JPS61133232A - Composite polysaccharide bonded with amino acid polymer and production thereof - Google Patents
Composite polysaccharide bonded with amino acid polymer and production thereofInfo
- Publication number
- JPS61133232A JPS61133232A JP25552484A JP25552484A JPS61133232A JP S61133232 A JPS61133232 A JP S61133232A JP 25552484 A JP25552484 A JP 25552484A JP 25552484 A JP25552484 A JP 25552484A JP S61133232 A JPS61133232 A JP S61133232A
- Authority
- JP
- Japan
- Prior art keywords
- amino acid
- polysaccharide
- acid polymer
- amino
- polymer
- 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
Landscapes
- Polyamides (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
Description
【発明の詳細な説明】
＝３・
”ご本発明は、アミノ酸及びアミノ酸重合体の結合４−
＋； ・
”ＩＩ”た多糖複合体及びその製造方法に関するもので
ある。[Detailed description of the invention]
+; - "II" relates to a polysaccharide complex and a method for producing the same.
多糖、アミノ酸及びアミノ酸重合体は、生物の体を構成
する物質であり、生体との親和性が良好であり、また場
合によっては、生体内吸収分解性を有する。また、多糖
とアミノ酸との複合体は、生体成分（酵素、抗体、ホル
モン等）と特異的な相互作用が期待され、免疫吸着剤、
酵素精製用り ゛ロマト担体等に応用できる。Polysaccharides, amino acids, and amino acid polymers are substances that constitute the bodies of living organisms, have good affinity with living organisms, and, in some cases, are bioabsorbable and decomposable. In addition, complexes of polysaccharides and amino acids are expected to have specific interactions with biological components (enzymes, antibodies, hormones, etc.), and immunoadsorbents,
It can be applied as a chromatographic carrier for enzyme purification.
本発明者らは、アミノ酸及びアミノ酸重合体と多糖との
複合体の［Ｊに鋭意努力した結果、Ｎ −力ルボキシア
ミノ酸無水物とアミノ基を有する多糖とを用いることに
よって、アミノ酸及びアミノ酸重合体をペプチド結合を
通して多糖に結合したｉ・杏体の合成に到達し、本発明
をなすに至った。The present inventors have made extensive efforts to develop complexes of amino acids and amino acid polymers with polysaccharides, and as a result, we have discovered that by using N-ruboxyamino acid anhydrides and polysaccharides having amino groups, The present invention was achieved by achieving the synthesis of i-apricots linked to polysaccharides through peptide bonds.
−片 ゛
〕この複合体においてアミノ酸及びアミノ酸重合体制御
することができる。多糖、それ自体では発現できないよ
うな、特異的吸着現象が可能−となる。- Part 1: Amino acids and amino acid polymers can be controlled in this complex. A specific adsorption phenomenon that cannot be achieved by polysaccharide itself becomes possible.
本発明のアミノＲ重合体としてＬ−グルタミン酸ベンジ
ル、Ｌ−アスパラギン酸ベンジル、Ｎ−ペンシルオキシ
カルボニル−し一リジン、Ｌ−メチメニン、し−ロイシ
ン、し−フェニルアラニン、Ｌ−バリン、Ｎ−ベンジル
オキシカルボニル−オルニチン、Ｌ−アスパラギン酸、
し−グルタミン酸、Ｎ−ヒドロキシエチル−Ｌ−グルタ
ミン、Ｎ−ヒドロキシプロピル−し−グルタミン、ＯＬ
−アラニン、ＤＬ−ロイシン、ＯＬ−メチオニン等の単
独重合体、またはそれらの２種以上が混合した共重合体
である。もう一方の成分であるアミノ基を有する多糖は
、部分的脱アセチル化キチン、キトサン、アミノエチル
アガロース、グリシルスターチ等である。溶媒としては
、ジメチルスルホキシド、ジメチルアセトアミド、ジメ
チルホルムアミド等のアミノ酸重合体を溶解させ同時に
、多糖を膨潤させるものを用いる。アミノ基を有する多
糖とアミノ酸重合体の構成比は、多糖が１０〜９０、、
ｌ：量％である。As the amino R polymer of the present invention, L-benzyl glutamate, L-benzyl aspartate, N-pencyloxycarbonyl-cytolysine, L-methimenin, di-leucine, di-phenylalanine, L-valine, N-benzyloxycarbonyl -ornithine, L-aspartic acid,
Shi-glutamic acid, N-hydroxyethyl-L-glutamine, N-hydroxypropyl-shi-glutamine, OL
- A homopolymer of alanine, DL-leucine, OL-methionine, etc., or a copolymer of two or more thereof. The other component, a polysaccharide having an amino group, is partially deacetylated chitin, chitosan, aminoethyl agarose, glycyl starch, or the like. As the solvent, one that dissolves the amino acid polymer and simultaneously swells the polysaccharide is used, such as dimethyl sulfoxide, dimethylacetamide, and dimethylformamide. The composition ratio of the polysaccharide having an amino group and the amino acid polymer is 10 to 90 for the polysaccharide.
l: Amount %.
アミド、メチルピロリドン、塩化リチウム（１０：１０
： １重量比）の混合溶媒に溶解し、Ｎ−カルボキシア
ミノ酸無水物を加えて、撹拌溶解させ、キチンのアミン
基にアミノ酸を順次結合させていく。amide, methylpyrrolidone, lithium chloride (10:10
: 1 weight ratio), add N-carboxyamino acid anhydride, stir and dissolve, and amino acids are sequentially bonded to the amine groups of chitin.
Ｎ−カルボキシアミノ酸無水物は、アミノ酸とホスゲン
を反応させることによって、合成される。N-carboxyamino acid anhydride is synthesized by reacting an amino acid with phosgene.
この反応を（Ｉ）式で示す。ここでアミノ酸をＮ、Ｈ２
ＣＨＲＣＯＯＨで表わし、Ｒはアミノ酸残基の側鎖であ
る。This reaction is shown by formula (I). Here, the amino acids are N, H2
It is represented by CHRCOOH, where R is the side chain of the amino acid residue.
得られたＮ−カルボキシアミノ酸無水物は、アＮ−カル
ボキシアミノ酸無水物が多糖のアミン基に対して過剰量
存在すれば、最初に結合したアミノ酸のアミノ基に更に
、Ｎ−カルボキシアミノ酸無水物が反応する。これを（
Ｉン式で示す。In the obtained N-carboxyamino acid anhydride, if the N-carboxyamino acid anhydride is present in an excess amount with respect to the amine group of the polysaccharide, the N-carboxyamino acid anhydride is further added to the amino group of the amino acid bonded initially. react. this(
It is shown in the I-in style.
ここでχは １から １００りらいが望ましい。Here, χ is preferably 1 to 100 or so.
また均−溶液系でなくとも、アミノ基を有する多糖に、
アミノＭ重合体を結合させることができる。キトサンの
粉末をジメチルスルホキシドにケンダクさせ、これに、
Ｎ−カルボキシアミノ酸無水物を加え、撹拌することに
より、アミノ酸重合体を結合したキトサン粉末を得るこ
とができる。In addition, even if it is not a homogeneous solution system, polysaccharides with amino groups,
Amino M polymers can be attached. Chitosan powder is dissolved in dimethyl sulfoxide, and this is mixed with
By adding N-carboxyamino acid anhydride and stirring, chitosan powder bonded with an amino acid polymer can be obtained.
この場合も反応は前式と同じである。In this case as well, the reaction is the same as in the previous equation.
多糖の濃度は０．１〜３０重堡％、Ｎ−カルボキシアミ
ノ酸無水物の濃度は０．１〜２０重倦％が適当であり、
多糖とＮ−カルボキシアミノ酸無水物との比は２０−０
．０５が適当である。The appropriate concentration of polysaccharide is 0.1 to 30% by weight, and the concentration of N-carboxyamino acid anhydride is 0.1 to 20% by weight.
The ratio of polysaccharide to N-carboxyamino acid anhydride is 20-0
．． 05 is appropriate.
次に本発明を実施例に基づき、さらに詳細に脱環、する
。Next, the present invention will be described in more detail based on Examples.
なアルカリキチン溶液とし、４４時間至温で放置した。An alkaline chitin solution was prepared and left at the lowest temperature for 44 hours.
これを５℃に保ちながら濃塩酸６０ｍ４を撹拌しながら
滴下し、更に２規定塩酸４０ｍ込を滴下し、ｐＨ７にし
た。このとき溶液は白潤し、キチンの沈澱が土じた。こ
れを遠心分離し、沈澱を水で洗浄することと遠心分離を
４回おこない、上澄に塩素イオンのないことを硝１銀に
よって確めた。更に、この沈澱に２９％アンモニア水を
加え、遠心分離し、次に、水による洗浄と遠心分離を４
回行い、最後に沈澱を乾燥させ、部分的脱アセチル化キ
チン１．８７ Ｃｌを得た。別にし一グルタミン酸ベン
ジル７゜６５ Ｃｌをジオキサン１００ｍ Ｑ、にケン
ダクさせ、トリクロロメチルクロロホーメイト ３゜０
ｒｒＮｌを活性炭上に滴下させて発生させたホスゲンガ
スを、それに導入し、５０℃で２時間反応させ、その後
、窒素ガスを１時間通した。ジオキサンを減圧下で蒸留
して除去し、Ｎ−カルボキシ−し−グルタミン酸ベンジ
ル無水物７．９５ Ｑを得た。部分的脱アセチル化キチ
ン０．５ｇをジメチルスルホキシド４０ｍ！Ｑにゲンダ
クさせ、Ｎ−カルボキシ−Ｌ−グルー・＝１
□冬ｉミン酸ベンジル無水物２．８２ ｇを加え１．室
温で１゛（・週間ｉ拌した。沈澱を遠心分離し、ジメチ
ルス１゜
ルホキシドで２回洗浄と遠心分離を行った。次にジオキ
サンで同様に３回処理した。得られた沈澱を乾燥した。While maintaining the temperature at 5° C., 60 m4 of concentrated hydrochloric acid was added dropwise with stirring, and then 40 m4 of 2N hydrochloric acid was added dropwise to adjust the pH to 7. At this time, the solution turned white and a chitin precipitate was removed. This was centrifuged, and the precipitate was washed with water and centrifuged four times, and the absence of chloride ions in the supernatant was confirmed using silver nitrate. Furthermore, 29% ammonia water was added to this precipitate, centrifuged, and then washed with water and centrifuged for 4 times.
The precipitate was finally dried to obtain 1.87 Cl of partially deacetylated chitin. Separately, 7°65 Cl of benzyl monoglutamate was dissolved in 100 mQ of dioxane, and 3°0 of trichloromethyl chloroformate was added.
Phosgene gas generated by dropping rrNl onto the activated carbon was introduced into it and allowed to react at 50° C. for 2 hours, after which nitrogen gas was passed for 1 hour. The dioxane was removed by distillation under reduced pressure to obtain 7.95 Q of benzyl N-carboxy-glutamate anhydride. 0.5 g of partially deacetylated chitin and 40 m of dimethyl sulfoxide! Add 2.82 g of N-carboxy-L-glue = 1 □ 2.82 g of benzyl mate anhydride.1. The mixture was stirred at room temperature for 1 week. The precipitate was centrifuged, washed twice with dimethyl sulfoxide and centrifuged. Then, it was treated with dioxane three times in the same way. The resulting precipitate was dried. .
このようにして製造した複合体の収率は１．３５０で重
量増加率は１７１％であった。The yield of the composite thus produced was 1.350, and the weight increase was 171%.
部分的脱アセチル化キチンと得られた複合体の赤外線吸
収スペクトルの特性吸収ピークを第１表に示す。カッコ
内のＳ 、Ｍ 、Ｗは吸収の強さ、つより強い、中
位、弱いをそれぞれ表す。Table 1 shows the characteristic absorption peaks of the infrared absorption spectrum of the partially deacetylated chitin and the resulting complex. S, M, and W in parentheses represent the strength of absorption, stronger than normal, medium, and weak, respectively.
アミノ酸重合体が結合していることを示す赤外線吸収が
、３２９０．１７３５．７５０． ７００ｃ ｍ−１に
現ねれていた。The infrared absorption indicating that the amino acid polymer is bound is 3290.1735.750. It appeared at 700 cm-1.
第１表
実施例２
アルカリキチンの放置時間を１６３時間にしたことを除
いて実施例１と同様に処理して得た、部分 、的脱
アセチル化キチン０．３６ ｇをジメチルスルホキシド
７０ｍ Ｑにケンダクさせ、実施例１と同様にして、Ｄ
Ｌ−アラニンから合成したＮ−カルボキシ−ＤＬ−アラ
ニン無水物ｉ、ｅｉ ｇを加え、１週間攪拌した。水に
よる洗浄と遠心分離を数回繰り返し、最後にアセトンを
加え、沈澱を濾過し、複合体０．６６９ｇを得た。重量
増加率８６％であった。Table 1 Example 2 0.36 g of partially deacetylated chitin, obtained by the same treatment as in Example 1 except that the alkali chitin was left to stand for 163 hours, was dissolved in 70 mQ of dimethyl sulfoxide. and D in the same manner as in Example 1.
N-carboxy-DL-alanine anhydride i and eig synthesized from L-alanine were added and stirred for one week. Washing with water and centrifugation were repeated several times, and finally acetone was added and the precipitate was filtered to obtain 0.669 g of a complex. The weight increase rate was 86%.
得られた複合体と１６３時間処理した部分的脱アセチル
化キチンの赤外線吸収スペクトルの特性吸収ピークを第
２表に示す。カッコ内のＳ 、Ｍ 、Ｗは実施例１
と同じである。Table 2 shows the characteristic absorption peaks of the infrared absorption spectra of the obtained composite and partially deacetylated chitin treated for 163 hours. S, M, and W in parentheses are Example 1
is the same as
第２表Table 2
Claims (1)
して多糖中のアミノ基に結合していることを特徴とする
アミノ酸重合体結合多糖複合体（２）アミノ酸及びアミ
ノ酸重合体をペプチド結合を通して多糖中のアミノ基に
結合していることを特徴とするアミノ酸重合体結合多糖
複合体の製法。(1) An amino acid polymer-bonded polysaccharide complex characterized in that an amino acid and an amino acid polymer are bonded to an amino group in a polysaccharide through a peptide bond. (2) An amino acid and an amino acid polymer are bonded to an amino group in a polysaccharide through a peptide bond. A method for producing an amino acid polymer-bonded polysaccharide complex, characterized in that it is bonded to a group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25552484A JPS61133232A (en) | 1984-12-03 | 1984-12-03 | Composite polysaccharide bonded with amino acid polymer and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25552484A JPS61133232A (en) | 1984-12-03 | 1984-12-03 | Composite polysaccharide bonded with amino acid polymer and production thereof |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26572788A Division JPH01152105A (en) | 1988-10-21 | 1988-10-21 | Polysaccharide composite containing amino acid or its polymer bonded thereto |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61133232A true JPS61133232A (en) | 1986-06-20 |
| JPH0129362B2 JPH0129362B2 (en) | 1989-06-09 |
Family
ID=17279936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25552484A Granted JPS61133232A (en) | 1984-12-03 | 1984-12-03 | Composite polysaccharide bonded with amino acid polymer and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61133232A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992003480A1 (en) * | 1990-08-17 | 1992-03-05 | Drug Delivery System Institute, Ltd. | N-acetylcarboxymethylchitosan derivative and production thereof |
-
1984
- 1984-12-03 JP JP25552484A patent/JPS61133232A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992003480A1 (en) * | 1990-08-17 | 1992-03-05 | Drug Delivery System Institute, Ltd. | N-acetylcarboxymethylchitosan derivative and production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0129362B2 (en) | 1989-06-09 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |