JPH0553145B2 - - Google Patents
Info
- Publication number
- JPH0553145B2 JPH0553145B2 JP1125539A JP12553989A JPH0553145B2 JP H0553145 B2 JPH0553145 B2 JP H0553145B2 JP 1125539 A JP1125539 A JP 1125539A JP 12553989 A JP12553989 A JP 12553989A JP H0553145 B2 JPH0553145 B2 JP H0553145B2
- Authority
- JP
- Japan
- Prior art keywords
- silicone rubber
- silk
- silk fibroin
- composite
- silk protein
- 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 - Lifetime
Links
- 229920002379 silicone rubber Polymers 0.000 claims description 39
- 239000004945 silicone rubber Substances 0.000 claims description 39
- 239000002131 composite material Substances 0.000 claims description 15
- 108090000623 proteins and genes Proteins 0.000 claims description 15
- 102000004169 proteins and genes Human genes 0.000 claims description 15
- 239000012567 medical material Substances 0.000 claims description 6
- 239000012460 protein solution Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000002062 proliferating effect Effects 0.000 claims 1
- 108010022355 Fibroins Proteins 0.000 description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- 230000004663 cell proliferation Effects 0.000 description 8
- 238000007654 immersion Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 241000255789 Bombyx mori Species 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 210000004907 gland Anatomy 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000021164 cell adhesion Effects 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 230000035755 proliferation Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000255794 Bombyx mandarina Species 0.000 description 1
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002473 artificial blood Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012091 fetal bovine serum Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000012758 nuclear staining Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000002504 physiological saline solution Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 229920000260 silastic Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
Landscapes
- Materials For Medical Uses (AREA)
Description
［技術分野］
本研究は、医療用材料として有用な絹タンパク
質被覆シリコーンゴム複合体に関するものであ
る。
［従来技術］
シリコーンゴムは生理的にはほとんど不活性で
あることから、医療用材料として用いられる。し
かし、シリコーンゴムは疎水性材料であるため生
体組織となじむようにするには親水性化処理を施
す必要がある。一方、絹タンパク質は、古くから
外科用縫合糸として用いられてきており、生体に
対して安全性が高い。また、絹フイブロインから
なる膜状物では細胞の付着・増殖性の良いことが
確認されている。
［目的］
本発明の目的は、シリコーンゴム表面に絹タン
パク質を被覆した複合体からなる医療用材料を提
供することにある。
［構成］
本発明は、シリコーンゴム表面を絹タンパク質
で被覆した複合体に関するもので、該複合体は細
胞の付着・増殖性が良好であることを特徴とする
医療用材料である。
本研究者は、シリコーンゴムを生体となじませ
るため、種々の研究を重ねた結果、シリコーンゴ
ム表面に絹タンパク質を被覆させることで調製し
た複合体は細胞の付着・増殖性が優れることを見
い出し、本発明を完成させるに到つた。
本明細書における医療用材料としては、血液、
輸血、透析液、電気などを対外へ導出あるいは体
内へ導入するために用いられる皮膚端子（あるい
は皮膚貫通管）などのようにその外面側が生体組
織細胞と密着することが要求される人工臓器、医
療用器具あるいは用具を作成するための材料を意
味する。
絹タンパク質で被覆するシリコーンゴムの形状
はシート状、チユーブ状、ビーズ状、繊維状、中
空糸状等いかなる形状を有するものでもよい。
本発明の複合体は、シリコーンゴムを絹タンパ
ク質水溶液中に浸漬し、その後、乾燥することに
よつて製造することができる。ただし、このまま
ではシリコーンゴム表面を被覆した絹タンパク質
は非晶質であるので、絹タンパク質を結晶化させ
る作用をもつエタノールやメタノール等の溶媒で
処理して結晶化度を増してもよい。
原料として用いる絹タンパク質は絹フイブロイ
ンであり、家蚕あるいは野蚕由来のものでもよ
い。また絹タンパク質水溶液は熟蚕体内の絹糸腺
より取り出した液状絹タンパク質を用いることが
できるし、吐糸繊維あるいは生糸を濃厚な中性塩
溶液で溶解させて調製した再生絹タンパク質溶液
でもよい。
［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。本発明はこれらの実施例によつて限定される
ものではない。
実施例 １
熟蚕期の家蚕（５齢５日目）体内より取り出
し、水洗いした絹糸腺のうち、液状絹物質が一番
多く含まれる中部糸腺内容物を材料として用い
た。絹糸腺細胞をピンセツトで除去して得られた
液状絹を蒸留水中に入れ、５℃で静置する。分散
時間が２時間以内で液状絹から溶出した分画をデ
カンテーシヨン法で除去した後、さらに蒸留水を
加え、分散時間が８時間後の試料溶液を絹フイブ
ロイン溶液とした。
シリコーンゴムはSilastic（Dow Corning社製
Non−reinforced 500−３ メデイカルグレー
ド）を使用した。25℃の絹フイブロイン水溶液
（濃度0.7％）にシリコーンゴムを所定時間浸漬し
て絹フイブロインを吸着させ、その後風乾して試
料を作成した。
実施例 ２
絹フイブロイン水溶液で30分間浸漬処理したシ
リコーンゴム（SF−30M）の全反射赤外吸収ス
ペクトル（IRスペクトル）には、未処理のシリ
コーンゴムのスペクトルと比較すると、タンパク
質の分子形態に帰属する3250cm-1、1655cm-1、
1540cm-1のピークが観察されるため、シリコーン
ゴムに絹フイブロインが吸着していることが確か
められた。
シリコーンゴム表面上の絹フイブロインの吸着
層の厚さを岩本らが提案した次の評価法［K.
Ohta and R.Iwamoto，Appl.Spectrosc.，39，
418（1985）］により試算した。内部反射エレメン
トとして入射角45°のゲルマニウムを用いたとき、
吸着層の厚さと吸光度との間には(1)式が成立す
る。
ｔ＝（−340000／Ｎ）1n［Ａ（ｔ）／Ａ（０）］
…(1)
ここでｔは表面層の厚さ（nm）、Ａ（ｔ）は絹
フイブロインが吸着した試料におけるシリコーン
ゴムに起因する特性バンドの吸光度、Ａ（０）は
未処理のシリコーンゴムに特有なバンドの吸光
度、Ｎは特性バンドの波数（cm-1である。ここで
はシリコーンゴムの特性バンドに波数1260cm-1を
選び、(1)式により絹フイブロイン層の厚さを求め
た。絹フイブロイン水溶液での浸漬時間が１分程
度以下でシリコーンゴム表面に付着した絹フイブ
ロイン層の厚さは急激に30〜40nmまで増加し、
その後徐々に層の厚さが増すような結果が得られ
た（第１図）。
差スペクトル法により、シリコーンゴム表面に
吸着した絹フイブロインのみのスペクトルを求め
た。吸着時間が短い試料（10分以下の試料）の
IRスペクトルにはアミドバンドが1630cm-1、
アミドバンドが1520cm-1に現れ、β型分子形態
の特徴と一致した結果が現われた。しかし吸着時
間が30分以上になると、複合体試料（SF−30M）
のIRスペクトルには、アミドバンドが1655cm-
１とアミドバンドが1540cm-1とに観察された。
SF−30Mを50％メタノール水溶液に浸漬して30
分間処理を行うと、β−構造に変化することか
ら、シリコーンゴム表面でランダムコイル状態の
絹フイブロインがメタノール処理でβ化すること
が確認された。
シリコーンゴムに吸着した絹フイブロインは、
純水および生理食塩水で浸漬処理しても脱着しな
かつた。
実施例 ３
絹フイブロイン水溶液中、時間を変えて浸漬処
理して作製したシリコーンゴム複合体に対する水
の接触角を測定した（第１表）。なお、水中にお
ける接触角は、水に浸漬した試料膜あるいは複合
体に微細な空気の泡を付着させ、付着点での泡の
接線と試料表面とのなす角から求めた、シリコー
ンゴムに絹フイブロインが吸着した複合体試料で
[Technical field] This research relates to a silk protein-coated silicone rubber composite useful as a medical material. [Prior Art] Silicone rubber is used as a medical material because it is almost physiologically inert. However, since silicone rubber is a hydrophobic material, it is necessary to perform hydrophilic treatment to make it compatible with living tissue. On the other hand, silk proteins have been used as surgical suture threads for a long time and are highly safe for living organisms. Furthermore, it has been confirmed that a membrane-like material made of silk fibroin has good cell attachment and proliferation properties. [Objective] An object of the present invention is to provide a medical material comprising a composite material in which the surface of silicone rubber is coated with silk protein. [Structure] The present invention relates to a composite in which a silicone rubber surface is coated with silk protein, and the composite is a medical material characterized by good cell adhesion and proliferation properties. After conducting various studies to make silicone rubber compatible with living organisms, the researchers found that a composite prepared by coating the silicone rubber surface with silk protein has excellent cell adhesion and proliferation properties. The present invention has now been completed. The medical materials used herein include blood,
Artificial organs and medical devices that require the outer surface to be in close contact with living tissue cells, such as skin terminals (or skin-penetrating tubes) used to conduct blood transfusions, dialysate, electricity, etc. to the outside or into the body. means a material for making a tool or tool. The silicone rubber coated with silk protein may have any shape such as sheet, tube, bead, fiber, or hollow fiber. The composite of the present invention can be produced by dipping silicone rubber into an aqueous silk protein solution and then drying it. However, since the silk protein coated on the silicone rubber surface is amorphous as it is, the degree of crystallinity may be increased by treatment with a solvent such as ethanol or methanol that has the effect of crystallizing silk protein. The silk protein used as a raw material is silk fibroin, which may be derived from domestic silkworms or wild silkworms. The aqueous silk protein solution may be a liquid silk protein extracted from the silk gland within a mature silkworm body, or may be a regenerated silk protein solution prepared by dissolving spun fibers or raw silk in a concentrated neutral salt solution. [Example] Next, the present invention will be explained in more detail with reference to Examples. The present invention is not limited to these examples. Example 1 Among the silk glands taken out from the body of a domestic silkworm at the mature silkworm stage (5 days old, 5 days old) and washed with water, the contents of the middle gland containing the most liquid silk substance were used as a material. The liquid silk obtained by removing the silk gland cells with tweezers is placed in distilled water and allowed to stand at 5°C. After the fraction eluted from the liquid silk within 2 hours of dispersion time was removed by a decantation method, distilled water was further added, and the sample solution after 8 hours of dispersion time was used as a silk fibroin solution. Silicone rubber is Silastic (manufactured by Dow Corning)
Non-reinforced 500-3 medical grade) was used. A silicone rubber was immersed in an aqueous silk fibroin solution (concentration 0.7%) at 25°C for a predetermined time to adsorb silk fibroin, and then air-dried to prepare a sample. Example 2 The total internal reflection infrared absorption spectrum (IR spectrum) of silicone rubber (SF-30M) immersed in a silk fibroin aqueous solution for 30 minutes shows that it can be attributed to the molecular form of protein when compared with the spectrum of untreated silicone rubber. 3250cm -1 , 1655cm -1 ,
Since a peak at 1540 cm -1 was observed, it was confirmed that silk fibroin was adsorbed to the silicone rubber. The thickness of the silk fibroin adsorption layer on the silicone rubber surface was evaluated using the following evaluation method proposed by Iwamoto et al. [K.
Ohta and R. Iwamoto, Appl. Spectrosc., 39,
418 (1985)]. When germanium with an incident angle of 45° is used as the internal reflection element,
Equation (1) holds true between the thickness of the adsorption layer and the absorbance. t=(-340000/N)1n[A(t)/A(0)]
...(1) Here, t is the thickness of the surface layer (nm), A(t) is the absorbance of the characteristic band caused by silicone rubber in the sample to which silk fibroin has been adsorbed, and A(0) is the absorbance of the characteristic band caused by silicone rubber in the sample to which silk fibroin has been adsorbed. The absorbance of the characteristic band, N is the wave number of the characteristic band (cm -1 ).Here, a wave number of 1260 cm -1 was chosen as the characteristic band of silicone rubber, and the thickness of the silk fibroin layer was determined using equation (1).Silk When immersed in an aqueous fibroin solution for less than 1 minute, the thickness of the silk fibroin layer attached to the silicone rubber surface rapidly increases to 30-40 nm.
After that, the result was that the layer thickness gradually increased (Fig. 1). The spectrum of only silk fibroin adsorbed on the silicone rubber surface was determined by difference spectroscopy. For samples with short adsorption time (10 minutes or less)
The IR spectrum has an amide band at 1630 cm -1 ,
An amide band appeared at 1520 cm -1 , a result consistent with the characteristics of the β-type molecular morphology. However, when the adsorption time exceeds 30 minutes, the composite sample (SF-30M)
The IR spectrum of has an amide band at 1655 cm -
1 and an amide band were observed at 1540 cm -1 .
SF-30M was immersed in 50% methanol aqueous solution for 30 minutes.
It was confirmed that silk fibroin, which is in a random coil state on the silicone rubber surface, becomes β-formed when treated with methanol because it changes to a β-structure when treated for minutes. Silk fibroin adsorbed to silicone rubber is
No desorption occurred even after immersion treatment in pure water and physiological saline. Example 3 The contact angle of water was measured for silicone rubber composites prepared by immersion in a silk fibroin aqueous solution for different times (Table 1). The contact angle in water was determined by attaching fine air bubbles to a sample membrane or composite immersed in water, and determining the angle between the tangent of the bubbles at the attachment point and the sample surface. In the composite sample with adsorbed
【表】
理した試料
は未吸着シリコーンゴムに比べて接触角が著しく
低下した。浸漬時間を変えても接触角がほとんど
変化せず、いずれも絹フイブロイン膜に対する値
とほぼ同一の値であつた。これらの結果から、シ
リコーンゴムを５秒間絹フイブロイン水溶液と接
触させ、シリコーンゴム表面に10nm程度の絹フ
イブロイン吸着層を生成することで、シリコーン
ゴム複合体表面は絹フイブロインの付着に基づ
き、完全に親水性表面に変化した。
実施例 ４
絹フイブロインで被覆したシリコーンゴムに対
する細胞の付着・増殖能を測定した。絹フイブロ
インで被覆したシリコーンゴム上に、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℃のインキユベータ内に静
置した。培養液は10％の牛胎児血清を含むEagle
MEMを用いた。50時間後、そのシリコーンゴム
上に付着している細胞の数をクリスタルバイオレ
ツトを用いた核染色法により定量した。
これらのシリコーンゴム複合体に付着した細胞
の数を標準試料（和光純薬工業株式会社製の組織
培養用プラスチツクシート）に付着した細胞の数
で割ることにより、細胞増殖率を求めた。その結
果を第２図に示す。
細胞増殖率は、未被覆シリコーンゴムでは約40
％であつたが、絹フイブロイン水溶液での浸漬時
間が１分以下で急激に約140％まで増加し、その
後ほぼ一定になる結果が得られた。この増殖率の
値は絹フイブロイン膜での値とほぼ一致してい
た。この細胞増殖率増加の傾向はシリコーンゴム
に吸着した絹フイブロイン層の厚化の傾向（第１
図）と符合しており、絹フイブロイン吸着層が薄
い場合（短時間の浸漬処理の場合）には下地であ
るシリコーンゴムの表面特性が細胞増殖に影響を
及ぼした。
［効果］
以上説明したように、本発明のシリコーンゴム
を絹タンパク質との複合体は、シリコーンゴムを
絹タンパク質水溶液中に短時間浸漬する簡単な処
理で調製することができ、さらにこの複合体は絹
タンパク質に帰属する優れた細胞の付着・増殖性
を持つていることから、医療分野で幅広く利用で
きる。[Table] The contact angle of the treated sample was significantly lower than that of unadsorbed silicone rubber. Even if the immersion time was changed, the contact angle hardly changed, and both values were almost the same as those for the silk fibroin membrane. From these results, we found that by bringing silicone rubber into contact with an aqueous silk fibroin solution for 5 seconds to generate a silk fibroin adsorption layer of approximately 10 nm on the silicone rubber surface, the surface of the silicone rubber composite becomes completely hydrophilic due to the adhesion of silk fibroin. changed to a sexual surface. Example 4 The adhesion and proliferation ability of cells to silicone rubber coated with silk fibroin was measured. The culture solution (approx.
100,000 pieces/ml) were left in contact with each other in an incubator at 37°C with a carbon dioxide concentration of 5% and humidity of 100%. The culture medium is Eagle containing 10% fetal bovine serum.
MEM was used. After 50 hours, the number of cells adhering to the silicone rubber was quantified by nuclear staining using crystal violet. The cell proliferation rate was determined by dividing the number of cells attached to these silicone rubber composites by the number of cells attached to a standard sample (plastic sheet for tissue culture manufactured by Wako Pure Chemical Industries, Ltd.). The results are shown in FIG. The cell proliferation rate is approximately 40 for uncoated silicone rubber.
%, but it rapidly increased to about 140% when the immersion time in the silk fibroin aqueous solution was less than 1 minute, and then became almost constant. This value of proliferation rate was almost in agreement with the value for silk fibroin membrane. This tendency of increasing cell proliferation rate is due to the tendency of thickening of the silk fibroin layer adsorbed to silicone rubber (the first
(Figure), when the silk fibroin adsorption layer was thin (in the case of short-time immersion treatment), the surface characteristics of the underlying silicone rubber affected cell proliferation. [Effect] As explained above, the complex of silicone rubber and silk protein of the present invention can be prepared by a simple process of immersing silicone rubber in an aqueous silk protein solution for a short time, and furthermore, this complex can be It has excellent cell adhesion and proliferation properties, which are characteristic of silk proteins, so it can be widely used in the medical field.
第１図 絹フイブロイン層の厚さと浸漬時間と
の関係、第２図 細胞増殖率と浸漬時間との関
係。
Figure 1: Relationship between silk fibroin layer thickness and immersion time. Figure 2: Relationship between cell proliferation rate and immersion time.
Claims (1)
た複合体。 ２ シリコーンゴムを絹タンパク質水溶液中に浸
漬させて複合体を製造する方法。 ３ シリコーンゴム表面を絹タンパク質で被覆し
た複合体から形成されており、かつ細胞の付着・
増殖性が良好であることを特徴とする医療用材
料。[Claims] 1. A composite in which a silicone rubber surface is coated with silk protein. 2. A method of manufacturing a composite by immersing silicone rubber in an aqueous silk protein solution. 3. It is formed from a composite material in which the silicone rubber surface is coated with silk protein, and it is highly effective for cell attachment and
A medical material characterized by good proliferative properties.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1125539A JPH03123561A (en) | 1989-05-17 | 1989-05-17 | Composite consisting of silicone rubber and silk protein and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1125539A JPH03123561A (en) | 1989-05-17 | 1989-05-17 | Composite consisting of silicone rubber and silk protein and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03123561A JPH03123561A (en) | 1991-05-27 |
| JPH0553145B2 true JPH0553145B2 (en) | 1993-08-09 |
Family
ID=14912697
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1125539A Granted JPH03123561A (en) | 1989-05-17 | 1989-05-17 | Composite consisting of silicone rubber and silk protein and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03123561A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9217017B2 (en) * | 2009-12-08 | 2015-12-22 | Amsilk Gmbh | Silk protein coatings |
| JP6544040B2 (en) * | 2015-05-21 | 2019-07-17 | 日立化成株式会社 | Fibroin nano thin film, nano thin film sheet and transfer method |
| JP6743939B2 (en) * | 2019-05-09 | 2020-08-19 | 日立化成株式会社 | Nano thin film transfer sheet and transfer method |
| WO2021046520A1 (en) | 2019-09-06 | 2021-03-11 | Zha Runye Helen | Methods for generating surface coatings via self-assembly of silk fibroin and silk fibroin-like macromolecules |
-
1989
- 1989-05-17 JP JP1125539A patent/JPH03123561A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03123561A (en) | 1991-05-27 |
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