JPH0148779B2 - - Google Patents
Info
- Publication number
- JPH0148779B2 JPH0148779B2 JP61174199A JP17419986A JPH0148779B2 JP H0148779 B2 JPH0148779 B2 JP H0148779B2 JP 61174199 A JP61174199 A JP 61174199A JP 17419986 A JP17419986 A JP 17419986A JP H0148779 B2 JPH0148779 B2 JP H0148779B2
- Authority
- JP
- Japan
- Prior art keywords
- leucine
- glutamic acid
- block copolymer
- film
- blood
- 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
Links
- 229920001400 block copolymer Polymers 0.000 claims description 14
- 239000008280 blood Substances 0.000 claims description 12
- 210000004369 blood Anatomy 0.000 claims description 12
- 150000001414 amino alcohols Chemical group 0.000 claims description 6
- 150000002306 glutamic acid derivatives Chemical class 0.000 claims description 6
- 210000004027 cell Anatomy 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- -1 amino alcohol-denatured Chemical compound 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000021164 cell adhesion Effects 0.000 description 4
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 3
- DHQUQYYPAWHGAR-UHFFFAOYSA-N dibenzyl 2-aminopentanedioate Chemical compound C=1C=CC=CC=1COC(=O)C(N)CCC(=O)OCC1=CC=CC=C1 DHQUQYYPAWHGAR-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-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 Natural products CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000017531 blood circulation Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WGMLPPNZSIBKNR-QTXLWBMRSA-N (2S)-2-amino-4-methylpentanoic acid (4S)-4-amino-5-oxo-5-phenylmethoxypentanoic acid Chemical compound N[C@@H](CCC(=O)O)C(=O)OCC1=CC=CC=C1.N[C@@H](CC(C)C)C(=O)O.N[C@@H](CCC(=O)O)C(=O)OCC1=CC=CC=C1 WGMLPPNZSIBKNR-QTXLWBMRSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- MXZROAOUCUVNHX-UHFFFAOYSA-N 2-Aminopropanol Chemical compound CCC(N)O MXZROAOUCUVNHX-UHFFFAOYSA-N 0.000 description 1
- LQGKDMHENBFVRC-UHFFFAOYSA-N 5-aminopentan-1-ol Chemical compound NCCCCCO LQGKDMHENBFVRC-UHFFFAOYSA-N 0.000 description 1
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- 208000007536 Thrombosis Diseases 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002473 artificial blood Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000004113 cell culture Methods 0.000 description 1
- IPDQVJYWUCDNBB-UHFFFAOYSA-N chloroform;2,2,2-trifluoroacetic acid Chemical compound ClC(Cl)Cl.OC(=O)C(F)(F)F IPDQVJYWUCDNBB-UHFFFAOYSA-N 0.000 description 1
- QSKWJTXWJJOJFP-UHFFFAOYSA-N chloroform;ethoxyethane Chemical compound ClC(Cl)Cl.CCOCC QSKWJTXWJJOJFP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 210000002919 epithelial cell Anatomy 0.000 description 1
- 229930195712 glutamate Natural products 0.000 description 1
- ZGEYCCHDTIDZAE-UHFFFAOYSA-N glutamic acid 5-methyl ester Chemical compound COC(=O)CCC(N)C(O)=O ZGEYCCHDTIDZAE-UHFFFAOYSA-N 0.000 description 1
- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 238000012758 nuclear staining Methods 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Materials For Medical Uses (AREA)
Description
(a) 発明の技術分野
本発明は、アミノアルコールで変性された（ロ
イシン−グルタミン酸誘導体）ブロツク共重合体
を内表面に有することにより、細胞が付着しにく
いことを特徴とする血液導管に関するものであ
る。
血液導管とは人工血管、カテーテル、シヤント
（血液を体外に導き出すために用いるもの）、透析
型人工腎臓、膜型人工肺、人工心臓などに用いら
れている管状の血液の流路を包含するものであ
る。
(b) 従来技術の説明
従来、血液導管は、シリコーンゴム、ポリウレ
タン、ポリテトラフルオロエチレン等の合成高分
子材料を用いて作製されているが、これらの材料
を用いた血液導管では、その材料表面に細胞が付
着し、すなわち血栓が生じ、血流を阻害する。し
たがつて、血液導管においては細胞の付着しない
材料が求められている。
(c) 発明の目的
本発明は、上記の問題を、アミノアルコールで
変性された（ロイシン−グルタミン酸誘導体）ブ
ロツク共重合体を用いることにより、細胞付着性
の少ない血液導管を提供することを目的とする。
(d) 発明の構成
本発明者は細胞の付着しにくい性質を有する材
料について種々研究を重ねたところ、アミノアル
コールで変性された（ロイシン−グルタミン酸誘
導体）ブロツク共重合体は細胞を著しく付着させ
ない性質を有しており、血液導管として好適であ
ることを見い出し、本発明を完成するに到つた。
即ち、本発明の血液導管は、（ロイシン−グル
タミン酸誘導体）ブロツク共重合体を目的とする
管状に成型した後、その管状物をアミノアルコー
ルで表面処理して得るか、あるいはあらかじめ他
の高分子材料で管状に成型した後、その内表面に
（ロイシン−グルタミン酸誘導体）ブロツク共重
合体を塗布した後、アミノアルコールで表面処理
して得る。
本発明のロイシン及びグルタミン酸誘導体はＤ
体、Ｌ体、ラセミ体でもよく、グルタミン酸誘導
体としてグルタミン酸誘導体としてグルタミン酸
−γ−メチル、グルタミン酸−γ−ベンジルなど
の脂肪族炭化水素及び芳香族炭化水素のエステル
などが用いられる。（ロイシン−グルタミン酸誘
導体）ブロツク共重合体の分子量はその皮膜が形
成される程度であればよく、またブロツク共重合
体中のグルタミン酸誘導体の含量は15〜50モル％
が好ましい。
アミノアルコールとして、エタノールアミン、
アミノプロパノールなどの他、
H2NC2H4OC2H4OHなどのアルキレングリコー
ル誘導体などが用いられる。表面処理時間はアミ
ノアルコールの種類・濃度及びグルタミン酸誘導
体の種類・含量に応じて適宜選択するが、いずれ
にしても表面処理により、管状物の内表面部分の
グルタミン酸誘導体成分の一部はグルタミン誘導
体に変換されるのが望ましい。
(e) 発明の実施例
次に本発明を実施例によりさらに詳細に説明す
る。
実施例 １
開始剤として１，６−ヘキサメチレンジアミン
を用いて、まず、Ｌ−ロイシン−Ｎ−カルボン酸
無水物を重合させ、その後Ｌ−グルタミン酸−γ
−ベンジル−カルボン酸無水物を加えてさらに重
合させ、グルタミン酸ベンジル−ロイシン−グル
タミン酸ベンジルのトリブロツク共重合体を合成
した。重合溶媒としてベンゼンとジオキサン
（19：１）の混合溶媒を用い、室温で20日間反応
させた。反応終了後、反応液を大過剰のメタノー
ル中に投入し、沈澱物を濾別した。この沈澱物を
メタノールで十分洗浄した後、真空乾燥した。単
一重合体を除くため、沈澱物をクロロホルム−ト
リフルオロ酢酸（９：１）の混合溶媒に溶解さ
せ、クロロホルム−エーテル（９：１）の混合溶
媒で沈澱させて精製した。得られた共重合体はグ
ルタミン酸ベンジルを36モル％含有していた。
流延溶媒としてベンゼンを用い、この共重合体
溶液をガラス板上に流延し、ベンゼンを蒸発させ
ることによりグルタミン酸ベンジル−ロイシン−
グルタミン酸ベンジルのブロツク共重合体フイル
ム（Ａ膜）を得た。
このフイルム（膜厚0.02mm）を３−アミノ−１
−プロパノール中に浸漬し、80℃で10日間反応さ
せた。反応後そのフイルムをエタノール中で十分
洗浄した後、水中で洗浄した。赤外吸収スペクト
ルにおける1730cm-3のエステルに基づく吸収が反
応後消滅し、3400cm-1の水酸基に基づく吸収が出
現したことから、［N5−（３−ヒドロキシプロピ
ル）−グルタミン］−ロイシン−［N5−３−ヒドロ
キシプロビル）−グルタミン］のブロツク共重合
体（Ｂ膜）が合成できたことを確認した。
実施例 ２
実施例１で得た皮膜上で、人由来の上皮性細胞
を含む培養液（約10万個／ml）を接触させたま
ま、炭酸ガス濃度５％、湿度100％、37℃の部屋
に静置した。17時間後、皮膜をリン酸緩衝液でか
るく洗浄し、皮膜上に付着している細胞の量を核
染色法により定量した。比較のため、（ロイシン
−グルタミン酸ベンジル）ランダム共重合体（グ
ルタミン酸ベンジルを30％含有）及びこのランダ
ム共重合体の３−アミノ−１−プロパノール処理
した皮膜（Ｃ膜）、血液導管に使用されているシ
リコーンゴム、標準試料として市販の細胞培養シ
ートを用いて、同様の細胞付着試験を行つた。皮
膜に付着した細胞の量を、標準試料に付着した細
胞の量で割ることにより、細胞付着率を求め、そ
の結果を第１表に示す。
(a) Technical Field of the Invention The present invention relates to a blood conduit characterized by having an amino alcohol-denatured (leucine-glutamic acid derivative) block copolymer on its inner surface, making it difficult for cells to adhere to it. be. Blood conduits include tubular blood flow paths used in artificial blood vessels, catheters, shunts (used to lead blood out of the body), dialysis-type artificial kidneys, membrane-type oxygenators, artificial hearts, etc. It is. (b) Description of the prior art Conventionally, blood conduits have been made using synthetic polymer materials such as silicone rubber, polyurethane, and polytetrafluoroethylene. Cells attach to the bloodstream, forming a blood clot, which obstructs blood flow. Therefore, materials to which cells do not adhere are required for blood conduits. (c) Purpose of the Invention The purpose of the present invention is to solve the above problem by providing a blood conduit with less cell adhesion by using a (leucine-glutamic acid derivative) block copolymer modified with amino alcohol. do. (d) Structure of the Invention The present inventor has conducted various studies on materials that have properties that make it difficult for cells to adhere to them, and has found that an amino alcohol-denatured (leucine-glutamic acid derivative) block copolymer has properties that do not allow cells to adhere significantly. The present inventors have discovered that the present invention is suitable for use as a blood conduit, and have completed the present invention. That is, the blood conduit of the present invention can be obtained by molding a (leucine-glutamic acid derivative) block copolymer into a desired tubular shape and then surface-treating the tubular product with amino alcohol, or by pre-forming the block copolymer with other polymeric materials. After molding into a tubular shape, a (leucine-glutamic acid derivative) block copolymer is coated on the inner surface, and the surface is treated with amino alcohol. The leucine and glutamic acid derivatives of the present invention are D
The glutamic acid derivatives may be glutamic acid derivatives such as esters of aliphatic hydrocarbons and aromatic hydrocarbons such as γ-methyl glutamate and γ-benzyl glutamate. (Leucine-glutamic acid derivative) The molecular weight of the block copolymer is sufficient as long as it forms a film, and the content of the glutamic acid derivative in the block copolymer is 15 to 50 mol%.
is preferred. As amino alcohol, ethanolamine,
In addition to aminopropanol,
Alkylene glycol derivatives such as H 2 NC 2 H 4 OC 2 H 4 OH are used. The surface treatment time is appropriately selected depending on the type and concentration of the amino alcohol and the type and content of the glutamic acid derivative. It is desirable to be converted. (e) Examples of the invention Next, the present invention will be explained in more detail using examples. Example 1 Using 1,6-hexamethylene diamine as an initiator, L-leucine-N-carboxylic acid anhydride was first polymerized, and then L-glutamic acid-γ
A triblock copolymer of benzyl glutamate-leucine-benzyl glutamate was synthesized by adding -benzyl-carboxylic acid anhydride and further polymerizing. A mixed solvent of benzene and dioxane (19:1) was used as a polymerization solvent, and the reaction was carried out at room temperature for 20 days. After the reaction was completed, the reaction solution was poured into a large excess of methanol, and the precipitate was filtered off. This precipitate was thoroughly washed with methanol and then dried in vacuum. To remove the homopolymer, the precipitate was purified by dissolving it in a mixed solvent of chloroform-trifluoroacetic acid (9:1) and precipitating it with a mixed solvent of chloroform-ether (9:1). The obtained copolymer contained 36 mol% of benzyl glutamate. Using benzene as a casting solvent, this copolymer solution was cast onto a glass plate and the benzene was evaporated to form benzyl leucine glutamate.
A block copolymer film (film A) of benzyl glutamate was obtained. This film (thickness 0.02 mm) was coated with 3-amino-1
- Immersed in propanol and reacted at 80°C for 10 days. After the reaction, the film was thoroughly washed in ethanol and then in water. In the infrared absorption spectrum, the absorption based on the ester at 1730 cm -3 disappeared after the reaction, and the absorption based on the hydroxyl group at 3400 cm -1 appeared, indicating that [N 5 -(3-hydroxypropyl)-glutamine]-leucine-[ It was confirmed that a block copolymer (film B) of N 5 -3-hydroxypropyl)-glutamine had been synthesized. Example 2 A culture solution containing human-derived epithelial cells (approximately 100,000 cells/ml) was placed on the film obtained in Example 1 at 5% carbon dioxide concentration, 100% humidity, and 37°C. I left it in the room. After 17 hours, the film was gently washed with phosphate buffer, and the amount of cells adhering to the film was quantified by nuclear staining. For comparison, a (leucine-benzyl glutamate) random copolymer (containing 30% benzyl glutamate) and a 3-amino-1-propanol-treated film (C film) of this random copolymer were used for blood conduits. A similar cell adhesion test was conducted using silicone rubber and a commercially available cell culture sheet as a standard sample. The cell attachment rate was determined by dividing the amount of cells attached to the film by the amount of cells attached to the standard sample, and the results are shown in Table 1.
【表】
実施例 ３
実施例１において、３−アミノ−１−プロパノ
ールのかわりに５−アミノ−１−ペンタノールを
用い、80℃で10日間反応させるかわりに80℃で14
日間反応させる以外は実施例１と同様にして、
［N5−（５−ヒドロキシペンチル）−グルタミン］
−ロイシン−［N5−（５−ヒドロキシペンチル）−
グルタミン］のブロツク共重合体膜を得た。
実施例 ４
ガラス管の内表面に実施例１の（ロイシン−グ
ルタミン酸誘導体）ブロツク共重合体を塗布し、
乾燥させた後、３−アミノ−１−プロパノール中
80℃で１日間処理し、エタノールで洗浄した後、
さらに80℃以上の熱水中に８時間以上浸漬させ、
乾燥後ガラス管からはずし、管状物を得た。
(f) 発明の効果
本発明は以上説明したように、細胞付着性の少
ないことを必要とする血液導管において、アミノ
アルコールで変性された（ロイシン−グルタミン
酸誘導体）ブロツク共重合体を内表面に成型する
ことにより細胞の付着を抑え、かつ、この血液導
管を任意の形状で得ることが可能である。[Table] Example 3 In Example 1, 5-amino-1-pentanol was used instead of 3-amino-1-propanol, and instead of reacting at 80°C for 10 days, 14
In the same manner as in Example 1 except for reacting for days,
[ N5- (5-hydroxypentyl)-glutamine]
-Leucine-[ N5- (5-hydroxypentyl)-
A block copolymer film of glutamine was obtained. Example 4 The (leucine-glutamic acid derivative) block copolymer of Example 1 was applied to the inner surface of a glass tube,
After drying, in 3-amino-1-propanol
After processing at 80°C for 1 day and washing with ethanol,
Furthermore, it is immersed in hot water of 80℃ or higher for 8 hours or more.
After drying, it was removed from the glass tube to obtain a tubular product. (f) Effects of the Invention As explained above, the present invention provides a blood conduit that requires low cell adhesion by molding an amino alcohol-denatured (leucine-glutamic acid derivative) block copolymer on the inner surface. By doing so, cell adhesion can be suppressed and the blood conduit can be obtained in any shape.
Claims (1)
グルタミン酸誘導体）ブロツク共重合体を内表面
に有する血液導管。1 Modified with amino alcohol (leucine-
A blood conduit that has a block copolymer (glutamic acid derivative) on its inner surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61174199A JPS6331670A (en) | 1986-07-24 | 1986-07-24 | Blood conduit |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61174199A JPS6331670A (en) | 1986-07-24 | 1986-07-24 | Blood conduit |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6331670A JPS6331670A (en) | 1988-02-10 |
| JPH0148779B2 true JPH0148779B2 (en) | 1989-10-20 |
Family
ID=15974458
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61174199A Granted JPS6331670A (en) | 1986-07-24 | 1986-07-24 | Blood conduit |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6331670A (en) |
-
1986
- 1986-07-24 JP JP61174199A patent/JPS6331670A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6331670A (en) | 1988-02-10 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |