WO2013146669A1 - Procédé de fabrication d'un polysaccharide phosphorylé - Google Patents

Procédé de fabrication d'un polysaccharide phosphorylé Download PDF

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Publication number
WO2013146669A1
WO2013146669A1 PCT/JP2013/058553 JP2013058553W WO2013146669A1 WO 2013146669 A1 WO2013146669 A1 WO 2013146669A1 JP 2013058553 W JP2013058553 W JP 2013058553W WO 2013146669 A1 WO2013146669 A1 WO 2013146669A1
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WIPO (PCT)
Prior art keywords
polysaccharide
phosphorylated
reaction
aqueous solution
compound
Prior art date
Application number
PCT/JP2013/058553
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English (en)
Japanese (ja)
Inventor
巧 沖原
翔吾 亀ノ上
靖弘 吉田
尚子 難波
昭博 松川
紀幸 長岡
Original Assignee
国立大学法人岡山大学
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Publication date
Application filed by 国立大学法人岡山大学 filed Critical 国立大学法人岡山大学
Priority to JP2014507863A priority Critical patent/JP5706579B2/ja
Publication of WO2013146669A1 publication Critical patent/WO2013146669A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/02—Esters
    • C08B31/06—Esters of inorganic acids
    • C08B31/066—Starch phosphates, e.g. phosphorylated starch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B33/00—Preparation of derivatives of amylose
    • C08B33/02—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
    • C08B37/0018—Pullulan, i.e. (alpha-1,4)(alpha-1,6)-D-glucan; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
    • C08B37/0021—Dextran, i.e. (alpha-1,4)-D-glucan; Derivatives thereof, e.g. Sephadex, i.e. crosslinked dextran
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
    • C08B37/0087—Glucomannans or galactomannans; Tara or tara gum, i.e. D-mannose and D-galactose units, e.g. from Cesalpinia spinosa; Tamarind gum, i.e. D-galactose, D-glucose and D-xylose units, e.g. from Tamarindus indica; Gum Arabic, i.e. L-arabinose, L-rhamnose, D-galactose and D-glucuronic acid units, e.g. from Acacia Senegal or Acacia Seyal; Derivatives thereof

Definitions

  • the present invention relates to a method for producing a phosphorylated polysaccharide. More specifically, the present invention relates to a method for synthesizing a phosphorylated polysaccharide in an aqueous solution at a low temperature.
  • Patent Document 1 discloses a method of reacting a saccharide (oligosaccharide, polysaccharide) and an alkali cyclotriphosphate in an alkaline aqueous solution.
  • Patent Document 2 there is a method in which lactic acid bacteria are fermented under predetermined conditions to produce phosphorylated sugar (see Patent Document 2).
  • Patent Document 3 a phosphorylated saccharide in which the binding position of a phosphate group is controlled by reacting a specific phosphatase with a phosphorylated saccharide prepared by reacting a potato starch solution with an amylolytic enzyme such as ⁇ -amylase. Is disclosed.
  • Patent Document 1 is not suitable for mass production because it is an alkali cyclotriphosphate.
  • Patent Documents 2 and 3 use an enzyme or the like, there is a problem in cost for industrial production.
  • An object of the present invention is to provide a method for easily synthesizing a phosphorylated polysaccharide having a high substitution rate and high solubility in water.
  • the present invention includes an aqueous solution containing a polysaccharide (a) containing at least one selected from the group consisting of pullulan, glucomannan, amylose, starch, dextran, and lentinan, and an alkaline compound (b), and phosphorus oxychloride.
  • the present invention relates to a method for producing a phosphorylated polysaccharide, characterized by mixing and reacting a phosphorus compound (c) at ⁇ 5 to 10 ° C.
  • the production method of the present invention there is an excellent effect that a phosphorylated polysaccharide having a high substitution rate and high solubility in water can be easily synthesized. Moreover, since the obtained phosphorylated polysaccharide does not cause a decrease in molecular weight due to heating or coloring due to oxidation, the phosphorylated polysaccharide can be more easily used in products using the phosphorylated polysaccharide.
  • the production method of the present invention is to produce a phosphorylated polysaccharide by reacting a polysaccharide with a phosphorylating agent.
  • the reaction is carried out by treating the polysaccharide in an aqueous solution of an alkali compound, and then subjecting the phosphorylating agent to a low temperature. It has a great feature in reacting.
  • the reaction is carried out by heating an aqueous solution containing the raw material.
  • the heating method is still not a sufficient method for selectively reacting polysaccharides having low reactivity due to high hydrogen bonding property between molecules or between molecules.
  • molecular weight reduction and coloring due to oxidation are also problems.
  • the obtained phosphorylated polysaccharide was found to have a low molecular weight fraction due to degradation and to suppress coloring due to oxidation.
  • the polysaccharide is treated with an alkali compound in advance to make the hydroxyl group more active and react with each other.
  • the phosphorylating agent is very active because it is in water, the hydrolysis proceeds with the phosphorylation of the polysaccharide, making it difficult for the phosphorylation to proceed, but the alkali treatment increases the phosphorylation reactivity of the polysaccharide, It is surmised that only the phosphorylation reaction is promoted.
  • a polysaccharide is treated in an aqueous solution of an alkali compound.
  • an aqueous solution containing a polysaccharide and an alkali compound is stirred and mixed to prepare an aqueous solution containing a polysaccharide and an alkali compound.
  • polysaccharide (a) in the present invention examples include lactose, sucrose, sucralose, cellobiose, trehalose, maltose, palatinose (registered trademark), maltotriose, maltodextrin, cyclodextrin, glycosyl sucrose, amylose, amylopectin, cycloamylose, Examples include glycogen, cellulose, agarose, cluster dextrin, mannan, glucomannan, pullulan, starch, dextran, and lentinan. These may be used alone or in combination of two or more, but amylose, glucomannan, pullulan, starch, dextran, and lentinan are preferable.
  • said polysaccharide what substituted some hydroxyl groups with functional groups other than a phosphate group is also contained.
  • alkali compound (b) in the present invention examples include sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, sodium carbonate, sodium sulfite, ammonia and the like. These can be used alone or in combination of two or more, but sodium hydroxide and potassium hydroxide are preferred.
  • the aqueous solution containing the polysaccharide and the alkali compound may be prepared by adding the polysaccharide to an aqueous alkali solution in which the alkali compound is previously dissolved in water and stirring and mixing the mixture. It may be prepared by adding and stirring and mixing, and after mixing the polysaccharide and the alkali compound in a solid state in advance, it may be further added to water and stirring and mixing.
  • the aqueous solution may be a solution in which the polysaccharide and the alkali compound are dissolved, but it is preferable to continue stirring from the viewpoint of ensuring uniform reactivity even after the dissolution.
  • the concentration of the alkali compound in the aqueous solution is preferably 0.1% by weight or more, more preferably 1 to 50% by weight, and still more preferably 10 to 30% by weight.
  • the amount ratio (b / a) between the alkali compound and the polysaccharide is preferably 0.1 / 1 to 20/1, more preferably 0.5 / 1 to 10 /, from the viewpoint of suppressing the hydrolysis of the polysaccharide. 1, more preferably 1/1 to 5/1.
  • the treatment temperature (stirring temperature) in the aqueous solution is preferably ⁇ 5 to 50 ° C., more preferably 0 to 50 ° C., and still more preferably 0 to 25 ° C. from the viewpoint of preventing coloring and hydration of the polysaccharide.
  • the treatment time is preferably 0.01 to 96 hours, more preferably 0.1 to 48 hours, and still more preferably 0.1 to 96 hours from the viewpoint of reliably proceeding the reaction and eliminating unreacted components. ⁇ 24 hours.
  • the pH of the solution at the time of treatment is not particularly limited, and it is alkaline by an alkali compound, preferably exhibits pH 10 or more.
  • the treatment in an aqueous solution of a polysaccharide alkali compound is performed.
  • the polysaccharide subjected to the treatment is reacted with a phosphorous compound (c) that is a phosphorylating agent.
  • a phosphorus compound is added to an aqueous solution containing a polysaccharide and an alkali compound, and the reaction is carried out by mixing with stirring.
  • Examples of the phosphorus compound (c) in the present invention include phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, phosphorus chloride alkyl ester, and the like. These can be used alone or in combination of two or more, and phosphorus oxychloride is preferred. Examples of phosphorus oxychloride include phosphoryl chloride.
  • the amount ratio between the polysaccharide (a) and the phosphorus compound (c) is appropriately adjusted according to the phosphorylation degree of the resulting phosphorylated polysaccharide (the ratio of all hydroxyl groups contained in one polysaccharide molecule to be replaced by a phosphate group). be able to.
  • the degree of phosphorylation varies depending on several factors such as the amount charged, reaction temperature, water content, etc., so adjustment is not easy and there is a limit on the degree of phosphorylation due to thermal equilibrium with the dissociation reaction.
  • the degree of phosphorylation can be adjusted by changing the charged amount, which solves the problems of the prior art.
  • the phosphorus compound is mixed in an aqueous solution containing a polysaccharide and an alkali compound, but there is no particular limitation on the mixing method.
  • the phosphorus compound is being stirred in an aqueous solution containing a polysaccharide and an alkali compound. Can be added dropwise.
  • the mixing temperature is preferably ⁇ 5 to 50 ° C., more preferably 0 to 45 ° C., and further preferably 0 to 10 ° C.
  • hydrolysis of the polysaccharide can be suppressed and coloring can also be prevented.
  • side reaction by suppressing the side reaction at a low temperature, it is possible to prevent a crosslinking reaction such as a diester.
  • the temperature means the temperature of the aqueous solution before adding the phosphorus compound, and the aqueous solution temperature is preferably kept within the temperature range during the addition and mixing of the phosphorus compound.
  • the solution pH at the time of addition and mixing of the phosphorus compound is not particularly limited, and is alkaline, preferably pH 8 or more because the alkali compound and the polysaccharide are mixed in advance.
  • the solution is preferably stirred and mixed for 0.1 to 96 hours, more preferably 0.1 to 48 hours, and even more preferably 0.1 to 24 hours. To advance the reaction.
  • a synthetic polymer etc. can be used within the range which does not impair the effect of this invention other than polysaccharide (a), an alkali compound (b), and a phosphorus compound (c).
  • the synthetic polymer is preferably a synthetic polymer having a hydroxyl group from the viewpoint of having a large number of hydroxyl groups, and more preferably polyvinyl alcohol.
  • the content of polyvinyl alcohol is preferably 0.01 to 10% by weight, more preferably 1 to 3% by weight in the aqueous solution used for the reaction.
  • a phosphorylated polysaccharide is obtained by the method of the present invention.
  • the phosphorylated polysaccharide is obtained in a dissolved state in an aqueous solution
  • the production method of the present invention can suppress a crosslinking reaction with an unnecessary phosphorus compound because of the reaction at a low temperature.
  • solid phosphorylated polysaccharide can be recovered except for by-products (eg, sodium phosphate, sodium chloride).
  • the obtained aqueous solution after the reaction is dialyzed using a regenerated cellulose membrane, an ultrafiltration membrane or the like to remove by-products, or further subjected to crossflow filtration using an ultrafiltration membrane. And can be concentrated and purified.
  • the recovered phosphorylated polysaccharide is subjected to the production method of the present invention at a low temperature, it can be redissolved without lowering the molecular weight or coloring. Therefore, since the preparation as a powder or a tablet is possible, the range of use is expanded. The individual structure can be confirmed by IR analysis, NMR analysis, or the like.
  • the production method of the present invention preferably comprises 0.5% or more, more preferably 1% or more, and even more preferably 2% or more of the polysaccharide used as the raw material. It has a yield of being oxidized.
  • the number average molecular weight (Mn) of the obtained phosphorylated polysaccharide is preferably the number average molecular weight of the polysaccharide (a) used from the viewpoint that it is less decomposed due to the reaction at low temperature and the high molecular weight can be maintained. It is desirable that there is no change and it is the same or larger. Specifically, for example, 2000 to 10000000 is preferable, 2000 to 1000000 is more preferable, and 2000 to 500000 is more preferable. In addition, in this specification, the number average molecular weight (Mn) of phosphorylated polysaccharide can be measured according to the method as described in the below-mentioned Example.
  • the phosphorylation degree of the phosphorylated polysaccharide is not particularly limited in the present invention, and at least about 1% by number of hydroxyl groups can be phosphorylated out of all hydroxyl groups contained in one molecule. Preferably, 1 to 30% by number, more preferably 5 to 20% by number of hydroxyl groups are phosphorylated. Further, the content ratio of the phosphoric acid group in one molecule is preferably 0.1 to 15% by weight, and more preferably 0.1 to 10% by weight.
  • the ratio of the number of phosphorylated hydroxyl groups in the phosphorylated polysaccharide was determined by conducting an elemental analysis of the phosphorylated polysaccharide using ICP emission analysis to measure the phosphorus content, and all the measured phosphorus was phosphorylated. It can be calculated as derived from a hydroxyl group. Moreover, the content rate of a phosphoric acid group is computable from the content rate of phosphorus, as all originating in a phosphoric acid group.
  • Phosphorylated polysaccharide has low irritation and high affinity to living tissue and exhibits bioabsorbability.
  • phosphorylated polysaccharide dissolves apatite whose phosphate group is a constituent inorganic component of living hard tissue, and releases a part of calcium, which is a constituent element of apatite, as an ion.
  • the acid group is adsorbed on bones and teeth by a new chelate bond.
  • it exhibits adsorptivity to the metal and ceramics that are prosthetic materials for living hard tissues by chelate bonding of the phosphate group of the phosphorylated polysaccharide.
  • the phosphorylated polysaccharide obtained by the production method of the present invention is a dentifrice, mouthwash, troche, tablet, cream, ointment, patch, mouse spray, Can be used for coatings on tooth surfaces and dental prostheses, anti-hypersensitivity agents, periodontal disease treatment agents applied to periodontal pockets, oral care wet tissues, mouth fresheners, chewing gum, or gargle .
  • the resulting reaction solution was subjected to dialysis with a regenerated cellulose membrane to remove by-products sodium phosphate and sodium chloride until the conductivity reached 30 ⁇ S or less. Subsequently, cross flow filtration was performed with an ultrafiltration membrane having a molecular weight cut-off of 5000, and after concentration, freeze-drying was performed to obtain phosphorylated pullulan (yield 20 g, yield 100%).
  • the structure of the obtained phosphorylated pullulan was confirmed by IR analysis, and the phosphoric acid group content ratio was 2.8% by weight, the hydroxyl group substitution ratio was 6% by number, the number average molecular weight was about 30,000, Met.
  • Comparative Example 1 Using a separable flask having an internal volume of 2 L, 45.0 g of the same pullulan as in Example 1 was dissolved in 205 g of distilled water at room temperature (20 ° C.). While stirring this solution, 1000 g of 1M phosphoric acid aqueous solution (adjusted to pH 5.5 with sodium hydroxide) was added and mixed, and then the whole amount was heated and vacuum dried until the water content became 9.7%. Then, the phosphorylated pullulan was obtained by heating at 170 ° C. for 5 hours (yield 25 g, yield 56%). The structure of the obtained phosphorylated pullulan was confirmed by IR analysis, and the phosphoric acid group content ratio was 2.8% by weight, the hydroxyl group substitution ratio was 6% by number, the number average molecular weight was about 22,000, brown Met.
  • Test Example 1 The solubility of the phosphorylated pullulan obtained in Examples 1 and 2 and Comparative Example 1 was examined. Specifically, 1 g of each phosphorylated pullulan was added to 10 mL of distilled water, and the solubility was visually confirmed by stirring.
  • the phosphorylated polysaccharide can be obtained as a dry solid, and the dry solid can be redissolved. Therefore, since the preparation as a powder or a tablet is possible, the range of use is expanded.
  • phosphorylated pullulan when phosphorylated pullulan is used as a bioabsorbable material, it is necessary to remove endotoxin endotoxin, but the phosphorylated pullulan produced by this method has a higher molecular weight than the conventional product. It can be easily removed.

Abstract

L'invention concerne un procédé de fabrication d'un polysaccharide phosphorylé, caractérisé par le mélange d'une solution aqueuse qui contient un polysaccharide (a) comprenant au moins un constituant choisi dans le groupe consistant en le pullulane, le glucomannane, l'amylose, l'amidon, le dextrane et le lentinane et un composé alcalin (b) avec un composé de phosphore (c) comprenant de l'oxychlorure de phosphore à -5 à 10°C pour amener ces constituants à réagir les uns avec les autres. Selon le procédé de fabrication de l'invention, un polysaccharide phosphorylé peut être obtenu sous la forme d'un solide séché, le solide séché peut être redissous et peut être préparé sous la forme d'une préparation pulvérulente ou d'un comprimé, et par conséquent l'applicabilité du polysaccharide phosphorylé peut être élargie.
PCT/JP2013/058553 2012-03-28 2013-03-25 Procédé de fabrication d'un polysaccharide phosphorylé WO2013146669A1 (fr)

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JP2014507863A JP5706579B2 (ja) 2012-03-28 2013-03-25 リン酸化多糖の製造方法

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JP2012-073934 2012-03-28
JP2012073934 2012-03-28

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104017104A (zh) * 2014-05-20 2014-09-03 江南大学 一种可溶性、高取代度磷酸化酵母葡聚糖的制备方法
CN110511297A (zh) * 2019-10-14 2019-11-29 武汉华联科生物技术有限公司 一种硒香菇多糖的提取分离纯化方法
US11319566B2 (en) 2017-04-14 2022-05-03 Capsugel Belgium Nv Process for making pullulan
US11576870B2 (en) 2017-04-14 2023-02-14 Capsugel Belgium Nv Pullulan capsules

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JPS53121887A (en) * 1977-04-01 1978-10-24 Sumitomo Chem Co Ltd Preparation of ionic pullulan gel
JPH04230637A (ja) * 1990-12-27 1992-08-19 Natl Starch & Chem Investment Holding Corp タブレット賦形剤としての酵素的に枝切りされたデンプン
JPH1180201A (ja) * 1997-09-01 1999-03-26 Kao Corp 新規多糖誘導体、その製造方法及びそれを含有する化粧料
JP2005519170A (ja) * 2002-03-08 2005-06-30 ジョージ ウエストン フーズ リミテッド 架橋されたワキシ小麦デンプン及びこれを含む食品

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US7803937B2 (en) * 2003-10-31 2010-09-28 Kowa Co., Ltd. Cellulose II phosphate ester and metal-adsorbing material using the same
JP6143230B2 (ja) * 2012-03-28 2017-06-07 国立大学法人 岡山大学 リン酸化多糖の固相合成方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53121887A (en) * 1977-04-01 1978-10-24 Sumitomo Chem Co Ltd Preparation of ionic pullulan gel
JPH04230637A (ja) * 1990-12-27 1992-08-19 Natl Starch & Chem Investment Holding Corp タブレット賦形剤としての酵素的に枝切りされたデンプン
JPH1180201A (ja) * 1997-09-01 1999-03-26 Kao Corp 新規多糖誘導体、その製造方法及びそれを含有する化粧料
JP2005519170A (ja) * 2002-03-08 2005-06-30 ジョージ ウエストン フーズ リミテッド 架橋されたワキシ小麦デンプン及びこれを含む食品

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104017104A (zh) * 2014-05-20 2014-09-03 江南大学 一种可溶性、高取代度磷酸化酵母葡聚糖的制备方法
CN104017104B (zh) * 2014-05-20 2016-05-25 江南大学 一种可溶性、高取代度磷酸化酵母葡聚糖的制备方法
US11319566B2 (en) 2017-04-14 2022-05-03 Capsugel Belgium Nv Process for making pullulan
US11576870B2 (en) 2017-04-14 2023-02-14 Capsugel Belgium Nv Pullulan capsules
US11878079B2 (en) 2017-04-14 2024-01-23 Capsugel Belgium Nv Pullulan capsules
CN110511297A (zh) * 2019-10-14 2019-11-29 武汉华联科生物技术有限公司 一种硒香菇多糖的提取分离纯化方法

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