone is 1: 4～4: 1 in the mixing solutions of described ethyl acetate-acetone, and its consumption is 5～10ml/ (a g camptothecine crude product).
10, according to the separating and extracting method of any one described camptothecine in the claim 1～6, it is characterized in that: the number of times of described recrystallization is 2～3 times.
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| CNA2008100737811A CN101348488A (en) | 2008-09-12 | 2008-09-12 | Separation and extraction method for camptothecine |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093375A (en) * | 2011-02-28 | 2011-06-15 | 中国科学院过程工程研究所 | Method for extracting steam explosion common camptotheca fruits and preparing camptothecin |
| CN102453035A (en) * | 2010-10-25 | 2012-05-16 | 温州大学 | Extraction and preparation method for camptothecin |
| CN110305144A (en) * | 2019-06-12 | 2019-10-08 | 苏州岚云医药科技有限公司 | A kind of technique using membrane technology separating natural anticancer drug |
-
2008
- 2008-09-12 CN CNA2008100737811A patent/CN101348488A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453035A (en) * | 2010-10-25 | 2012-05-16 | 温州大学 | Extraction and preparation method for camptothecin |
| CN102453035B (en) * | 2010-10-25 | 2014-07-02 | 温州大学 | Extraction and preparation method for camptothecin |
| CN102093375A (en) * | 2011-02-28 | 2011-06-15 | 中国科学院过程工程研究所 | Method for extracting steam explosion common camptotheca fruits and preparing camptothecin |
| CN110305144A (en) * | 2019-06-12 | 2019-10-08 | 苏州岚云医药科技有限公司 | A kind of technique using membrane technology separating natural anticancer drug |
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