JPH04263611A - Water-insoluble solid fibroin formed article and its production - Google Patents
Water-insoluble solid fibroin formed article and its productionInfo
- Publication number
- JPH04263611A JPH04263611A JP4432591A JP4432591A JPH04263611A JP H04263611 A JPH04263611 A JP H04263611A JP 4432591 A JP4432591 A JP 4432591A JP 4432591 A JP4432591 A JP 4432591A JP H04263611 A JPH04263611 A JP H04263611A
- Authority
- JP
- Japan
- Prior art keywords
- fibroin
- water
- insoluble solid
- formed article
- solution
- 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.)
- Pending
Links
- 108010022355 Fibroins Proteins 0.000 title claims abstract description 71
- 239000007787 solid Substances 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 8
- 238000001962 electrophoresis Methods 0.000 claims abstract description 5
- 238000000151 deposition Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 8
- 230000008021 deposition Effects 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 8
- 210000004907 gland Anatomy 0.000 description 5
- 241000255789 Bombyx mori Species 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 241000238631 Hexapoda Species 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 108010013296 Sericins Proteins 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000000502 dialysis Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000009991 scouring Methods 0.000 description 3
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- YUUKIOKWOBAUSK-UHFFFAOYSA-L [OH-].[OH-].[Cu+2].NCCN Chemical compound [OH-].[OH-].[Cu+2].NCCN YUUKIOKWOBAUSK-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000000762 glandular Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 210000001835 viscera Anatomy 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Peptides Or Proteins (AREA)
- Artificial Filaments (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、水不溶性固形フィブロ
イン成形物及びその製造法に関し、更に詳しくは、所望
の形状をした安定で均質なゲル状の水不溶性固形フィブ
ロイン成形物と、これを一段階の操作で短時間に、得る
ことに関する。[Field of Industrial Application] The present invention relates to a water-insoluble solid fibroin molded product and a method for producing the same, and more particularly, to a stable and homogeneous gel-like water-insoluble solid fibroin molded product having a desired shape, and a method for manufacturing the same. Concerning obtaining, in a short time, step-by-step operations.
【０００２】0002
【従来の技術】絹糸は衣料用のみならず縫合糸等の様に
医療分野でも幅広く利用されている。絹糸の主成分はフ
ィブロインというタンパク質であり、蚕等の昆虫体内で
合成され、絹糸腺と呼ばれる体内器官に蓄積されている
。このフィブロインは、昆虫体内では液状を呈しており
水に対して可溶性である。BACKGROUND OF THE INVENTION Silk threads are widely used not only for clothing but also in the medical field, such as suture threads. The main component of silk is a protein called fibroin, which is synthesized within the bodies of insects such as silkworms and is stored in internal organs called silk glands. This fibroin is liquid in the insect body and is soluble in water.
【０００３】また、フィブロインは、延伸やずり応力と
いった物理的作用や極性有機溶媒による脱水変性作用と
いった化学的作用（例えば、馬越淳，高分子，３４［２
］，９７（１９８５）．など参照）や架橋剤の作用（例
えば、特開平０１−１１８５３０号など参照）によって
、水に対して不溶化する性質を持っている。[0003] Fibroin is also affected by physical effects such as stretching and shear stress, and chemical effects such as dehydration and modification by polar organic solvents (for example, Jun Umakoshi, Polymers, 34 [2
], 97 (1985). etc.) or the action of a crosslinking agent (see, for example, JP-A No. 01-118530), it has the property of becoming insoluble in water.
【０００４】一方、絹糸は、蚕が吐糸することによりず
り応力が加わり、液状絹フィブロインが不溶化したもの
である。絹糸を再び水に可溶なものにするには生糸をマ
ルセル石鹸等で浸漬することにより精練して、フィブロ
イン繊維を取り囲んでいるセリシンを除去した後、臭化
リチウム等の塩溶液を高濃度で作用させる方法などがあ
る。[0004] On the other hand, silk thread is made by insolubilizing liquid silk fibroin due to shear stress applied by silkworms. To make the silk thread soluble in water again, the raw silk is scoured by soaking it in Marcel soap to remove the sericin surrounding the fibroin fibers, and then soaked in a highly concentrated salt solution such as lithium bromide. There are ways to make it work.
【０００５】尚、フィブロインは生物に対して無毒と言
われ、また生分解性であるため生体内や適度な条件下で
は微生物により分解される。また、紫外線やγ線によっ
ても分解される。燃焼しても有毒ガスを出すことはない
。[0005] Fibroin is said to be non-toxic to living organisms, and is biodegradable, so it can be decomposed in vivo or by microorganisms under appropriate conditions. It is also decomposed by ultraviolet rays and gamma rays. It does not emit toxic gas when burned.
【０００６】次に、水不溶性固形フィブロイン成形物の
製造法としては、次の二段階の方式が一般的である。ま
ず第一段階として、フィブロインを精練し水に溶かした
ものを型にいれて乾燥する。但し、得られる形状は平面
的なものに限定されてしまい、また、この状態では通常
は水にとける。そこで、第２段階としてメタノールに３
０秒以上浸漬する方法により分子状態を変化させ水に不
溶化する。しかし、メタノールの濃度や浸漬する時間な
どの条件により強度や伸度といった物理的性質も変化し
、安定した品質を得るのが難しい。[0006] Next, as a method for producing a water-insoluble solid fibroin molded article, the following two-stage method is generally used. The first step is to refine the fibroin, dissolve it in water, put it into a mold, and dry it. However, the shape obtained is limited to a flat shape, and in this state it usually dissolves in water. Therefore, in the second step, 3
The molecular state is changed by immersion for 0 seconds or more to make it insoluble in water. However, physical properties such as strength and elongation change depending on conditions such as methanol concentration and immersion time, making it difficult to obtain stable quality.
【０００７】また、水不溶性固形フィブロイン成形物の
製造法としては、精練絹の粉砕等の方法により得た微粉
体を型にいれ圧力と熱を加えて成形する方法（例えば、
平林潔，高分子，３８［１２］，１０６２（１９８９）
．など参照）も知られているが、大きさや品質の制御が
難しく、実用時に課題が残る。[0007] In addition, as a method for producing a water-insoluble solid fibroin molded product, a fine powder obtained by a method such as pulverization of scouring silk is placed in a mold and molded by applying pressure and heat (for example,
Kiyoshi Hirabayashi, Kobunshi, 38[12], 1062 (1989)
．． ) are also known, but it is difficult to control the size and quality, and problems remain in practical use.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、所望の形状
をした安定で均質なゲル状の水不溶性固形フィブロイン
成形物であり、しかも一段階の操作で短時間に得ること
を課題とした。SUMMARY OF THE INVENTION The object of the present invention is to provide a stable, homogeneous, gel-like, water-insoluble solid fibroin molded product having a desired shape, which can be obtained in a short time by a one-step operation.
【０００９】[0009]
【課題を解決するための手段】本発明者らは、永年フィ
ブロインの研究を行っている。フィブロイン水溶液のフ
ィブロイン分子は、マイナスにチャージしていることに
着目し、直流電圧を印加するとフィブロイン分子は陽極
に引き寄せられ、析出されるのではないかと考えた。一
方、水溶性フィブロインを水不溶性フィブロインにする
方法の一つに、延伸が知られているが、これは、延伸す
ることにより分子の方向が揃い、分子間で水素結合をお
こしフィブロイン蛋白分子が結晶構造をとるためと推測
される。しかるに、直流電圧を印加した場合、フィブロ
イン分子は方向性を持って電極に引き寄せられ、延伸し
たのと同様の効果を持つことを期待した。しかも、電流
の強弱によらずその方向は一致するので安定した性質を
得ることができるものと考えた。かかる知見をもとに、
本発明を完成するにいたった。[Means for Solving the Problems] The present inventors have been conducting research on fibroin for many years. Noting that the fibroin molecules in the fibroin aqueous solution are negatively charged, they thought that when a DC voltage was applied, the fibroin molecules would be attracted to the anode and deposited. On the other hand, stretching is known as one of the methods for converting water-soluble fibroin into water-insoluble fibroin.Stretching aligns the direction of the molecules, creates hydrogen bonds between molecules, and crystallizes the fibroin protein molecules. It is assumed that this is because it has a structure. However, when a DC voltage was applied, the fibroin molecules were directionally attracted to the electrode, which was expected to have the same effect as stretching. Moreover, since the direction is the same regardless of the strength of the current, it was thought that stable properties could be obtained. Based on this knowledge,
This led to the completion of the present invention.
【００１０】すなわち、本発明はフィブロインを含む電
解液から電気的泳動により電極附近に析出させて得られ
る水不溶性固形フィブロイン成形物であり、また電解槽
内に、濃度０．５〜２５重量％のフィブロインを含む電
解液をとり、直流電圧を印加し、電極附近にフィブロイ
ン分子を析出させて得られる水不溶性固形フィブロイン
成形物の製造法であり、好ましくは電解液に減極剤を加
えた製造法である。That is, the present invention is a water-insoluble solid fibroin molded product obtained by depositing fibroin in the vicinity of an electrode by electrophoresis from an electrolytic solution containing fibroin. This is a method for producing a water-insoluble solid fibroin molded product obtained by taking an electrolytic solution containing fibroin, applying a DC voltage, and precipitating fibroin molecules near the electrode, preferably a method in which a depolarizer is added to the electrolytic solution. It is.
【００１１】以下、本発明を詳しく説明する。The present invention will be explained in detail below.
【００１２】本発明で用いるフィブロイン水溶液は、生
糸、絹紡糸、生糸屑、キキ、ビス、屑繭、ブーレット等
の絹及び絹原料を、常法によりセリシンや他のきょう雑
物を精練除去した後、例えば銅−アンモニア水溶液、水
酸化銅−エチレンジアミン水溶液、ロダン酸塩水溶液、
臭化リチウム水溶液、塩化カルシウム水溶液、硝酸カル
シウム、あるいは硝酸マグネシウム水溶液等の塩溶液に
溶解し、更に水に対して透析脱塩することにより調製す
ることもできる。また別法としては、蚕等の絹糸腺を、
昆虫生体内より取り出して水に溶解しフィブロイン水溶
液を調製することもできる。The fibroin aqueous solution used in the present invention is obtained by scouring and removing sericin and other impurities from silk and silk raw materials such as raw silk, silk spun, raw silk waste, kiki, bis, waste cocoons, and boulette by a conventional method. , such as copper-ammonia aqueous solution, copper hydroxide-ethylenediamine aqueous solution, rhodanate aqueous solution,
It can also be prepared by dissolving it in a salt solution such as a lithium bromide aqueous solution, a calcium chloride aqueous solution, calcium nitrate, or a magnesium nitrate aqueous solution, and further desalting by dialysis against water. Another method is to use the silk glands of silkworms etc.
Fibroin can also be removed from the living body of an insect and dissolved in water to prepare an aqueous fibroin solution.
【００１３】本発明で用いるフィブロイン水溶液のフィ
ブロインの濃度は、０．５〜２５重量％であるが、好ま
しくは２〜２０重量％である。０．５重量％より低濃度
では、通電性がおち、ゲルが出来にくくなる。一方２５
重量％より高濃度になると、粘度が高くなりすぎ、流動
性が劣り、成形性が悪くなって好ましくない。The concentration of fibroin in the aqueous fibroin solution used in the present invention is 0.5 to 25% by weight, preferably 2 to 20% by weight. If the concentration is lower than 0.5% by weight, the electrical conductivity decreases and it becomes difficult to form a gel. On the other hand 25
If the concentration is higher than % by weight, the viscosity becomes too high, fluidity is poor, and moldability becomes poor, which is not preferable.
【００１４】本発明で用いる電解槽内での直流電圧は、
電極間の距離、電解液の通電性、フィブロインの濃度な
どによって異なるが通常２０Ｖから１５，０００Ｖまで
が好ましい。[0014] The DC voltage in the electrolytic cell used in the present invention is:
Although it varies depending on the distance between the electrodes, the conductivity of the electrolyte, the concentration of fibroin, etc., it is usually preferably from 20V to 15,000V.
【００１５】本発明は、電解槽を水不溶性固形フィブロ
イン成形物の所望の型に加工し、陽電極として使用し、
通電する場合もある。尚、陰極には、炭素棒が適してい
る。[0015] In the present invention, an electrolytic cell is processed into a desired shape of a water-insoluble solid fibroin molded product and used as a positive electrode.
Sometimes it is energized. Note that a carbon rod is suitable for the cathode.
【００１６】本発明に用いる減極剤は、通電時、陰極付
近で水素ガスの発生を予防するものであり、例えば硝酸
、過酸化水素水、重クロム酸カリウム、酸化マンガンな
どであり、必要に応じ適量加える。The depolarizer used in the present invention is one that prevents the generation of hydrogen gas near the cathode when electricity is applied, and examples thereof include nitric acid, hydrogen peroxide, potassium dichromate, and manganese oxide. Add appropriate amount.
【００１７】その他本発明の電解液に添加されるものと
して、水やリン酸緩衝液、トリス緩衝液などの一般的な
緩衝液や極微量の塩類などを適宜選択して用いることが
できる。Other additives to the electrolytic solution of the present invention include water, general buffer solutions such as phosphate buffer and Tris buffer, and trace amounts of salts, etc., which can be appropriately selected and used.
【００１８】本発明の水不溶性固形フィブロイン成形物
は、食品、化粧品、医療品材料として、また乾燥固化す
ればプラスチック類にかわる材料としての容器などに利
用することができる。The water-insoluble solid fibroin molded product of the present invention can be used as a material for foods, cosmetics, and medical products, and when dried and solidified, it can be used for containers as a material to replace plastics.
【００１９】[0019]
【実施例】以下、本発明を実施例にて説明するが、本発
明はこれら実施例に限定されるものではない。[Examples] The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.
【００２０】まず、本発明に用いるフィブロイン水溶液
の製造例を示す。First, an example of producing an aqueous fibroin solution used in the present invention will be described.
【００２１】製造例１．
生糸と０．５％のマルセル石鹸水溶液との浴比を２００
として、１００℃で３０分の精練を２回行った後に、蒸
留水で洗浄して高純度のフィブロイン繊維を得た。この
高純度のフィブロイン繊維を、９Ｍの臭化リチウム水溶
液に４０℃で溶解後セルロース製の透析膜を用いて、透
析水に臭化リチウムが検出されなくなるまで透析をくり
返すと、４重量％のフィブロイン水溶液が得られた。Production example 1. The bath ratio of raw silk and 0.5% Marcel soap aqueous solution was 200.
After performing scouring for 30 minutes at 100° C. twice, the fibers were washed with distilled water to obtain highly pure fibroin fibers. After dissolving this high-purity fibroin fiber in a 9M lithium bromide aqueous solution at 40°C, dialysis was repeated using a cellulose dialysis membrane until lithium bromide was no longer detected in the dialysed water. A fibroin aqueous solution was obtained.
【００２２】製造例２．
最終令の蚕を切開して取り出した絹糸腺より、外層の腺
細胞とセリシンを除去し、液状フィブロインを得る。こ
れを水に溶解せしめ、１０重量％のフィブロイン水溶液
を得る。絹糸腺は、フィブロインの収量の多い中部糸腺
前区を使用するのが好ましい。Production example 2. Liquid fibroin is obtained by removing the outer layer of glandular cells and sericin from the silk gland, which is taken out by dissecting the last instar silkworm. This is dissolved in water to obtain a 10% by weight fibroin aqueous solution. As for the silk gland, it is preferable to use the middle anterior section of the silk gland, which has a high yield of fibroin.
【００２３】実施例１．容器
銅板を加工して、直径１０ｃｍの逆紡錘状の電解槽を作
る。この電解槽を陽極とし、製造例１で得たフィブロイ
ン水溶液をとる。一方、電解槽に接触しないように、そ
の中心部に炭素棒を陰極として差し込む。１０００Ｖの
直流電圧を１０分間通電すると、電気的泳動により陽極
附近に電解槽の形状をした均質なゲル状の水不溶性固形
フィブロイン成形物を一段階の操作でしかも短時間にう
ることができた。Example 1. A reverse spindle-shaped electrolytic cell with a diameter of 10 cm is made by processing the container copper plate. Using this electrolytic cell as an anode, the aqueous fibroin solution obtained in Production Example 1 was taken. On the other hand, a carbon rod is inserted into the center of the electrolytic cell as a cathode so as not to touch it. When a DC voltage of 1000 V was applied for 10 minutes, a homogeneous gel-like water-insoluble solid fibroin molded product in the shape of an electrolytic cell could be obtained near the anode by electrophoresis in a single step and in a short time.
【００２４】次に、フィブロイン水溶液のフィブロイン
濃度と水不溶性フィブロイン成形物のゲルの状態との関
係をテストした。Next, the relationship between the fibroin concentration of the fibroin aqueous solution and the gel state of the water-insoluble fibroin molded article was tested.
【００２５】（試料）製造例１の４重量％のフィブロイ
ン水溶液をとる。これより低濃度のものは蒸留水で希釈
して作った。また、これより高濃度のものは室温にて水
分を蒸散濃縮して作った。各濃度のフィブロイン水溶液
を使って、実施例１の方法に準拠してゲル状の水不溶性
固形フィブロイン成形物を製造し試料とした。(Sample) Take the 4% by weight aqueous fibroin solution of Production Example 1. Lower concentrations were prepared by diluting with distilled water. In addition, products with higher concentrations were made by evaporating and concentrating water at room temperature. Using fibroin aqueous solutions of various concentrations, gel-like water-insoluble solid fibroin molded products were manufactured according to the method of Example 1 and used as samples.
【００２６】（結果）(Result)
【表１】
表１の結果より明らかなように、フィブロイン水溶液の
フィブロインの濃度は０．５〜２５重量％が適している
。この範囲を越えるとゲルが出来にくくなったり、ゲル
の経日安定性が悪くなるので好ましくない。[Table 1] As is clear from the results in Table 1, the suitable concentration of fibroin in the aqueous fibroin solution is 0.5 to 25% by weight. If it exceeds this range, it becomes difficult to form a gel and the stability of the gel deteriorates over time, which is not preferable.
【００２７】実施例２．中空円筒状成形物電解槽内に製
造例２で得た１０重量％フィブロイン水溶液をとる。こ
のフィブロイン水溶液に対し、減極剤として３５％過酸
化水素水を０．１％になるよう加える。電解槽内に炭素
電極を２本つるし、直流電圧２，０００Ｖを印加し、３
分間通電する。陽極炭素棒附近に本発明のゲル状の水不
溶性固形フィブロインの中空円筒状成形物を得る。Example 2. The 10% by weight aqueous fibroin solution obtained in Production Example 2 is placed in a hollow cylindrical molded electrolytic cell. To this aqueous fibroin solution, 35% hydrogen peroxide solution is added as a depolarizer to a concentration of 0.1%. Two carbon electrodes were suspended in the electrolytic cell, a DC voltage of 2,000 V was applied, and 3
Turn on electricity for a minute. A hollow cylindrical molded product of the gel-like water-insoluble solid fibroin of the present invention is obtained near the anode carbon rod.
【００２８】[0028]
【発明の効果】本発明は、所望の形状をした安定で均質
なゲル状の水不溶性固形フィブロイン成形物であり、フ
ィブロイン水溶液のフィブロインの濃度を０．５〜２５
重量％にとり、電気的泳動により一段階の操作で短時間
に水不溶性固形フィブロイン成形物を得ることができた
。Effects of the Invention The present invention provides a stable and homogeneous gel-like water-insoluble solid fibroin molded product having a desired shape, and the concentration of fibroin in an aqueous fibroin solution is 0.5 to 25.
In terms of weight percent, a water-insoluble solid fibroin molded product could be obtained in a short time by electrophoresis in one step.
Claims (3)
泳動により電極附近に析出させて得られる水不溶性固形
フィブロイン成形物。1. A water-insoluble solid fibroin molded product obtained by depositing fibroin in the vicinity of an electrode by electrophoresis from an electrolytic solution containing fibroin.
のフィブロインを含む電解液をとり、直流電圧を印加し
、電極附近にフィブロイン分子を析出させて得られる水
不溶性固形フィブロイン成形物の製造法。[Claim 2] In the electrolytic cell, the concentration is 0.5 to 25% by weight.
A method for producing a water-insoluble solid fibroin molded article obtained by taking an electrolytic solution containing fibroin, applying a DC voltage, and depositing fibroin molecules near the electrode.
する請求項２記載の水不溶性固形フィブロイン成形物の
製造法。3. The method for producing a water-insoluble solid fibroin molded article according to claim 2, characterized in that a depolarizer is added to the electrolytic solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4432591A JPH04263611A (en) | 1991-02-16 | 1991-02-16 | Water-insoluble solid fibroin formed article and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4432591A JPH04263611A (en) | 1991-02-16 | 1991-02-16 | Water-insoluble solid fibroin formed article and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04263611A true JPH04263611A (en) | 1992-09-18 |
Family
ID=12688349
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4432591A Pending JPH04263611A (en) | 1991-02-16 | 1991-02-16 | Water-insoluble solid fibroin formed article and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04263611A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010036992A3 (en) * | 2008-09-26 | 2010-05-20 | Trustees Of Tufts College | Active silk muco-adhesives, silk electrogelation process, and devices |
| EP2483460A2 (en) * | 2009-09-28 | 2012-08-08 | Trustees Of Tufts College | Drawn silk egel fibers and methods of making same |
| US8501172B2 (en) | 2008-09-26 | 2013-08-06 | Trustees Of Tufts College | pH-induced silk gels and uses thereof |
| US8715740B2 (en) | 2009-09-29 | 2014-05-06 | Trustees Of Tufts College | Silk nanospheres and microspheres and methods of making same |
| US8722067B2 (en) | 2007-05-29 | 2014-05-13 | Trustees Of Tufts College | Method for silk fibroin gelation using sonication |
| US9102916B2 (en) | 2007-02-27 | 2015-08-11 | Trustees Of Tufts College | Tissue-engineered silk organs |
| US9504575B2 (en) | 2008-02-07 | 2016-11-29 | Trustees Of Tufts College | 3-dimensional silk hydroxyapatite compositions |
| US9566365B2 (en) | 2010-09-01 | 2017-02-14 | Trustees Of Tufts College | Silk fibroin and polyethylene glycol-based biomaterials |
| US9603971B2 (en) | 2010-03-05 | 2017-03-28 | Trustees Of Tufts College | Silk-based ionomeric compositions |
| US10335519B2 (en) | 2011-04-20 | 2019-07-02 | Trustees Of Tufts College | Dynamic silk coatings for implantable devices |
| US10933173B2 (en) | 2010-10-19 | 2021-03-02 | Trustees Of Tufts College | Silk fibroin-based microneedles and methods of making the same |
-
1991
- 1991-02-16 JP JP4432591A patent/JPH04263611A/en active Pending
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9102916B2 (en) | 2007-02-27 | 2015-08-11 | Trustees Of Tufts College | Tissue-engineered silk organs |
| US10478524B2 (en) | 2007-02-27 | 2019-11-19 | Trustees Of Tufts College | Tissue-engineered silk organs |
| US9655993B2 (en) | 2007-02-27 | 2017-05-23 | Trustees Of Tufts College | Tissue-engineered silk organs |
| US9254333B2 (en) | 2007-05-29 | 2016-02-09 | Trustees Of Tufts College | Method for silk fibroin gelation using sonication |
| US8722067B2 (en) | 2007-05-29 | 2014-05-13 | Trustees Of Tufts College | Method for silk fibroin gelation using sonication |
| US9504575B2 (en) | 2008-02-07 | 2016-11-29 | Trustees Of Tufts College | 3-dimensional silk hydroxyapatite compositions |
| US9694082B2 (en) | 2008-09-26 | 2017-07-04 | Trustees Of Tufts College | pH induced silk gels and uses thereof |
| US8501172B2 (en) | 2008-09-26 | 2013-08-06 | Trustees Of Tufts College | pH-induced silk gels and uses thereof |
| JP2012509252A (en) * | 2008-09-26 | 2012-04-19 | トラスティーズ オブ タフツ カレッジ | Active silk mucus adhesive, silk electrogelation method, and device |
| JP2015212254A (en) * | 2008-09-26 | 2015-11-26 | タフツ ユニバーシティー／トラスティーズ オブ タフツ カレッジ | Active silk muco-adhesive, silk electrogelation process, and device |
| WO2010036992A3 (en) * | 2008-09-26 | 2010-05-20 | Trustees Of Tufts College | Active silk muco-adhesives, silk electrogelation process, and devices |
| EP2483460A2 (en) * | 2009-09-28 | 2012-08-08 | Trustees Of Tufts College | Drawn silk egel fibers and methods of making same |
| US9074302B2 (en) | 2009-09-28 | 2015-07-07 | Trustees Of Tufts College | Methods of making drawn silk fibers |
| EP2483460A4 (en) * | 2009-09-28 | 2013-05-29 | Tufts College | Drawn silk egel fibers and methods of making same |
| US9381164B2 (en) | 2009-09-29 | 2016-07-05 | Trustees Of Tufts College | Silk nanospheres and microspheres and methods of making same |
| US8715740B2 (en) | 2009-09-29 | 2014-05-06 | Trustees Of Tufts College | Silk nanospheres and microspheres and methods of making same |
| US9603971B2 (en) | 2010-03-05 | 2017-03-28 | Trustees Of Tufts College | Silk-based ionomeric compositions |
| US9566365B2 (en) | 2010-09-01 | 2017-02-14 | Trustees Of Tufts College | Silk fibroin and polyethylene glycol-based biomaterials |
| US10933173B2 (en) | 2010-10-19 | 2021-03-02 | Trustees Of Tufts College | Silk fibroin-based microneedles and methods of making the same |
| US10335519B2 (en) | 2011-04-20 | 2019-07-02 | Trustees Of Tufts College | Dynamic silk coatings for implantable devices |
| US11266339B2 (en) | 2011-04-20 | 2022-03-08 | Trustees Of Tufts College | Dynamic silk coatings for implantable devices |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Peng et al. | Structural and mechanical properties of silk from different instars of Bombyx mori | |
| JP5186671B2 (en) | Silk protein nanofiber and method for producing the same, silk protein composite nanofiber and method for producing the same | |
| Liu et al. | Thixotropic silk nanofibril-based hydrogel with extracellular matrix-like structure | |
| JPH04263611A (en) | Water-insoluble solid fibroin formed article and its production | |
| Zhou et al. | Humidity-sensitive, shape-controllable, and transient zinc-ion batteries based on plasticizing gelatin-silk protein electrolytes | |
| Razal et al. | Carbon nanotube biofiber formation in a polymer‐free coagulation bath | |
| Choi et al. | Keratin/poly (vinyl alcohol) blended nanofibers with high optical transmittance | |
| Shen et al. | Dissolution behavior of silk fibroin in a low concentration CaCl2-methanol solvent: From morphology to nanostructure | |
| KR20040065550A (en) | Dissolution and processing of cellulose using ionic liquids | |
| Wang et al. | Facile production of natural silk nanofibers for electronic device applications | |
| Sun et al. | An extremely tough and ionic conductive natural-polymer-based double network hydrogel | |
| US20100311949A1 (en) | Aligned collagen and method therefor | |
| Khakkulov et al. | Electrochemical Reduction Of Macroiones As A Surface-Active Nanocoating And Nanocomposites | |
| Badawy et al. | Natural silk for energy and sensing applications: a review | |
| JP2006257013A (en) | Collagen gel derived from scale and method for preparing the same gel | |
| CN111040197A (en) | High-strength multifunctional ion conductive hydrogel and preparation method and application thereof | |
| KR20160021673A (en) | Bio sensor using three-dimensional graphene-silk complex and sensing system using the same | |
| CN114230812A (en) | Functional hydrogel and preparation method and application thereof | |
| JP5875761B2 (en) | Collagen fiber gel and use thereof | |
| Yang et al. | The fractal network structure of silk fibroin molecules and its effect on spinning of silkworm silk | |
| JP5453690B2 (en) | Collagen / chitosan composite fibrous porous body and method for producing the same | |
| CN106222718B (en) | A kind of electro-deposition method of carboxymethyl cellulose | |
| Müller et al. | Functionalisation of recombinant spider silk with conjugated polyelectrolytes | |
| CN110028703A (en) | A kind of preparation method of nano biological matter base high-strength and high-transparent degree large format composite membrane | |
| JP2507885B2 (en) | Silk fibroin hydrogel |