JPH01308431A - Silk fibroin hydrogel - Google Patents
Silk fibroin hydrogelInfo
- Publication number
- JPH01308431A JPH01308431A JP14025388A JP14025388A JPH01308431A JP H01308431 A JPH01308431 A JP H01308431A JP 14025388 A JP14025388 A JP 14025388A JP 14025388 A JP14025388 A JP 14025388A JP H01308431 A JPH01308431 A JP H01308431A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogel
- silk
- silk fibroin
- solution
- freezing
- 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
- 239000000017 hydrogel Substances 0.000 title claims abstract description 45
- 108010022355 Fibroins Proteins 0.000 title claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- 238000007710 freezing Methods 0.000 abstract description 13
- 230000008014 freezing Effects 0.000 abstract description 13
- 238000010257 thawing Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 9
- 239000007788 liquid Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 241000255789 Bombyx mori Species 0.000 abstract description 4
- 229940034586 silk sericin Drugs 0.000 abstract description 4
- 230000002411 adverse Effects 0.000 abstract description 2
- 210000004204 blood vessel Anatomy 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 210000004907 gland Anatomy 0.000 abstract description 2
- 210000003205 muscle Anatomy 0.000 abstract description 2
- 239000002473 artificial blood Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- 102000004190 Enzymes Human genes 0.000 description 7
- 108090000790 Enzymes Proteins 0.000 description 7
- 239000000499 gel Substances 0.000 description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 238000000034 method Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 108090000623 proteins and genes Proteins 0.000 description 4
- 102000004169 proteins and genes Human genes 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000004113 cell culture Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000013268 sustained release Methods 0.000 description 2
- 239000012730 sustained-release form Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 241000255794 Bombyx mandarina Species 0.000 description 1
- 235000009852 Cucurbita pepo Nutrition 0.000 description 1
- 241000219104 Cucurbitaceae Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000012773 agricultural material Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 210000000695 crystalline len Anatomy 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000002523 gelfiltration Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000829 suppository Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔技術分野〕
本発明は絹フィブロインのハイドロゲルに関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a silk fibroin hydrogel.
高分子ハイドロゲルは、医用材料、農業用材料、食品工
業材料として、＃広い産業分野で使用されている６例え
ば、ポリエチレンオキサイド系高分子は徐放医薬用ヒド
ロゲルとして使用されるが、反応条件の微妙な違いによ
りハイドロゲルの粘度。Polymer hydrogels are used in a wide range of industrial fields, such as medical materials, agricultural materials, and food industrial materials.6 For example, polyethylene oxide polymers are used as sustained-release pharmaceutical hydrogels, but depending on the reaction conditions. There are subtle differences in the viscosity of hydrogels.
結晶化度、架橋度が変化するため調整条件を厳密にコン
トロールしなければならず、必ずしも使用容易な製品で
あるとはいえない、この他の合成高分子ハイドロゲルの
素材としては、ポリメチルメタクリレート、塩基性グラ
フトコポリマーあるいはアニオン性ポリイオンコンプレ
ックス、ポリエーテル製ポリウレタン等があるが、これ
らの作製時においても反応条件を適宜制御する必要があ
る。Polymethyl methacrylate is another synthetic polymer hydrogel material that requires strict control of the adjustment conditions because the degree of crystallinity and degree of crosslinking changes, and is not necessarily an easy-to-use product. , basic graft copolymers, anionic polyion complexes, polyether polyurethanes, etc., but it is necessary to appropriately control the reaction conditions when producing these.
またこうした高分子を用いた場合高強度のゲルを得るこ
とは困難である場合が多い、またポリビニールアルコー
ル溶液を凍結後、解凍することでポリビニールアルコー
ルのハイドロゲルが得られることが知られている（特開
昭４７−１２８５４：特開昭５９−５６４４６）、 Ｌ
、かじ、ポリビニールアルコールのハイドロゲルよりも
更に良好な生体適合性を有するものとしては、生体組織
の化学構造に類似した組成を有する生体蛋白質のハイド
ロゲルが考えられる。Furthermore, it is often difficult to obtain a high-strength gel when using such polymers, and it is known that a polyvinyl alcohol hydrogel can be obtained by freezing and then thawing a polyvinyl alcohol solution. (Japanese Patent Publication No. 47-12854: Japanese Patent Application Publication No. 59-56446), L
Hydrogels of biological proteins, which have a composition similar to the chemical structure of biological tissues, are considered to have better biocompatibility than hydrogels of polyvinyl alcohol.
医薬用のハイドロゲル素材は、医薬用担体として生体内
での使用が前提となるため、ゲル強度が高く、かつ生体
適合性の良好な素材であることが望まれている。Since hydrogel materials for pharmaceutical use are intended to be used in vivo as pharmaceutical carriers, they are desired to have high gel strength and good biocompatibility.
本発明は、生体に対して悪影響を及ぼす恐れのある有機
試薬を用いることなく、前記の如き問題を含まない新し
い素材からなるハイドロゲルを提供することを目的とす
る。An object of the present invention is to provide a hydrogel made of a new material that does not involve the above-mentioned problems and does not use organic reagents that may have an adverse effect on living organisms.
本発明によれば、特別な製造装置を用いることなく、絹
フィブロイン溶液を凍結・解凍あるいはその繰り返しを
行うなどの簡単な処理により得られる。粘着性が無く、
ゲル強度が高く、かつ高含水率の絹フィブロインハイド
ロゲルが提供される。According to the present invention, a silk fibroin solution can be obtained by simple processing such as freezing and thawing or repeating the same without using any special production equipment. No stickiness,
A silk fibroin hydrogel with high gel strength and high water content is provided.
本発明者は、絹蛋白質の構造と物性との関連に注目し、
特に溶解性におよぼす微細構造の影響ならびに絹蛋白質
の機能を生かした高次利用技術の開発について種々研究
を重ねた結果、絹フィブロインの濃厚溶液を凍結・乾燥
することで粘着性が無く、生体適合性の良好な絹ブイプ
ロインのハイドロゲルが容易に作製できることを見出し
、本発明を完成するに到った。The present inventor focused on the relationship between the structure and physical properties of silk proteins,
In particular, as a result of various studies on the influence of microstructure on solubility and the development of advanced utilization technology that takes advantage of the functions of silk proteins, we found that by freezing and drying a concentrated solution of silk fibroin, it becomes non-sticky and biocompatible. The present inventors have discovered that a hydrogel of silk buproin with good properties can be easily produced, and have completed the present invention.
本発明の絹フィブロインハイドロゲルは、２％以上、好
ましくは４％以上の絹フィブロインの水溶液を一５℃以
下、好ましくは一１５℃以下で一旦凍結させ、５℃以上
、好ましくは２５℃以上で徐々に解凍することで、試料
に含まれる自由水が放出する過程で該ハイドロゲルが容
易に製造できる。この際、ハイドロゲルを製造するため
の特別な製造装置は不用である。原料としての絹フィブ
ロインとしては、家蚕あるいは野蚕由来のものでよい、
また絹フィブロイン溶液は、熟蚕体内の絹糸腺より取り
出し、その外層を覆っている絹セリシン分画を除去した
後の液状絹フィブロイン゛を用いることも可能である。The silk fibroin hydrogel of the present invention can be prepared by freezing an aqueous solution of silk fibroin containing 2% or more, preferably 4% or more at a temperature of 15°C or lower, preferably 115°C or lower, and then freezing it at 5°C or higher, preferably 25°C or higher. By gradually thawing the sample, the hydrogel can be easily produced in the process of releasing free water contained in the sample. At this time, no special manufacturing equipment is required for manufacturing the hydrogel. Silk fibroin as a raw material may be derived from domestic silkworms or wild silkworms.
Further, as the silk fibroin solution, it is also possible to use liquid silk fibroin extracted from the silk gland in the mature silkworm body and after removing the silk sericin fraction covering the outer layer.
あるいは繭糸あるいは絹糸状繊維を精練により絹セリシ
ンを除去したものを濃厚中性液溶液で溶解することで得
られる再生絹フィブロイン溶液を用いることも可能であ
る。絹フィブロインハイドロゲルは、ゲル作製時の容器
あるいは絹フィブロイン溶液の充填方法を適宜変えるこ
とで。Alternatively, it is also possible to use a regenerated silk fibroin solution obtained by dissolving cocoon filaments or silk-like fibers from which silk sericin has been removed by scouring in a concentrated neutral liquid solution. Silk fibroin hydrogel can be produced by changing the container or filling method of silk fibroin solution as appropriate during gel production.
フィルム状や管状の他、ブロック状等任意の形状とする
ことができる０本発明の絹フィブロインハイドロゲルは
、粘着性が無く、かつ絹フィブロイン以外の不純物を含
まず、毒性の無いこと、生体適合性が良好なことにおい
て特徴を持っている。The silk fibroin hydrogel of the present invention is non-adhesive, contains no impurities other than silk fibroin, is non-toxic, and is biocompatible. It is characterized by good sexual characteristics.
本発明における絹ブイプロインハイドロゲルの強度等の
機械的性質は、ポリビニールアルコールハイドロゲルの
研究結果（特公昭５９−５６４４６）と同様、絹のフィ
ブロイン濃度、凍結、・解凍温度ならびに凍結・解凍の
繰り返し数等によって自由に調節できる。またハイドロ
ゲルの含水率もこれら作用要因の組み合わせで調整でき
る。 ・
本発明においては、このような絹フィブロインハイドロ
ゲル中には、各種酵素や、触媒、医薬品等の薬理活性物
質を含有させることができる。このような酵素、触媒、
あるいは薬理活性物質は。The mechanical properties such as strength of the silk buoyproin hydrogel in the present invention are similar to the research results of polyvinyl alcohol hydrogel (Japanese Patent Publication No. 59-56446), the fibroin concentration of silk, the freezing/thawing temperature, and the freezing/thawing temperature. It can be freely adjusted depending on the number of repetitions, etc. The water content of the hydrogel can also be adjusted by combining these factors. - In the present invention, such silk fibroin hydrogel can contain pharmacologically active substances such as various enzymes, catalysts, and pharmaceuticals. Such enzymes, catalysts,
Or pharmacologically active substances.
絹フィブロイン溶液作製時に溶解ないし分散することで
ハイドロゲル中に均一に、または絹フィブロインハイド
ロゲル作製後これらの酵素等の溶液に接触膨潤させれば
ハイドロゲルの表面に極在して含有させることも可能で
ある。It can be contained uniformly in a hydrogel by dissolving or dispersing it during the preparation of a silk fibroin solution, or it can be contained locally on the surface of the hydrogel by contacting and swelling with a solution of these enzymes after preparing a silk fibroin hydrogel. It is possible.
低分子量の酵素固定担体としてハイドロゲルを用いる場
合においては、上記の方法でこれら酵素等を含有した絹
フィブロインハイドロゲルの表面を酵素の活性を失わな
い範囲でエタノールあるいはメタノール等の絹蛋白質に
対する貧溶媒あるいは酢酸等の水溶性有機溶媒あるいは
水溶性有機酸による不溶化処理等を施すことにより、酵
素を固定化した絹フィブロインハイドロゲルを得ること
ができる。When using a hydrogel as a low-molecular-weight enzyme-immobilized carrier, the surface of the silk fibroin hydrogel containing these enzymes is coated with ethanol or methanol, a poor solvent for silk proteins, to the extent that enzyme activity is not lost. Alternatively, an enzyme-immobilized silk fibroin hydrogel can be obtained by performing insolubilization treatment with a water-soluble organic solvent such as acetic acid or a water-soluble organic acid.
本発明の絹フィブロインハイドロゲルは、含水率９７〜
３０％を示し、従来の高分子ハイドロゲルと同様に種々
の分野において利用し得るものであり、例えば食品分野
、酵素を触媒とする医薬品製造のバイオリアクター、バ
イオセンサーの酵素固定化素材、人工水晶体、人工筋肉
、座薬、生体内分解ヒドロゲル素材、医薬・農薬徐放用
担体、電子顕微鏡用浮遊細胞包埋材、ゲル濾過、土壌改
質材。The silk fibroin hydrogel of the present invention has a water content of 97 to
30%, and like conventional polymer hydrogels, it can be used in various fields, such as the food field, bioreactors for pharmaceutical production using enzymes as catalysts, enzyme immobilization materials for biosensors, and artificial crystalline lenses. , artificial muscles, suppositories, biodegradable hydrogel materials, carriers for sustained release of pharmaceuticals and agricultural chemicals, floating cell embedding materials for electron microscopes, gel filtration, and soil reforming materials.
細胞培養担体、細胞培養床、血液適合性の高い血管壁素
材等として利用することができる。It can be used as a cell culture carrier, a cell culture bed, a blood vessel wall material with high blood compatibility, etc.
次に本発明を実施例によりさらに詳細に説明する。 Next, the present invention will be explained in more detail with reference to Examples.
実施例１
熟蚕より取り出した８５ｇの絹糸服内液状絹（絶乾重量
で約３０幻をポリエチレンフィルム上に、できるだけ平
坦となるように敷きつめた上、 ２００ｍ１の蒸留水を
加え５℃の冷Ｊｌ＆庫中で５時間放置した。液状絹の外
周を覆っている絹セリシン分画を除き絹フィブロインの
みの分画を得るため、デカンテーションにより上澄部分
を除去した後、再び１００ａ＋１の蒸留水を加え、５℃
の冷蔵庫に２０時間放置した。Example 1 85 g of liquid silk (absolutely dry weight: about 30 g) taken from a mature silkworm was spread on a polyethylene film as flat as possible, and 200 ml of distilled water was added to it in cold water at 5°C. It was left in a refrigerator for 5 hours.To obtain a fraction containing only silk fibroin except for the silk sericin fraction covering the outer periphery of the liquid silk, the supernatant was removed by decantation, and 100a+1 distilled water was added again. ,5℃
It was left in the refrigerator for 20 hours.
デカンテーションにより上澄液を取り除くことによって
、ポリエチレンフィルムには、ゲル状の高濃度の紹ブイ
プロイン（６，５幻が得ら九る。−２０℃の冷凍庫中、
４時間処理して凍結した該絹フィブロインを２５℃、湿
度６０％ＲＨで解凍させると、付着性が無く高い含水率
（９３％）の絹フィブロインバイドロゲルが調製できる
。同試料を一２０℃ならびに２５℃で再び凍結・解凍処
理を繰り返す際、繰り返し数を増すことでゲルの強度を
増加した。By removing the supernatant liquid by decantation, a gel-like high concentration of polyproin (6,5%) was obtained on the polyethylene film.
When the silk fibroin treated for 4 hours and frozen is thawed at 25° C. and 60% RH, a non-adhesive silk fibroin vidrogel with a high water content (93%) can be prepared. When the same sample was repeatedly frozen and thawed at -20°C and 25°C, the strength of the gel was increased by increasing the number of repetitions.
実施例２
実施例１の方法と同様にして、３．４％の絹フィブロイ
ン溶液を作製した。−２０℃と２５℃との凍結・乾燥処
理を２回繰り返すことで高含水率（９５％）（乾燥重量
法で求めた値）の絹フィブロインハイドロゲルが得られ
た。この絹フィブロインハイドロゲルは高粘弾性的挙動
を示し、力を加えて一時的に変形させても、除重すると
直ちに元の形状に回復した。このハイドロゲルを２５℃
の蒸留水に浸漬して４日後の重量変化ならびに膨潤状態
を観察したところ、微小であった。Example 2 A 3.4% silk fibroin solution was prepared in the same manner as in Example 1. Silk fibroin hydrogel with a high water content (95%) (value determined by dry weight method) was obtained by repeating the freeze/dry treatment at -20°C and 25°C twice. This silk fibroin hydrogel exhibited highly viscoelastic behavior, and even if it was temporarily deformed by applying force, it immediately recovered its original shape when the weight was removed. This hydrogel was heated at 25°C.
After 4 days of immersion in distilled water, the weight change and swelling state were observed and found to be minute.
実施例３
実施例２で得られた絹フィブロインハイドロゲルを更に
一２０℃と２０℃とでそれぞれ凍結・解凍を繰借返し試
料の含水率が７４％となるように調整した。Example 3 The silk fibroin hydrogel obtained in Example 2 was further frozen and thawed repeatedly at -20°C and 20°C, respectively, to adjust the water content of the sample to 74%.
このようにして得たハイドロゲルを温度２５℃、湿度６
０％に設定した恒温恒温室に放置した際の時間経過と試
料重量の変化を表−１に示す。The hydrogel thus obtained was heated at a temperature of 25°C and a humidity of 6°C.
Table 1 shows the change in sample weight over time when the sample was left in a constant temperature room set at 0%.
表−１
比較例１
凍結・解凍ならびにその繰り返しにより作製できるもの
として知られているポリビニールアルコールハイドロゲ
ルを既知（特開昭５９−５６４４６）の方法でｔＲＨし
た。なお用いたポリビニールアルコールの重合度は２０
００、けん化度は９９モル％であった。Table 1 Comparative Example 1 Polyvinyl alcohol hydrogel, which is known to be able to be produced by freezing and thawing and its repetition, was subjected to tRH using a known method (Japanese Patent Laid-open No. 59-56446). The degree of polymerization of the polyvinyl alcohol used was 20.
00, and the degree of saponification was 99 mol%.
凍結・解凍とを繰り返し含水率８１％のハイドロゲルを
調整した。これを実施例３と同様にして温度２５℃、湿
度６０％に設定した恒温恒湿室に放置した際の時間経過
と試料重量の変化を表−２に示す。A hydrogel with a water content of 81% was prepared by repeating freezing and thawing. Table 2 shows the change in sample weight over time when the sample was left in a constant temperature and humidity chamber set at a temperature of 25° C. and a humidity of 60% in the same manner as in Example 3.
表−２
実施例４
精練絹糸を、４０℃の臭化リチウムの飽和溶液で溶解さ
せた後、セルロース透析膜を用で純水で透析することに
より濃度が０．５％の再生絹フィブロイン溶液を調製す
る。同溶液をポリエチレンフィルム上に置き、送風乾燥
により溶液の濃度を順次高めて３．２瓢の絹フィブロイ
ン溶液を作製した。これを−８０℃で凍結した後、２５
℃で解凍することによりゲル強度の高い絹フィブロイン
ハイドロゲルがｔ！）られた、これを再度−８０℃、２
５℃でそれぞれ凍結、解凍することにより更にゲル強度
の高い絹フィブロインハイドロゲルが得られた。Table 2 Example 4 Regenerated silk fibroin solution with a concentration of 0.5% was obtained by dissolving refined silk thread in a saturated solution of lithium bromide at 40°C and dialyzing it against pure water using a cellulose dialysis membrane. Prepare. The same solution was placed on a polyethylene film, and the concentration of the solution was gradually increased by air drying to prepare 3.2 gourds of silk fibroin solution. After freezing this at -80℃, 25
Silk fibroin hydrogel with high gel strength is produced by thawing at ℃! ), this was heated again at -80℃, 2
Silk fibroin hydrogel with even higher gel strength was obtained by freezing and thawing at 5°C.
Claims (1)
ブロインのハイドロゲル。(1) A silk fibroin hydrogel consisting of a frozen and thawed silk fibroin solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63140253A JP2507885B2 (en) | 1988-06-06 | 1988-06-06 | Silk fibroin hydrogel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63140253A JP2507885B2 (en) | 1988-06-06 | 1988-06-06 | Silk fibroin hydrogel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01308431A true JPH01308431A (en) | 1989-12-13 |
| JP2507885B2 JP2507885B2 (en) | 1996-06-19 |
Family
ID=15264480
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63140253A Expired - Lifetime JP2507885B2 (en) | 1988-06-06 | 1988-06-06 | Silk fibroin hydrogel |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2507885B2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005510268A (en) * | 2001-10-25 | 2005-04-21 | ユニヴァーシティー オブ コネティカット | Bioactive material, method for producing bioactive material and method of use thereof |
| JP2006504852A (en) * | 2002-11-01 | 2006-02-09 | トラスティーズ オブ タフツ カレッジ | Templated natural silk smectic gel |
| JP2009508540A (en) * | 2005-08-17 | 2009-03-05 | オックスフォード バイオマテリアリルズ リミテッド | Implantable cartilage repair device |
| WO2011126031A1 (en) * | 2010-04-06 | 2011-10-13 | 日立化成工業株式会社 | Silk fibroin porous material and method for producing same |
| CN102417733A (en) * | 2011-11-11 | 2012-04-18 | 苏州大学 | Preparation method of silk fibroin nanosphere |
| JP2012080915A (en) * | 2010-10-06 | 2012-04-26 | Hitachi Chemical Co Ltd | Wound covering material |
| CN103981561A (en) * | 2014-05-23 | 2014-08-13 | 苏州大学 | Method and device for preparing electro-polymerized silk fibroin hydrogel membrane and application of fibroin hydrogel membrane |
| CN106421902A (en) * | 2016-11-28 | 2017-02-22 | 武汉纺织大学 | Quick-gelatinization silk fibroin solution and preparation method thereof |
| JP2017186264A (en) * | 2016-04-04 | 2017-10-12 | 三洋化成工業株式会社 | Protein composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01254164A (en) * | 1988-04-01 | 1989-10-11 | Terumo Corp | Wound protecting material and production thereof |
| JPH01256350A (en) * | 1988-04-01 | 1989-10-12 | Terumo Corp | Food using silk fibroin and production thereof |
-
1988
- 1988-06-06 JP JP63140253A patent/JP2507885B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01254164A (en) * | 1988-04-01 | 1989-10-11 | Terumo Corp | Wound protecting material and production thereof |
| JPH01256350A (en) * | 1988-04-01 | 1989-10-12 | Terumo Corp | Food using silk fibroin and production thereof |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005510268A (en) * | 2001-10-25 | 2005-04-21 | ユニヴァーシティー オブ コネティカット | Bioactive material, method for producing bioactive material and method of use thereof |
| JP2006504852A (en) * | 2002-11-01 | 2006-02-09 | トラスティーズ オブ タフツ カレッジ | Templated natural silk smectic gel |
| JP2011202170A (en) * | 2002-11-01 | 2011-10-13 | Trustees Of Tufts College | Templated native silk smectic gel |
| JP4800622B2 (en) * | 2002-11-01 | 2011-10-26 | トラスティーズ オブ タフツ カレッジ | Templated natural silk smectic gel |
| JP2009508540A (en) * | 2005-08-17 | 2009-03-05 | オックスフォード バイオマテリアリルズ リミテッド | Implantable cartilage repair device |
| US9226992B2 (en) | 2005-08-17 | 2016-01-05 | Orthox Limited | Implantable cartilaginous tissue repair device |
| US9090703B2 (en) | 2010-04-06 | 2015-07-28 | Hitachi Chemical Company, Ltd. | Silk fibroin porous material and method for producing same |
| WO2011126031A1 (en) * | 2010-04-06 | 2011-10-13 | 日立化成工業株式会社 | Silk fibroin porous material and method for producing same |
| JP2012080915A (en) * | 2010-10-06 | 2012-04-26 | Hitachi Chemical Co Ltd | Wound covering material |
| CN102417733A (en) * | 2011-11-11 | 2012-04-18 | 苏州大学 | Preparation method of silk fibroin nanosphere |
| CN103981561A (en) * | 2014-05-23 | 2014-08-13 | 苏州大学 | Method and device for preparing electro-polymerized silk fibroin hydrogel membrane and application of fibroin hydrogel membrane |
| JP2017186264A (en) * | 2016-04-04 | 2017-10-12 | 三洋化成工業株式会社 | Protein composition |
| CN106421902A (en) * | 2016-11-28 | 2017-02-22 | 武汉纺织大学 | Quick-gelatinization silk fibroin solution and preparation method thereof |
| CN106421902B (en) * | 2016-11-28 | 2020-02-07 | 武汉纺织大学 | Rapid-gelation silk fibroin solution and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2507885B2 (en) | 1996-06-19 |
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