CN1124249A - Antineoplastic new poria polysaccharide water soluble derivative - Google Patents
Antineoplastic new poria polysaccharide water soluble derivative Download PDFInfo
- Publication number
- CN1124249A CN1124249A CN 94112670 CN94112670A CN1124249A CN 1124249 A CN1124249 A CN 1124249A CN 94112670 CN94112670 CN 94112670 CN 94112670 A CN94112670 A CN 94112670A CN 1124249 A CN1124249 A CN 1124249A
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- Prior art keywords
- pachymaran
- sulfonylation
- new
- acetylation
- pachymose
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- Polysaccharides And Polysaccharide Derivatives (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The Smith degradation method is used to remove the glycosyl branched chain in the pachyman to obtain new pachyman possessing of the antimitotic activeness. The new pachyman is the pure beta (1-3) combined dextran which is unsoluble in water and cannot be made into injection solution, it is fail to respond to oral administration. Said invention uses the methods of oxidizing, sulphonylizing and acetylizing separately to derive the new pachyman into water soluble oxidized new pachyman, sulphenylized new pachyman and acetylized new pachyman. These new water soluble derivants of new pachyman are proved by animal test to have the antimitotic action and immunoenhancement function.
Description
Contain Pachymose in the Poria cocos, its structure is a β (1 → 6) bonded glucosyl group side chain and 1～2 β (1 → 6) bonded glucosyl group to be arranged at interval in per 50 β (1 → 3) bonded glucose unit.Anti-tumor experiment shows that Pachymose does not have anti-tumor activity, and β in the Pachymose (1 → 6) bonded glucose unit is removed with the Smith degradation method, promptly obtains the pachymaran of anti-tumor activity.Pachymaran is water insoluble, can't make injection liquid, and is oral invalid, influenced further pharmacological research and clinical application.Once there was patent report pachymaran to be made soluble derivatives such as carboxymethyl, hydroxyethyl and urea element, but studied more than two decades, do not enter clinical application.This patent with glucose unit in the pachymaran-CH
2OH is oxidized to COOH, again with the alkali salify, promptly make can be water-soluble have antitumor and oxidation pachymaran raise immunity.---triethylamine---chlorsulfonic acid is the hydroxyl sulfonation of sulphonating agent with glucose unit in the pachymaran with dimethyl formamide, again with the alkali salify, promptly makes the water-soluble part sulfonylation pachymaran of energy.With dimethyl sulfoxide (DMSO)---pyridine---diacetyl oxide be acetylizing agent with the pachymaran acetylize, promptly make can be water-soluble the partial acetylation pachymaran.Part sulfonylation and partial acetylation pachymaran also have antitumor, raise immunity effect.
Japan has sulfonation and the acetylate of bibliographical information Curdlan (also being β (1 → 3) bonded dextran) that anti-tumor activity is arranged; but pachymaran is different polysaccharide with Curdlan; the pachymaran molecular weight is about 30,000, and the Curdlan molecular weight is about 90,000.
Pachymose is dissolved with phosphoric acid, and phosphoric acid concentration should be controlled at 20～70%, and phosphoric acid concentration is too high, and then to be dissolved in its medium viscosity big for polysaccharide, can't stir, and the low excessively oxidizing reaction that is unfavorable for is carried out.
Pachymose is the energy homodisperse in dimethyl formamide, is beneficial to sulfonylation and evenly carries out.
Pachymose is soluble in DMSO, so be that solvent carries out acetylize with DMSO.
Embodiment 1
Get Poria powder 20g, extract with 1M NaOH stirring at room, extracting solution adds acetic acid and gets the Pachymose precipitation, and centrifugal repeatedly again, washing and dialysis are with NaIO
46g adds in the suspension of Pachymose, transfers PH to 5, and the room temperature lucifuge stirred after 3 days, and glycerol adding 5ml stirred 4 hours, dialysis, and dialyzed solution is transferred about PH to 7, adds NaBH
42g, stirring at room 4 hours adds sulfuric acid again and is 2,100 ℃ to PH and stirred hydrolysis 2 hours, and is centrifugal, dialyse precipitation, drying precipitated, promptly obtain pachymaran.Pachymaran is dissolved in 30% phosphoric acid, adds Sodium Nitrite 10g, stirring at room 4 hours is transferred about PH to 7 with NaOH, the centrifugal precipitation of going, and supernatant liquor is centrifugal, and dialysis with the dialyzed solution drying, promptly obtains oxidation pachymaran (12g).Glucuronic acid content is 55% in the oxidation pachymaran that obtains in this way, has the effect of anti-tumor activity and raise immunity.
Embodiment 2
Get Poria powder 20g, extract with 1M NaOH stirring at room, extracting solution adds acetic acid and gets the Pachymose precipitation, and centrifugal repeatedly again, washing and dialysis are with NaIO
46g adds in the suspension of Pachymose, transfers PH to 5, and the room temperature lucifuge stirred after 3 days, and glycerol adding 5ml stirred 4 hours, dialysis, and dialyzed solution is transferred about PH to 7, adds NaBH
42g, stirring at room 4 hours adds sulfuric acid again and is 2,100 ℃ to PH and stirred hydrolysis 2 hours, and is centrifugal, dialyse precipitation, drying precipitated, promptly obtain pachymaran.Pachymaran is dissolved in 60% phosphoric acid, adds Sodium Nitrite 15g, stirring at room 6 hours is transferred about PH to 7 with NaOH, and the centrifugal precipitation of going with the supernatant liquor dialysis, with the dialyzed solution drying, promptly obtains oxidation pachymaran (13g).The content of glucuronic acid is 90% in the oxidation pachymaran that obtains in this way, has the effect of anti-tumor activity and raise immunity.
Embodiment 3
Get Poria powder 20g, extract with 1M NaOH stirring at room, extracting solution adds acetic acid and gets the Pachymose precipitation, and centrifugal repeatedly again, washing and dialysis are with NaIO
46g adds in the suspension of Pachymose, transfers PH to 5, and the room temperature lucifuge stirred after 3 days, and glycerol adding 5ml stirred 4 hours, dialysis, and dialyzed solution is transferred about PH to 7, adds NaBH
42g, stirring at room 4 hours adds sulfuric acid again and is 2,100 ℃ to PH and stirred hydrolysis 2 hours, and is centrifugal, dialyse precipitation, drying precipitated, promptly obtain pachymaran.Will.Pachymaran is dissolved in the dimethyl formamide, adds the 10ml triethylamine, and the ice bath state drips chlorsulfonic acid 8ml down, stirs 2 hours, transfers about PH to 7 with NaOH, the centrifugal supernatant liquor that gets, and dialysis with the dialyzed solution drying, promptly obtains sulfonylation pachymaran (10g).The sulfonylation degree of the sulfonylation pachymaran that obtains in this way is 0.6, has antitumor, raise immunity and AIDS resisting virus function.
Embodiment 4
Get Poria powder 20g, extract with 1M NaOH stirring at room, extracting solution adds acetic acid and gets the Pachymose precipitation, and centrifugal repeatedly again, washing and dialysis are with NaIO
46g adds in the suspension of Pachymose, transfers PH to 5, and the room temperature lucifuge stirred after 3 days, and glycerol adding 5ml stirred 4 hours, dialysis, and dialyzed solution is transferred about PH to 7, adds NaBH
42g, stirring at room 4 hours adds sulfuric acid again and is 2,100 ℃ to PH and stirred hydrolysis 2 hours, and is centrifugal, dialyse precipitation, drying precipitated, promptly obtain pachymaran.Pachymaran is dissolved in the dimethyl formamide, adds the 20ml triethylamine, the ice bath state drips chlorsulfonic acid 20ml down; stirred 2 hours, and transferred about PH to 7, the centrifugal supernatant liquor that gets with NaOH; dialysis with the dialyzed solution drying, promptly obtains sulfonylation pachymaran (11g).The sulfonylation degree of the sulfonylation pachymaran that obtains in this way is 1.1, has antitumor, raise immunity and AIDS resisting virus function.
Embodiment 5
Get Poria powder 20g, extract with 1M NaOH stirring at room, extracting solution adds acetic acid and gets the Pachymose precipitation, and centrifugal repeatedly again, washing and dialysis are with NaIO
46g adds in the suspension of Pachymose, transfers PH to 5, and the room temperature lucifuge stirred after 3 days, and glycerol adding 5ml stirred 4 hours, dialysis, and dialyzed solution is transferred about PH to 7, adds NaBH
42g, stirring at room 4 hours adds sulfuric acid again and is 2,100 ℃ to PH and stirred hydrolysis 2 hours, and is centrifugal, dialyse precipitation, drying precipitated, promptly obtain pachymaran.Pachymaran is dissolved in the dimethyl sulfoxide (DMSO), adds 10ml pyridine and 50ml diacetyl oxide, 100 ℃ were refluxed 3 hours, transferred about PH to 7 with NaOH, the centrifugal supernatant liquor that gets, and dialysis with the dialyzed solution drying, promptly obtains acetylize pachymaran (9g).The acetylize pachymaran degree of acetylation that obtains in this way is 1.1, has antitumor and the raise immunity effect.
Embodiment 6
Get Poria powder 20g, extract with 1M NaOH stirring at room, extracting solution adds acetic acid and gets the Pachymose precipitation, and centrifugal repeatedly again, washing and dialysis are with NaIO
46g adds in the suspension of Pachymose, transfers PH to 5, and the room temperature lucifuge stirred after 3 days, and glycerol adding 5ml stirred 4 hours, dialysis, and dialyzed solution is transferred about PH to 7, adds NaBH
42g, stirring at room 4 hours adds sulfuric acid again and is 2,100 ℃ to PH and stirred hydrolysis 2 hours, and is centrifugal, dialyse precipitation, drying precipitated, promptly obtain pachymaran.Pachymaran is dissolved in the dimethyl sulfoxide (DMSO), adds 30ml pyridine and 70ml diacetyl oxide, 100 ℃ were refluxed 3 hours, transferred about PH to 7 with NaOH, the centrifugal supernatant liquor that gets, and dialysis with the dialyzed solution drying, promptly obtains acetylize pachymaran (12g).The acetylize pachymaran degree of acetylation that obtains in this way is 1.5, has antitumor and the raise immunity effect.
Claims (7)
1. from Poria powder, extract Pachymose with the alkaline extraction acid precipitation method, be prepared using Smith degradation method oxidation removing β in the Pachymose (1 → 6) bonded glucose unit again with the Pachymose, promptly made β (1 → 3) bonded dextran (pachymaran).With phosphoric acid-Sodium Nitrite is oxygenant, with glucose unit in the pachymaran-CH
2OH is oxidized to COOH, again with the alkali salify, promptly make can be water-soluble have antitumor and oxidation pachymaran raise immunity.---triethylamine---chlorsulfonic acid is the hydroxyl sulfonation of sulphonating agent with glucose unit in the pachymaran with dimethyl formamide, again with the alkali salify, promptly makes the water-soluble part sulfonylation pachymaran of energy.With dimethyl sulfoxide (DMSO)---pyridine---diacetyl oxide be acetylizing agent with the pachymaran acetylize, promptly make can be water-soluble the partial acetylation pachymaran.Part sulfonylation and partial acetylation pachymaran also have antitumor and the raise immunity effect.Their structure is as follows:
The integer of oxidation pachymaran n=40～1000, R
1=CH
2OH or COOH, R
2=R
3=H
Glucuronic acid content is the integer of 10%～90% sulfonylation pachymaran n=40～400, R
1=CH
2OH or CH
2OSO
3H,
R
2=H or SO
3H, R
3=H or SO
3H
The sulfonylation degree is that 0.2～2.5 (all hydroxyls are by sulfonylation in the pachymaran
Then the sulfonylation degree is 3) integer of acetylize pachymaran n=40～400, R
1=CH
2OH or CH
2OAc
R
2=H or Ac, R
3=H or Ac
Degree of acetylation is that 0.2～1.5 (all hydroxyls are acetylation in the pachymaran
Then degree of acetylation is 3)
2. according to claim 1 described technology, it is characterized in that the phosphoric acid with 20～70% is the dissolution with solvents Pachymose, is oxygenant with the Sodium Nitrite, and stirring at room prepares the oxidation pachymaran.
3. according to claim 1 described technology, it is characterized in that 10～90% glucose unit in the pachymaran is oxidized to that the product of gained all has antitumor and the raise immunity effect after the glucuronic acid unit, and water soluble.
4. according to claim 1 described technology, it is characterized in that with the dimethyl formamide being solvent, is catalyzer with the triethylamine, under cold condition, is that sulphonating agent is with the pachymaran sulfonation with the chlorsulfonic acid.
5. according to claim 1 described technology, it is characterized in that the many sulfonylation degree of the new Poria cocos of final product sulfonylation are 0.2～2.5, have antitumor and the raise immunity effect.
6. according to claim 1 described technology, it is characterized in that with the dimethyl sulfoxide (DMSO) being solvent, is catalyzer with the pyridine, under 100 ℃ of reflux conditionss, is that acetylizing agent is with the pachymaran acetylize with the diacetyl oxide.
7. according to claim 1 described technology, the degree of acetylation that it is characterized in that the partial acetylation pachymaran is 0.2～1.5, and products therefrom all can be water-soluble, have antitumor and the raise immunity effect.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94112670 CN1124249A (en) | 1994-12-09 | 1994-12-09 | Antineoplastic new poria polysaccharide water soluble derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94112670 CN1124249A (en) | 1994-12-09 | 1994-12-09 | Antineoplastic new poria polysaccharide water soluble derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1124249A true CN1124249A (en) | 1996-06-12 |
Family
ID=5036342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 94112670 Pending CN1124249A (en) | 1994-12-09 | 1994-12-09 | Antineoplastic new poria polysaccharide water soluble derivative |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1124249A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1309731C (en) * | 2005-07-29 | 2007-04-11 | 武汉大学 | Poria cocos mycellium glucan sulphate derivative and its preparation method and use |
| CN100379763C (en) * | 2006-01-12 | 2008-04-09 | 武汉大学 | Cross-linked pachyman, its prepn. and uses |
| CN101289516B (en) * | 2007-04-16 | 2010-09-22 | 郑明义 | Hydroxyethyl pachyman sulfuric acid ester and method for preparing same |
| CN102690321A (en) * | 2012-06-05 | 2012-09-26 | 惠州市鑫福来实业发展有限公司 | Process for extracting protein of cordyceps militaris, and optimization method for optimal extraction conditions of process |
| CN104490943A (en) * | 2014-11-30 | 2015-04-08 | 郑州后羿制药有限公司 | Poria cocos injection and preparation method thereof |
| CN106562203A (en) * | 2016-11-13 | 2017-04-19 | 合肥学院 | Preparation method of modified poria cocos noodles |
| CN115176890A (en) * | 2022-06-29 | 2022-10-14 | 瑞普高科(天津)生物技术有限公司 | Application of poria beta-1,3-D-glucan in preparation of feed additive for improving growth performance |
-
1994
- 1994-12-09 CN CN 94112670 patent/CN1124249A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1309731C (en) * | 2005-07-29 | 2007-04-11 | 武汉大学 | Poria cocos mycellium glucan sulphate derivative and its preparation method and use |
| CN100379763C (en) * | 2006-01-12 | 2008-04-09 | 武汉大学 | Cross-linked pachyman, its prepn. and uses |
| CN101289516B (en) * | 2007-04-16 | 2010-09-22 | 郑明义 | Hydroxyethyl pachyman sulfuric acid ester and method for preparing same |
| CN102690321A (en) * | 2012-06-05 | 2012-09-26 | 惠州市鑫福来实业发展有限公司 | Process for extracting protein of cordyceps militaris, and optimization method for optimal extraction conditions of process |
| CN104490943A (en) * | 2014-11-30 | 2015-04-08 | 郑州后羿制药有限公司 | Poria cocos injection and preparation method thereof |
| CN106562203A (en) * | 2016-11-13 | 2017-04-19 | 合肥学院 | Preparation method of modified poria cocos noodles |
| CN115176890A (en) * | 2022-06-29 | 2022-10-14 | 瑞普高科(天津)生物技术有限公司 | Application of poria beta-1,3-D-glucan in preparation of feed additive for improving growth performance |
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| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |