JPH03220202A - Chitosan oligomer and its production - Google Patents
Chitosan oligomer and its productionInfo
- Publication number
- JPH03220202A JPH03220202A JP1565990A JP1565990A JPH03220202A JP H03220202 A JPH03220202 A JP H03220202A JP 1565990 A JP1565990 A JP 1565990A JP 1565990 A JP1565990 A JP 1565990A JP H03220202 A JPH03220202 A JP H03220202A
- Authority
- JP
- Japan
- Prior art keywords
- chitosan
- polymerization
- degree
- phosphoric acid
- chitosan oligomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 24
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 18
- 238000009826 distribution Methods 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 229920002101 Chitin Polymers 0.000 abstract description 6
- 230000000850 deacetylating effect Effects 0.000 abstract description 4
- 230000006196 deacetylation Effects 0.000 abstract description 4
- 238000003381 deacetylation reaction Methods 0.000 abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 241000238557 Decapoda Species 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 108010089807 chitosanase Proteins 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical compound N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 0.000 description 1
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- 241000238424 Crustacea Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000008406 cosmetic ingredient Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002328 demineralizing effect Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XDUKCSCITZQGGB-UHFFFAOYSA-N ethanamine;methanol Chemical compound OC.CCN XDUKCSCITZQGGB-UHFFFAOYSA-N 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000007974 sodium acetate buffer Substances 0.000 description 1
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、キチンを脱アセチル化して得られる高重合度
のキトサンからキトサンオリコマ−を製造する方法の改
良、並びに得られた重合度分布が単分散に近いキトサン
オリゴマーに関する。Detailed Description of the Invention [Field of Industrial Application] The present invention aims to improve a method for producing a chitosan oligomer from chitosan with a high degree of polymerization obtained by deacetylating chitin, and to improve the obtained degree of polymerization distribution. relates to chitosan oligomers that are close to monodisperse.
エビ、カニ等の甲殻類の甲皮、きのこ、細菌細胞壁等か
ら得られるキチンを脱アセチル化することにより、工業
用、医薬用あるいは食品用等の蛋白質凝集剤や、整髪料
等の化粧品等として用いられるキトサンが製造される。By deacetylating chitin obtained from the carapace of crustaceans such as shrimp and crabs, mushrooms, and bacterial cell walls, it can be used as a protein flocculant for industrial, pharmaceutical, and food applications, as well as cosmetics such as hair conditioners. The chitosan used is produced.
ところが、このようなキトサンは、一般に高重合度であ
り、溶液とした場合の粘度が高すぎて扱いにくいもので
あるため、高濃度の溶液を作ることができない。従って
、このようなキトサンを工業的に使用する場合には、多
量の溶液が必要となるため作業性が悪い。例えば、通常
の高重合度キトサンを希酸に溶解したものでは、１重量
％程度の溶液でも低粘度になることは少なく、非常に高
粘度である。However, such chitosan generally has a high degree of polymerization, and when made into a solution, the viscosity is too high and it is difficult to handle, so a highly concentrated solution cannot be prepared. Therefore, when such chitosan is used industrially, a large amount of solution is required, resulting in poor workability. For example, when ordinary chitosan with a high degree of polymerization is dissolved in a dilute acid, even a solution of about 1% by weight rarely has a low viscosity, and has a very high viscosity.
また、高重合度のキトサンを整髪料として使用する場合
には、毛髪への吸着を十分に行うことができない。Furthermore, when chitosan with a high degree of polymerization is used as a hair styling agent, it cannot be sufficiently adsorbed onto the hair.
そこで、従来キトサンを低分子化して高濃度且つ低粘度
のキトサン溶液を得るため種々の提示がなされている。Therefore, various proposals have been made to obtain chitosan solutions with high concentration and low viscosity by reducing the molecular weight of chitosan.
キトサンを低分子化する代表的な方法としては、酵素を
用いて分解する方法、硫酸を用いて低分子化反応を行う
方法等が知られているが、これらの方法で得られる低分
子化キトサンは重合度分布が広いため、その利用価値が
劣り、また収率も低いという欠点も有している。Typical methods for reducing the molecular weight of chitosan include a method of decomposing it using enzymes and a method of performing a reaction of reducing the molecular weight using sulfuric acid. has a wide distribution of degree of polymerization, so its utility value is inferior and the yield is also low.
本発明の目的は、従来技術の有する欠点を克服し、高重
合度のキトサンからキトサンの低分子量体、即ちオリコ
マ−であって、単分散に近いものを提供することにある
。特に、単分散に近い狭い重合度分布を有するキトサン
オリゴマーを収率よく得る製造法を提供するにある。An object of the present invention is to overcome the drawbacks of the prior art and to provide a low molecular weight chitosan, ie, an oricomer, made from chitosan with a high degree of polymerization, which is close to monodisperse. In particular, it is an object of the present invention to provide a method for producing chitosan oligomers having a narrow distribution of degree of polymerization close to monodisperse in good yield.
本発明者等は種々検討の結果、リン酸水溶液中でキトサ
ンを解重合させることにより、単分散に近い重合度分布
を有する低重合度キトサン（キトサンオリゴマー）が得
られることを見出して本発明に到ったものである。As a result of various studies, the present inventors discovered that by depolymerizing chitosan in an aqueous phosphoric acid solution, a low degree of polymerization chitosan (chitosan oligomer) having a degree of polymerization distribution close to monodisperse could be obtained, and the present invention was developed based on this finding. It has arrived.
即ち、本発明は、重合度分布が重量平均重合度をＤＰｗ
、数平均重合度をＤＰｎとする時、ＤＰ、／ＤＰｗ、＜
２゜０であるキトサンオリゴマーに係るものである。That is, in the present invention, the degree of polymerization distribution has a weight average degree of polymerization of DPw.
, when the number average degree of polymerization is DPn, DP, /DPw, <
This relates to a chitosan oligomer with a molecular weight of 2°0.
更に本発明は、リン酸水溶液中でキトサンを解重合させ
ることにより、上記の如き単分散に近い狭い重合度分布
を有するオリゴマーを得るキトサンオリゴマーの製造法
に係るものである。Furthermore, the present invention relates to a method for producing a chitosan oligomer, which obtains an oligomer having a narrow polymerization degree distribution close to monodisperse as described above by depolymerizing chitosan in an aqueous phosphoric acid solution.
本発明において低分子化反応に用いるリン酸としては、
リン酸濃度が７５〜９３重量％のものが好ましく、特に
８２〜８６重量％濃度のリン酸水溶液が好ましい。In the present invention, the phosphoric acid used in the molecular weight reduction reaction is as follows:
A phosphoric acid aqueous solution having a phosphoric acid concentration of 75 to 93% by weight is preferred, and a phosphoric acid aqueous solution having a concentration of 82 to 86% by weight is particularly preferred.
本発明において原料として用いるキトサンは、従来公知
のものが適用でき、例えば市販されているキチン又は天
然に存在するキチンを常法により脱アセチル化して得ら
れるキトサン等が挙げられる。後者の例としては、例え
ば、カニ殻を脱灰、脱タンパクして得られたキチンを、
濃度３０〜５０％の水酸化ナトリウム水溶液に浸漬し、
５０〜１３０℃で反応させた後、アルカリを除去し、次
いで水洗乾燥して得られたフレーク状、又はさらに粉砕
工程を経た粉末状の乾燥物がある。As the chitosan used as a raw material in the present invention, conventionally known chitosan can be used, such as chitosan obtained by deacetylating commercially available chitin or naturally occurring chitin by a conventional method. As an example of the latter, for example, chitin obtained by demineralizing and deproteinizing crab shells,
Immersed in a sodium hydroxide aqueous solution with a concentration of 30 to 50%,
After reacting at 50 to 130°C, the alkali is removed, followed by washing with water and drying to obtain a flake-like product, or a powder-like dried product that is further subjected to a pulverization process.
また、原料キトサンは、脱アセチル化率が６０％未満の
ものでは反応性に乏しいことから、少なくとも脱アセチ
ル化率が６０％以上のものを用いることが望ましく、ま
た、キトサンに含有される水分は、リン酸水溶液を有効
に浸透させるために３０％以下にすることが好ましい。In addition, if the raw material chitosan has a deacetylation rate of less than 60%, it will have poor reactivity, so it is desirable to use one with a deacetylation rate of at least 60% or more. In order to effectively penetrate the phosphoric acid aqueous solution, the content is preferably 30% or less.
本発明においては、かかるキトサンをリン酸水溶液中に
溶解乃至分散させた後、低分子化反応を行わせる。この
分解反応の反応温度及び反応時間は、この発明では特に
限定されない。反応は室温でも進行し、適当な期間、例
えば３０日間室温にて静置すれば、目的とするキトサン
オリゴマーが得られる。また加温して反応を促進するこ
とが出来る。、通常２０〜９０℃の範囲内、好ましくは
３０〜７０℃の範囲から選択される。In the present invention, after such chitosan is dissolved or dispersed in an aqueous phosphoric acid solution, a molecular weight reduction reaction is performed. The reaction temperature and reaction time of this decomposition reaction are not particularly limited in the present invention. The reaction proceeds even at room temperature, and the desired chitosan oligomer can be obtained by allowing it to stand at room temperature for an appropriate period of time, for example, 30 days. The reaction can also be accelerated by heating. , usually within the range of 20 to 90°C, preferably within the range of 30 to 70°C.
キトサンの低分子化反応が進み、所期のキトサンオリゴ
マーが得られる時期に反応を終了させる。即ち、反応溶
液をメタノール、エタノール、イソプロパツール、アセ
トン等の有機溶媒と混合させて沈殿を生成させた後、こ
の沈殿物を濾過して分散し、有機溶媒による洗浄を行い
、乾燥させれば、キトサンオリゴマーが得られる。The reaction to lower the molecular weight of chitosan progresses and the reaction is terminated when the desired chitosan oligomer is obtained. That is, after mixing the reaction solution with an organic solvent such as methanol, ethanol, isopropanol, or acetone to form a precipitate, the precipitate is filtered and dispersed, washed with an organic solvent, and dried. , chitosan oligomers are obtained.
このようにして高濃度リン酸水溶液を用いた低分子化反
応によって得られたキトサンオリゴマーにおいては、重
合度分布の巾が非常に狭く、ＤＰ、／ＤＰ、が２以下と
いう単分散に近い製品を得ることができる。また本発明
の製造方法によれば、かかるキトサンオリゴマーを高収
率で得ることができる。The chitosan oligomer obtained by the low-molecularization reaction using a high-concentration phosphoric acid aqueous solution has a very narrow polymerization degree distribution, and is a nearly monodisperse product with a DP, /DP of 2 or less. Obtainable. Moreover, according to the production method of the present invention, such chitosan oligomers can be obtained in high yield.
本発明のキトサンオリゴマーは、単分散に近くその分子
量分布が狭いため、食品添加物、化粧品成分、医薬品あ
るいは医療材料など広範な用途において有用である。Since the chitosan oligomer of the present invention is nearly monodisperse and has a narrow molecular weight distribution, it is useful in a wide range of applications such as food additives, cosmetic ingredients, pharmaceuticals, and medical materials.
以下本発明を実施例について説明するが、本発明はこれ
らの実施例に限定されるものではない。The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples.
実施例１
原料キトサン試料としてはＮ、Ｆ、Ｉ、 ＬＡＢＯＲＡ
ＴロＲＩＥＳ製キトサンＰＳＨを使用し、次の調製方法
によりキトサンオリゴマーを製造した。Example 1 Raw chitosan samples include N, F, I, and LABORA.
A chitosan oligomer was produced using chitosan PSH manufactured by TRIES according to the following preparation method.
■）８３％リン酸３００ｇが入った５００ｍ１容共栓付
き三角フラスコ中にキトサン１５ｇをかき混ぜながら加
え、溶解させた。この溶液を室温にて３０日間静置した
。(2) 15 g of chitosan was added to a 500 ml Erlenmeyer flask with a stopper containing 300 g of 83% phosphoric acid with stirring and dissolved. This solution was allowed to stand at room temperature for 30 days.
２）９９％メタノール約２１が入った３ｆ！容三角フラ
スコを３個用意し、それぞれにキトサン溶液を攪拌しな
がら徐々に注加し、再生させた。さらに、そのまま３６
時間攪拌を続けた。2) 3f containing about 21% 99% methanol! Three Erlenmeyer flasks were prepared, and the chitosan solution was gradually poured into each with stirring to regenerate the flasks. Furthermore, as it is 36
Stirring was continued for an hour.
傾斜法により上澄み液と沈殿部分に分離した後、沈殿を
三角フラスコ１個に集め、その中へ２０％（Ｖ／Ｖ）
）リエチルアミンーメタノール溶液を注ぎ、−夜攪拌
した。溶液を傾斜法により交換し、同様の処理を２回行
った。After separating into supernatant liquid and precipitate part by decanting method, collect the precipitate in one Erlenmeyer flask and add 20% (V/V) into it.
) Ethylamine-methanol solution was poured and stirred overnight. The solution was exchanged by decanting and the same treatment was carried out twice.
３） 沈殿を濾別し、メタノールで十分洗浄後、水約１
．５１２とともに三角フラスコに移し一昼夜攪拌した。3) Separate the precipitate by filtration, wash thoroughly with methanol, and add about 1 liter of water.
．． The mixture was transferred to an Erlenmeyer flask together with 512 and stirred overnight.
懸濁液を十分に傾斜させた後に濾別した。沈殿部分は凍
結乾燥した。濾過が十分にできないために、濾液及び第
一洗液（約３β）を１７３に濃縮し、遠心分離にかけた
。ざらに濾液を半量に濃縮後、４倍容メタノール中に注
ぎ再沈させた。沈殿を集め、ベンゼン置換後凍結乾燥し
た。The suspension was filtered off after sufficient decanting. The precipitated portion was lyophilized. Due to insufficient filtration, the filtrate and first wash (approximately 3β) were concentrated to 173 and centrifuged. After roughly concentrating the filtrate to half its volume, it was poured into 4 volumes of methanol and reprecipitated. The precipitate was collected, substituted with benzene, and lyophilized.
４） 上記２つの凍結乾燥物を粉砕し、混合して、目的
物であるキトサンオリゴマー１３．４ ｇを得た。これ
は対キトサン収率としては８９．３％となる。4) The above two freeze-dried products were crushed and mixed to obtain 13.4 g of the target chitosan oligomer. This results in a yield of 89.3% based on chitosan.
得られたキトサンオリゴマーについて次の分析方法によ
り、固有粘度〔η〕、重量平均重合度ＤＰ、及び数平均
重合度ＤＰイを求めた。The intrinsic viscosity [η], weight average degree of polymerization DP, and number average degree of polymerization DPi of the obtained chitosan oligomer were determined by the following analytical methods.
分析方法
１） ｐＨ４，９の酢酸−酢酸ナトリウム緩衝溶液を
用いて、２５℃で固有粘度を求めた。Analysis method 1) Intrinsic viscosity was determined at 25°C using an acetic acid-sodium acetate buffer solution of pH 4.9.
２） ＧＰＣにより分子量を求め、これよりＤＰ、。2) Determine the molecular weight by GPC, and from this DP.
ＤＰｗ、を計算する。Calculate DPw.
ＧＰＣ；試料０．０２ ｇをピリジン０．５ｍｌ中に浸
漬シ、イソシアン酸フェニル０．Ｉｍｊ！を加え、８０
℃で３６時間保持する。トルエン５−を加え、６０℃で
エバポレートする。ＴＨＦを加え生成物を溶解しＧＰＣ
に供する。GPC: 0.02 g of sample was immersed in 0.5 ml of pyridine, and 0.02 g of phenyl isocyanate was immersed in 0.5 ml of pyridine. Imj! Add 80
Hold at ℃ for 36 hours. Add toluene 5- and evaporate at 60°C. Add THF to dissolve the product and perform GPC
Serve.
算出式ｐｓ−ｓｔａｎｃｉａｒｄ換算値（ＤＰ’）から
の補正式
％式％
分析結果は次の如くであった。Correction formula % formula % from calculation formula ps-standciard conversion value (DP') The analysis results were as follows.
０．２５７ １３．４ ９．３１．４比較例
１
酵素を使用してキトサンの低分子化反応を次の如く行っ
た。0.257 13.4 9.31.4 Comparative Example 1 A reaction to reduce the molecular weight of chitosan using an enzyme was carried out as follows.
１） キトサン（脱アセチル化度９９％０５ｇヲ１００
艷の水に分散させ、１Ｍ乳酸７０−に溶解させ、３００
−まで希釈する。（５％キトサン溶液ｐＨ２） ｂａ
ｃｉｌｌｕｓ ｓｐ、 Ｎｏ、７−Ｍ由来のキトサナー
ゼを精製する。（比活性２１７ｕｎｉｔｓ／ｍｇ ｐｒ
ｏｔｅｉｎ）３）５％キトサン溶液５０−にキトサナー
ゼ５−（５２，５ｕｎｉｔｓ）を加え、３７℃で６時間
培養後、３分間煮沸する。1) Chitosan (degree of deacetylation 99% 05g 100
Dispersed in water, dissolved in 1M lactic acid, 300
Dilute to -. (5% chitosan solution pH2) ba
Chitosanase from Cillus sp. No. 7-M is purified. (Specific activity 217 units/mg pr
3) Add chitosanase 5-(52,5 units) to 5% chitosan solution 50-, incubate at 37°C for 6 hours, and then boil for 3 minutes.
４） 塩酸塩の形にして、イオンクロマトグラフィで処
理して、不純物を除去した。キトサンオリゴマー〇収率
（対キトサン）は６２％であった。4) Formed into hydrochloride salt and treated with ion chromatography to remove impurities. The chitosan oligomer yield (relative to chitosan) was 62%.
得られたキトサンオリゴマーを分析すると、重合度分布
は次の如くであり、分布が非常に広い。When the obtained chitosan oligomer was analyzed, the degree of polymerization distribution was as follows, and the distribution was very wide.
単分子 −０ ２量体 １４．０％ ３〃４２．０％ ４〃３１．９％ ５” １２．１％ ６ ／／ ′＝、０Single molecule -0 Dimer 14.0% 3〃42.0% 4 31.9% 5” 12.1% 6 // ′=, 0
Claims (1)
合度をＤＰ＿ｎとする時、ＤＰ＿ｗ／ＤＰ＿ｎ＜２．０
であるキトサンオリゴマー。 ２ リン酸水溶液中でキトサンを解重合させることを特
徴とする請求項１記載のキトサンオリゴマーの製造法。 ３ リン酸水溶液のリン酸濃度が７５〜９３重量％であ
る請求項２記載のキトサンオリゴマーの製造法。 ４ リン酸水溶液のリン酸濃度が８２〜８６重量％であ
る請求項２記載のキトサンオリゴマーの製造法。[Claims] 1. When the degree of polymerization distribution is DP_w for the weight average degree and DP_n for the number average degree of polymerization, DP_w/DP_n<2.0.
chitosan oligomer. 2. The method for producing a chitosan oligomer according to claim 1, characterized in that chitosan is depolymerized in an aqueous phosphoric acid solution. 3. The method for producing a chitosan oligomer according to claim 2, wherein the phosphoric acid concentration of the phosphoric acid aqueous solution is 75 to 93% by weight. 4. The method for producing a chitosan oligomer according to claim 2, wherein the phosphoric acid concentration of the phosphoric acid aqueous solution is 82 to 86% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1565990A JP2758475B2 (en) | 1990-01-24 | 1990-01-24 | Chitosan oligomer and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1565990A JP2758475B2 (en) | 1990-01-24 | 1990-01-24 | Chitosan oligomer and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03220202A true JPH03220202A (en) | 1991-09-27 |
| JP2758475B2 JP2758475B2 (en) | 1998-05-28 |
Family
ID=11894864
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1565990A Expired - Fee Related JP2758475B2 (en) | 1990-01-24 | 1990-01-24 | Chitosan oligomer and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2758475B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020093721A (en) * | 2002-11-20 | 2002-12-16 | 김세권 | Phosphorylated chitosan oligosaccharide with low molecular weight as calcium absorption accelerator |
| WO2006070662A1 (en) | 2004-12-27 | 2006-07-06 | Daicel Chemical Industries, Ltd. | Material for cigarette filer and cigarette filter |
| KR20190061828A (en) | 2017-11-27 | 2019-06-05 | 이보균 | Method for producing chitosan for forage use |
-
1990
- 1990-01-24 JP JP1565990A patent/JP2758475B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020093721A (en) * | 2002-11-20 | 2002-12-16 | 김세권 | Phosphorylated chitosan oligosaccharide with low molecular weight as calcium absorption accelerator |
| WO2006070662A1 (en) | 2004-12-27 | 2006-07-06 | Daicel Chemical Industries, Ltd. | Material for cigarette filer and cigarette filter |
| KR20190061828A (en) | 2017-11-27 | 2019-06-05 | 이보균 | Method for producing chitosan for forage use |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2758475B2 (en) | 1998-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4806474A (en) | Preparation of mycelial chitosan and glucan fractions from microbial biomass | |
| Teng | From chitin to chitosan | |
| JPH04158796A (en) | Production of aqueous solution of sodium hyaluronate | |
| CN101168570B (en) | Method for degrading kelp polysaccharide sulfate | |
| CN102020724B (en) | Method for extracting sodium hyaluronate from fermentation liquor containing hyaluronic acid | |
| CN109721740B (en) | Method for continuously preparing chitin/chitosan solution with different deacetylation degrees | |
| RU2670767C1 (en) | Method for producing low molecular weight heparin | |
| JP2870871B2 (en) | A method for treating crustacean shells using enzymes | |
| JPH03220202A (en) | Chitosan oligomer and its production | |
| JP2901176B2 (en) | Low viscosity chitosan and method for producing the same | |
| CN101280330A (en) | Method for preparing chitosan oligosaccharide with trichoderma reesei cellulase | |
| JPH05184378A (en) | Production of chitosan | |
| CN113248633B (en) | Preparation method of low-molecular chitosan | |
| JPH02200196A (en) | Production of low molecular weight chitosan | |
| JPH02145601A (en) | Anti-hiv agent | |
| CN113354750B (en) | Extraction method and application of bletilla striata polysaccharide with moisturizing effect | |
| JPS6363388A (en) | Production of low molecular weight chitosan | |
| JPS62184002A (en) | Production of low-molecular weight water-soluble chitosan | |
| US20050159593A1 (en) | Method for deproteinization of chitosan | |
| JPH02240101A (en) | Sulfated chitosan derivative and its production | |
| JPH01185301A (en) | Manufacture of low-molecular chitosan | |
| KR100252704B1 (en) | Method of making n,o-carboxy methyl chitosan with high purity crystallization and a method of controlling a molecular weight of water-soluble chitosan | |
| JPS62179503A (en) | Production of chitosan | |
| JPH0133482B2 (en) | ||
| JP2529729B2 (en) | Method for producing chitosan derivative |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313532 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| LAPS | Cancellation because of no payment of annual fees |