JPH0129362B2 - - Google Patents
Info
- Publication number
- JPH0129362B2 JPH0129362B2 JP25552484A JP25552484A JPH0129362B2 JP H0129362 B2 JPH0129362 B2 JP H0129362B2 JP 25552484 A JP25552484 A JP 25552484A JP 25552484 A JP25552484 A JP 25552484A JP H0129362 B2 JPH0129362 B2 JP H0129362B2
- Authority
- JP
- Japan
- Prior art keywords
- polysaccharide
- amino acid
- amino
- chitin
- carboxyamino
- 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.)
- Expired
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- 150000004676 glycans Chemical class 0.000 claims description 19
- 229920001282 polysaccharide Polymers 0.000 claims description 19
- 239000005017 polysaccharide Substances 0.000 claims description 19
- 229920000642 polymer Chemical group 0.000 claims description 12
- -1 N-carboxyamino acid anhydride Chemical class 0.000 claims description 11
- 125000003277 amino group Chemical group 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000003275 alpha amino acid group Chemical group 0.000 claims 1
- 229940024606 amino acid Drugs 0.000 description 23
- 235000001014 amino acid Nutrition 0.000 description 23
- 150000001413 amino acids Chemical class 0.000 description 23
- 229920002101 Chitin Polymers 0.000 description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- 229920001661 Chitosan Polymers 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HFZKKJHBHCZXTQ-JTQLQIEISA-N (4s)-4-azaniumyl-5-oxo-5-phenylmethoxypentanoate Chemical compound OC(=O)CC[C@H](N)C(=O)OCC1=CC=CC=C1 HFZKKJHBHCZXTQ-JTQLQIEISA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QNAYBMKLOCPYGJ-UHFFFAOYSA-N Alanine Chemical compound CC([NH3+])C([O-])=O QNAYBMKLOCPYGJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FFEARJCKVFRZRR-UHFFFAOYSA-N L-Methionine Natural products CSCCC(N)C(O)=O FFEARJCKVFRZRR-UHFFFAOYSA-N 0.000 description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 2
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 description 2
- ROHFNLRQFUQHCH-UHFFFAOYSA-N Leucine Chemical compound CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- NJSRYBIBUXBNSW-VIFPVBQESA-N (3s)-3-azaniumyl-4-oxo-4-phenylmethoxybutanoate Chemical compound [O-]C(=O)C[C@H]([NH3+])C(=O)OCC1=CC=CC=C1 NJSRYBIBUXBNSW-VIFPVBQESA-N 0.000 description 1
- MSWZFWKMSRAUBD-IVMDWMLBSA-N 2-amino-2-deoxy-D-glucopyranose Chemical compound N[C@H]1C(O)O[C@H](CO)[C@@H](O)[C@@H]1O MSWZFWKMSRAUBD-IVMDWMLBSA-N 0.000 description 1
- QDGAVODICPCDMU-UHFFFAOYSA-N 2-amino-3-[3-[bis(2-chloroethyl)amino]phenyl]propanoic acid Chemical compound OC(=O)C(N)CC1=CC=CC(N(CCCl)CCCl)=C1 QDGAVODICPCDMU-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- 229920000936 Agarose Polymers 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- CKLJMWTZIZZHCS-UHFFFAOYSA-N D-OH-Asp Natural products OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 description 1
- 239000004470 DL Methionine Substances 0.000 description 1
- CKLJMWTZIZZHCS-UWTATZPHSA-N L-Aspartic acid Natural products OC(=O)[C@H](N)CC(O)=O CKLJMWTZIZZHCS-UWTATZPHSA-N 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- 239000004395 L-leucine Substances 0.000 description 1
- 235000019454 L-leucine Nutrition 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- 229930195722 L-methionine Natural products 0.000 description 1
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 description 1
- DUKURNFHYQXCJG-UHFFFAOYSA-N Lewis A pentasaccharide Natural products OC1C(O)C(O)C(C)OC1OC1C(OC2C(C(O)C(O)C(CO)O2)O)C(NC(C)=O)C(OC2C(C(OC3C(OC(O)C(O)C3O)CO)OC(CO)C2O)O)OC1CO DUKURNFHYQXCJG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- OVRNDRQMDRJTHS-FMDGEEDCSA-N N-acetyl-beta-D-glucosamine Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O OVRNDRQMDRJTHS-FMDGEEDCSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- GNWDDDINCIDABX-UHFFFAOYSA-N [1-[2-(carboxyamino)propanoyloxy]-1-oxopropan-2-yl]carbamic acid Chemical compound OC(=O)NC(C)C(=O)OC(=O)C(C)NC(O)=O GNWDDDINCIDABX-UHFFFAOYSA-N 0.000 description 1
- 229960003767 alanine Drugs 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 125000000539 amino acid group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229960005261 aspartic acid Drugs 0.000 description 1
- MSWZFWKMSRAUBD-UHFFFAOYSA-N beta-D-galactosamine Natural products NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- HCUYBXPSSCRKRF-UHFFFAOYSA-N diphosgene Chemical compound ClC(=O)OC(Cl)(Cl)Cl HCUYBXPSSCRKRF-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229950010030 dl-alanine Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229960002442 glucosamine Drugs 0.000 description 1
- 229960002989 glutamic acid Drugs 0.000 description 1
- 125000003630 glycyl group Chemical group [H]N([H])C([H])([H])C(*)=O 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229960003136 leucine Drugs 0.000 description 1
- 229960004452 methionine Drugs 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 235000006109 methionine Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229950006780 n-acetylglucosamine Drugs 0.000 description 1
- 229960003104 ornithine Drugs 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Polyamides (AREA)
Description
本発明は、アミノ酸及びアミノ酸重合体の結合
した多糖複合体の製造方法に関するものである。
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、また場合によつては、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、酵素精製用ク
ロマト担体等に応用できる。
本発明者らは、アミノ酸及びアミノ酸重合体と
多糖との複合体の調製に鋭意努力した結果、Ｎ−
カ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つて、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
複合体の合成に到達し、本発明をなすに至つた。
この複合体においてアミノ酸及びアミノ酸重合体
の種類とアミノ酸の結合量を変化させることによ
つて生体内吸収分解性あるいは、酵素の吸着性を
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。
本発明の多糖複合体に結合するアミノ酸重合体
を例示すれば、例えば、Ｌ−グルタミン酸ベンジ
ル、Ｌ−アスパラギン酸ベンジル、Ｎ−ベンジル
オキシカルボニル−Ｌ−リジン、Ｌ−メチオニ
ン、Ｌ−ロイシン、Ｌ−フエニルアラニン、Ｌ−
バリン、Ｎ−ベンジルオキシカルボニル−Ｌ−オ
ルニチン、Ｌ−アスパラギン酸、Ｌ−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−Ｌ−グルタミン、DL−
アラニン、DL−ロイシン、DL−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重
量％である。
本発明の複合体の製造は以下のように行う。例
えば部分的脱アセチル化キチンをジメチルアセト
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、攪拌溶解させ、キ
チンのアミノ基にアミノ酸を順次結合させてい
く。
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つて、合成され
る。
この反応を（）式で示す。ここでアミノ酸を
NH2CHRCOOHで表わし、Ｒはアミノ酸残基の
側鎖である。
得られたＮ−カルボキシアミノ酸無水物は、ア
ミノ基と室温で容易に反応し、アミノ酸を結合し
た多糖になる。部分的脱アセチル化キチンは、Ｎ
−アセチルグルコサミンとグルコサミンの共重合
体であるので、この反応は（）式のようにな
る。
Ｎ−カルボキシアミノ酸無水物が多糖のアミノ
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（）式で示す。
ここでｘは１から100くらいが望ましい。
また均一溶液系でなくとも、アミノ基を有する
多糖に、アミノ酸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、攪拌することにより、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。
この場合も反応は前式と同じである。
多糖の濃度は0.1〜30重量％、Ｎ−カルボキシ
アミノ酸無水物の濃度は0.1〜20重量％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。
次に本発明を実施例に基づき、さらに詳細に説
明する。
実施例 １
カニガラより製造されたキチン粉末3.0ｇを40
％水酸化ナトリウム水溶液に浸漬し、室温で３時
間放置した。これに氷225ｇを加え攪拌し、均一
なアルカリキチン溶液とし、44時間室温で放置し
た。これを５℃に保ちながら濃塩酸60mlを攪拌し
ながら滴下し、更に２規定塩酸40mlを滴下し、PH
７にした。このとき溶液は白濁し、キチンの沈澱
が生じた。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酸銀によつて確めた。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1.87ｇを得た。別にＬ−グルタミン酸ベンジル
7.65ｇをジオキサン100mlにケンダクさせ、トリ
クロロメチルクロロホーメイト3.0ml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−Ｌ−グルタミン酸ベ
ンジル無水物7.95ｇ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40mlにゲン
ダクさせ、Ｎ−カルボキシ−Ｌ−グルタミン酸ベ
ンジル無水物2.82ｇを加え、室温で１週間攪拌し
た。沈澱を遠心分離し、ジメチルスルホキシドで
２回洗浄と遠心分離を行つた。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。
このようにして製造した複合体の収率は1.35ｇ
で重量増加率は171％であつた。
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。カツコ内のＳ、Ｍ、Ｗは吸収の強さ、つ
まり強い、中位、弱いをそれぞれ示す。
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、700cm-1に現われて
いた。
The present invention relates to a method for producing a polysaccharide complex in which amino acids and amino acid polymers are bonded. 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, the complex of polysaccharide and amino acid is
It is expected to have specific interactions with biological components (enzymes, antibodies, hormones, etc.) and can be applied to immunoadsorbents, chromatography carriers for enzyme purification, etc. As a result of our earnest efforts to prepare complexes of amino acids and amino acid polymers with polysaccharides, the present inventors have discovered that N-
By using a carboxyamino acid anhydride and a polysaccharide having an amino group, the inventors achieved the synthesis of a complex in which an amino acid and an amino acid polymer are bonded to a polysaccharide through a peptide bond, leading to the present invention.
In this complex, by changing the types of amino acids and amino acid polymers and the binding amount of amino acids, the bioabsorption and decomposition properties or adsorption of enzymes can be controlled. A specific adsorption phenomenon that cannot be achieved with polysaccharide itself becomes possible. Examples of amino acid polymers that bind to the polysaccharide complex of the present invention include benzyl L-glutamate, benzyl L-aspartate, N-benzyloxycarbonyl-L-lysine, L-methionine, L-leucine, L- Phenylalanine, L-
Valine, N-benzyloxycarbonyl-L-ornithine, L-aspartic acid, L-glutamic acid, N-hydroxyethyl-L-glutamine, N
-Hydroxypropyl-L-glutamine, DL-
It is a homopolymer of alanine, DL-leucine, DL-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% by weight of the polysaccharide. The composite of the present invention is produced as follows. For example, partially deacetylated chitin can be mixed with dimethylacetamide, methylpyrrolidone, lithium chloride (10:
10:1 weight ratio), add N-carboxyamino acid anhydride, stir and dissolve, and amino acids are sequentially bonded to the amino groups of chitin. N-carboxyamino acid anhydride is synthesized by reacting an amino acid with phosgene. This reaction is shown by equation (). Here, the amino acid
It is represented by NH 2 CHRCOOH, where R is the side chain of the amino acid residue. The obtained N-carboxyamino acid anhydride easily reacts with amino groups at room temperature to form a polysaccharide bonded with amino acids. Partially deacetylated chitin is N
- Since it is a copolymer of acetylglucosamine and glucosamine, this reaction is as shown in equation (). If the N-carboxyamino acid anhydride is present in an excess amount with respect to the amino group of the polysaccharide, the N-carboxyamino acid anhydride further reacts with the amino group of the first bonded amino acid. This is shown in equation (). Here, x is preferably between 1 and 100. Furthermore, even if the system is not a homogeneous solution, it is possible to bond an amino acid polymer to a polysaccharide having an amino group. Chitosan powder bound to an amino acid polymer can be obtained by mixing chitosan powder with dimethyl sulfoxide, adding N-carboxyamino acid anhydride, and stirring.
In this case as well, the reaction is the same as in the previous equation. The appropriate concentration of polysaccharide is 0.1 to 30% by weight, the concentration of N-carboxyamino acid anhydride is 0.1 to 20% by weight, and the appropriate ratio of polysaccharide to N-carboxyamino acid anhydride is 20 to 0.05. Next, the present invention will be explained in more detail based on examples. Example 1 3.0g of chitin powder produced from crab shell was added to 40
% sodium hydroxide aqueous solution and left at room temperature for 3 hours. 225 g of ice was added and stirred to form a homogeneous alkaline chitin solution, which was left at room temperature for 44 hours. While keeping this at 5℃, add 60ml of concentrated hydrochloric acid dropwise while stirring, then add dropwise 40ml of 2N hydrochloric acid,
I made it 7. At this time, the solution became cloudy and chitin precipitated. 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 4 times.
Finally, the precipitate was dried to obtain 1.87 g of partially deacetylated chitin. Separately, benzyl L-glutamate
7.65 g was dissolved in 100 ml of dioxane, and 3.0 ml of trichloromethyl chloroformate was dropped onto activated carbon to generate phosgene gas, which was introduced into the mixture and reacted at 50°C for 2 hours, and then nitrogen gas was passed through it for 1 hour. . Dioxane was removed by distillation under reduced pressure to obtain 7.95 g of benzyl N-carboxy-L-glutamate anhydride. 0.5 g of partially deacetylated chitin was dissolved in 40 ml of dimethyl sulfoxide, 2.82 g of benzyl N-carboxy-L-glutamate anhydride was added, and the mixture was stirred at room temperature for one week. The precipitate was centrifuged, washed twice with dimethyl sulfoxide, and centrifuged. Next, it was treated with dioxane three times in the same manner. The obtained precipitate was dried. The yield of the complex thus produced was 1.35 g.
The weight increase rate was 171%. 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 the cutout indicate the strength of absorption, that is, strong, medium, and weak, respectively. Infrared absorption indicating that amino acid polymers were bound appeared at 3290, 1735, 750, and 700 cm -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0.36ｇをジメチルスルホキ
シド70mlにケンダクさせ、実施例１と同様にし
て、DL−アラニンから合成したＮ−カルボキシ
−DL−アラニン無水物1.61ｇ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％であつた。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。カツコ内のＳ、Ｍ、Ｗは実
施例１と同じである。[Table] Example 2 0.36 g of partially deacetylated chitin obtained by the same treatment as in Example 1 except that the alkaline chitin was left to stand for 163 hours was dissolved in 70 ml of dimethyl sulfoxide. 1.61 g of N-carboxy-DL-alanine anhydride synthesized from DL-alanine in the same manner as in 1 was 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%. 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 the cutlet are the same as in the first embodiment.
Claims (1)
ノ酸無水物を反応させることを特徴とするアミノ
酸又はその重合体の結合した多糖複合体の製法。1. A method for producing a polysaccharide complex bound to an amino acid or a polymer thereof, which comprises reacting a polysaccharide having an amino group with an N-carboxyamino acid anhydride.
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 JPS61133232A (en) | 1986-06-20 |
| JPH0129362B2 true 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) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5463022A (en) * | 1990-08-17 | 1995-10-31 | Drug Delivery System Institute, Ltd. | N-acetylcarboxymethylchitosan derivatives and process for preparation thereof |
-
1984
- 1984-12-03 JP JP25552484A patent/JPS61133232A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61133232A (en) | 1986-06-20 |
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