JPH0764953B2 - Chitosan-silica composite and method for producing the same - Google Patents
Chitosan-silica composite and method for producing the sameInfo
- Publication number
- JPH0764953B2 JPH0764953B2 JP2269642A JP26964290A JPH0764953B2 JP H0764953 B2 JPH0764953 B2 JP H0764953B2 JP 2269642 A JP2269642 A JP 2269642A JP 26964290 A JP26964290 A JP 26964290A JP H0764953 B2 JPH0764953 B2 JP H0764953B2
- Authority
- JP
- Japan
- Prior art keywords
- chitosan
- silica
- raw material
- silicon alkoxide
- producing
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 93
- 239000000377 silicon dioxide Substances 0.000 title claims description 53
- 239000002131 composite material Substances 0.000 title claims description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229920001661 Chitosan Polymers 0.000 claims description 36
- -1 silicon alkoxide Chemical class 0.000 claims description 19
- 229910052710 silicon Inorganic materials 0.000 claims description 18
- 239000010703 silicon Substances 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 16
- 230000003301 hydrolyzing effect Effects 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 239000007789 gas Substances 0.000 description 10
- 239000012528 membrane Substances 0.000 description 8
- 230000035699 permeability Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- HTTJABKRGRZYRN-UHFFFAOYSA-N Heparin Chemical compound OC1C(NC(=O)C)C(O)OC(COS(O)(=O)=O)C1OC1C(OS(O)(=O)=O)C(O)C(OC2C(C(OS(O)(=O)=O)C(OC3C(C(O)C(O)C(O3)C(O)=O)OS(O)(=O)=O)C(CO)O2)NS(O)(=O)=O)C(C(O)=O)O1 HTTJABKRGRZYRN-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229960002897 heparin Drugs 0.000 description 3
- 229920000669 heparin Polymers 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002473 artificial blood Substances 0.000 description 2
- 239000000560 biocompatible material Substances 0.000 description 2
- 210000004204 blood vessel Anatomy 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 229910014571 C—O—Si Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009739 binding Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000008279 sol Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Materials For Medical Uses (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、気体透過膜、液体分離膜等の分離膜、または
人工皮膚、人工肺、人工血管等の生体適合性材料に使用
するのに適するキトサン・シリカ系複合体及びその製造
方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is used for a separation membrane such as a gas permeable membrane or a liquid separation membrane, or a biocompatible material such as artificial skin, artificial lung, or artificial blood vessel. The present invention relates to a suitable chitosan-silica composite and a method for producing the same.
シリカは生体中の成長に関連した部位に多く見られ、生
体と適合性が良い。例えば、Chem.in Britain,Feb,199
0,p.141にはSiとAlとの生体におけるSiの重要性とその
諸影響を論じている。従って、従来からシリカは生体適
合性材料の素材に用いてきた。具体的にシリカを用いた
生体適合性複合体の例として、清水らの「ポリビリルア
ルコール−シリカ複合体による人工血管の開発」（機能
材料 1984年９月号）に記載のものを挙げることができ
る。これは、ポリビニルアルコール水溶液とテトラエチ
ルシリケートを混合、反応させ、ゾル化、乾燥し、ポリ
ビニルアルコール−シリカ複合体のキセロゲルを得るも
のである。さらにこの作成過程においてヘパリンを加え
固定化したものを開示している。Silica is often found in the part related to growth in the living body and has good compatibility with the living body. For example, Chem.in Britain, Feb, 199
0, p.141 discusses the importance of Si and its effects in the living body of Si and Al. Therefore, conventionally, silica has been used as a raw material for biocompatible materials. Specific examples of biocompatible composites using silica include those described in "Development of artificial blood vessels using poly (vinyl alcohol) -silica composites" by Shimizu et al. (Functional material, September 1984 issue). it can. This is to obtain a polyvinyl alcohol-silica composite xerogel by mixing an aqueous solution of polyvinyl alcohol and tetraethyl silicate, reacting them, forming a sol, and drying. Further, it discloses that immobilized by adding heparin in the preparation process.
一方、上記ヘパリンに相当する機能を有するキトサンは
安価で耐有機溶媒性が高いことから、パーベーパレーシ
ョン膜等の分離膜、また、人工皮膚等に応用されてい
る。On the other hand, chitosan having a function equivalent to the above heparin is inexpensive and has high resistance to organic solvents, and is therefore applied to separation membranes such as pervaporation membranes and artificial skin.
しかし、これらキトサンを用いた材料はまだ気体透過性
が低い問題がある。また、シリカのみでは膜、管等に成
形した場合、強度や可撓性に問題がある。However, materials using these chitosans still have a problem of low gas permeability. In addition, silica alone has a problem in strength and flexibility when formed into a film, a tube or the like.
本発明は高い気体透過性を有し、また、生体適合性が高
く、更に高い強度と可撓性を有するキトサン・シリカ系
複合体およびその製造方法を提供することを課題とす
る。An object of the present invention is to provide a chitosan-silica composite having high gas permeability, high biocompatibility, high strength and flexibility, and a method for producing the same.
本発明は、下記の手段により前記の課題を解決した。 The present invention has solved the above problems by the following means.
（１） シリコンアルコキシドまたはそれを部分的に加
水分解して生成した多量体シリコンアルコキシドを主成
分とするシリカ原料にキトサンを混合し、その混合物の
シリカ原料を加水分解することにより得た、キトサンに
対し１重量％〜80重量％のシリカを含むキトサン・シリ
カ系複合体。(1) Chitosan obtained by mixing chitosan with a silica raw material whose main component is a silicon alkoxide or a multimeric silicon alkoxide produced by partially hydrolyzing the silicon alkoxide, and hydrolyzing the silica raw material of the mixture. A chitosan-silica composite containing 1 to 80% by weight of silica.
（２） シリコンアルコキシドまたはそれを部分的に加
水分解して生成した多量体シリコンアルコキシドを主成
分とするシリカ原料にキトサンを混合し、その混合物の
シリカ原料を加水分解することを特徴とするキトサンに
対し１重量％〜80重量％のシリカを含むキトサン・シリ
カ系複合体の製造方法。(2) A chitosan characterized by mixing a silica raw material mainly composed of a silicon alkoxide or a multimeric silicon alkoxide produced by partially hydrolyzing the silicon alkoxide with chitosan and hydrolyzing the silica raw material of the mixture. A method for producing a chitosan-silica composite containing 1% to 80% by weight of silica.
本発明のキトサン・シリカ系複合体とは、少なくともキ
トサンとシリカとが互いに均一に分散した、かつ少なく
とも部分的にキトサン分子とシリカ分子が結合している
複合構造を（全体として）有する、常温、常圧で固体状
の複合体を意味する。例えば、酸素を介してＣ−Ｏ−Si
結合等を有しているものが挙げられる。The chitosan-silica-based composite of the present invention has at least a composite structure in which at least chitosan and silica are uniformly dispersed in each other, and at least partially a chitosan molecule and a silica molecule are bonded, at room temperature, It means a complex that is solid at atmospheric pressure. For example, through oxygen, C-O-Si
Those having a bond or the like can be mentioned.
本発明のキトサン・シリカ系複合体は、キトサンの他に
コラーゲン、ヘパリンなどを含有してもよい。また、シ
リカの他にチタニア、ジルコニア等を含有していてもよ
い。The chitosan-silica composite of the present invention may contain collagen, heparin or the like in addition to chitosan. In addition to silica, it may contain titania, zirconia, or the like.
本発明のキトサン・シリカ系複合体の形状は、特に制限
なく、公知の成形手段を用いて成形することができ、成
形形状は使用目的に応じて適宜選定することができる
が、特に膜状が好適である。The shape of the chitosan / silica-based composite of the present invention is not particularly limited and can be formed by using a known forming means. The formed shape can be appropriately selected according to the purpose of use, but a film-like shape is particularly preferable. It is suitable.
本発明のキトサン・シリカ系複合体の製造方法は上記条
件を満足するのであれば特に制限はない。The method for producing the chitosan-silica composite of the present invention is not particularly limited as long as it satisfies the above conditions.
上記（２）において、シリカ原料とキトサンとは一般的
には少なくとも水を介して混合分散され、同時にシリカ
分子とキトサン分子との結合反応が生起するように設定
される。In the above (2), the silica raw material and chitosan are generally mixed and dispersed through at least water, and at the same time, the binding reaction between the silica molecule and the chitosan molecule is set to occur.
この場合、キトサンは、好ましくは溶液の形態で使用す
ることが望ましいが、特にその媒体は制限されない。好
ましい媒体の例としては、水を主体としたものが挙げら
れる。In this case, chitosan is preferably used in the form of a solution, but the medium is not particularly limited. An example of a preferable medium is a medium mainly composed of water.
特に、キトサンを酢酸水溶液、好ましくは1wt％〜20wt
％の酢酸水溶液に溶解して用いることがシリカと均一に
混合させる上で好ましい。Particularly, chitosan is added to an acetic acid aqueous solution, preferably 1 wt% to 20 wt.
%, It is preferable to use it by dissolving it in an acetic acid aqueous solution in order to uniformly mix it with silica.
本発明において、シリカのゲル化、ひいてはキトサン・
シリカ系複合体のゲル化の条件は、特に制限されない
が、通常、上記シリカ原料を加水分解するための水の量
として、該シリカ原料の加水分解可能な基に対して0.5
〜100モル以上の範囲で、温度０℃〜80℃、通常常圧下
でゲル化することが挙げられる。In the present invention, gelation of silica, and thus chitosan
The conditions for gelling the silica-based composite are not particularly limited, but usually, the amount of water for hydrolyzing the silica raw material is 0.5 with respect to the hydrolyzable groups of the silica raw material.
In the range of -100 mol or more, the gelling may be carried out at a temperature of 0 ° C to 80 ° C and usually under normal pressure.
キトサン・シリカ系複合体の乾燥条件も、特に制限され
ず、公知の乾燥手段を用いることができるが、好ましく
は、温度30℃〜70℃、通常常圧化で乾燥することが挙げ
られる。The drying conditions for the chitosan / silica-based composite are not particularly limited, and known drying means can be used, but preferably, the temperature is 30 ° C. to 70 ° C. and the drying is usually performed under normal pressure.
また、得られるキトサン・シリカ系複合体の強度増強、
酸性環境における不溶化等を図るためにキトサンを架橋
剤、例えば、グルタルアルデヒド等により処理すること
ができる。この場合の架橋剤の添加時間は、キトサンと
シリカの混合時が好ましい。Also, strength enhancement of the resulting chitosan-silica composite,
Chitosan can be treated with a cross-linking agent such as glutaraldehyde for the purpose of insolubilization in an acidic environment. In this case, the addition time of the cross-linking agent is preferably when chitosan and silica are mixed.
本発明に使用されるキトサンとしては、分子量が500〜1
00,000、好ましくは1000〜10,000の範囲のものが挙げら
れる。The chitosan used in the present invention has a molecular weight of 500 to 1
Those in the range of 00,000, preferably 1000 to 10,000 are mentioned.
本発明に使用されるシリカ原料のシリコンアルコキシド
としては、特に限定されないが、好ましくは、式Si（O
R）４（Ｒは、メチル、エチル、プロピル、ブチル等を
表す）で表される化合物が挙げられ、また、多量体シリ
コンアルコキシドとは、シリコンアルコキシドの加水分
解生成物同志が複数個、通常、２〜40個が縮合したもの
を言う。The silicon alkoxide of the silica raw material used in the present invention is not particularly limited, but is preferably of the formula Si (O
R) 4 (R represents methyl, ethyl, propyl, butyl, etc.), and the multimeric silicon alkoxide means a plurality of hydrolysis products of silicon alkoxide, usually, 2 to 40 condensed.
また、該シリカ原料としては、上記シリコンアルコキシ
ド等に加えチタンアルコキシド、ジルコニウムアルコキ
シド等を含んでもよい。Further, the silica raw material may contain titanium alkoxide, zirconium alkoxide and the like in addition to the above silicon alkoxide and the like.
本発明は、シリカ原料を加水分解すると共にキトサンと
混合・分散することにより、キトサンと生成シリカとが
互いに均一に分散し、かつキトサン構成原子とシリカ原
料の加水分解生成物とが反応して、キトサンとシリカと
の間に共有結合が形成される。特に、反応媒体として酢
酸水溶液を使用することにより、キトサンを酢酸塩の形
で水に溶かすことができ、また、シリコンアルコキシド
の加水分解時に酸触媒として働きシリカがより線状に重
合し、またキトサンとの相溶性もよいので両者は均一、
一様に複合化する。また、酢酸は生体に対して毒性もな
く、複合体中に少量残存しても問題がない。The present invention, by hydrolyzing the silica raw material and mixing and dispersing with chitosan, the chitosan and the produced silica are uniformly dispersed with each other, and the chitosan constituent atoms and the hydrolysis product of the silica raw material react, A covalent bond is formed between chitosan and silica. In particular, by using an aqueous acetic acid solution as a reaction medium, chitosan can be dissolved in water in the form of an acetate salt, and silica acts as an acid catalyst during the hydrolysis of silicon alkoxide to polymerize silica more linearly. The compatibility with is also good, so both are uniform,
Combine uniformly. Further, acetic acid is not toxic to living organisms, and there is no problem even if a small amount remains in the complex.
キトサン0.5gを濃酢酸1mlを添加した水100mlに溶かす。
これにエチルシリケート40: で表されるオリゴマーを0.5g加え、撹拌する。これを一
体量シャーレに流し入れ、60℃、約24間保ち乾燥させ
た。Dissolve 0.5 g of chitosan in 100 ml of water with the addition of 1 ml of concentrated acetic acid.
To this the ethyl silicate 40: Add 0.5 g of the oligomer represented by and stir. An integral amount of this was poured into a petri dish and dried at 60 ° C. for about 24 hours.
また、グルタルアルデヒドを用いてキトサンを架橋し、
不溶化処理を行った。Also, crosslink chitosan with glutaraldehyde,
Insolubilization treatment was performed.
この複合体の気体透過性を測定したところ、Heガスでは
キトサンのみのものに比べ、約220倍の気体透過性を示
し、また、O2ガスではキトサンのみのものがほとんど透
過性を示さないのに対し、キトサン・シリカ系複合膜で
はHeガスの時と同程度の気体透過性を示した。尚、実験
条件は、共に2kg f/cm2、２分で厚さ0.021mm、シリカ：
キトサン＝50:50（重量比）の膜を使用し行った。When the gas permeability of this complex was measured, He gas showed a gas permeability of about 220 times that of chitosan alone, and O 2 gas of chitosan alone showed almost no permeability. On the other hand, the chitosan-silica composite membrane showed the same gas permeability as that of He gas. The experimental conditions were both 2 kg f / cm 2 , a thickness of 0.021 mm in 2 minutes, and silica:
It was carried out using a membrane of chitosan = 50:50 (weight ratio).
本発明は、複雑な装置を用いることなくキトサンの添加
量を所定量限定すると共にシリコンアルコキシドと混
合、シリコンアルコキシドを加水分解することのみで簡
単に可撓性を有しかつ気体透過性を良好な強靱なキトサ
ン・シリカ系複合体を製造することができるので、低コ
ストの分離膜、人工皮膚等を提供できる。The present invention limits the addition amount of chitosan to a predetermined amount without using a complicated device, mixes with silicon alkoxide, and hydrolyzes silicon alkoxide to easily provide flexibility and good gas permeability. Since a tough chitosan-silica composite can be produced, a low-cost separation membrane, artificial skin, etc. can be provided.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ａ６１Ｌ 31/00 Ｔ Ｂ０１Ｄ 71/08 9153−4Ｄ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location A61L 31/00 T B01D 71/08 9153-4D
Claims (2)
に加水分解して生成した多量体シリコンアルコキシドを
主成分とするシリカ原料にキトサンを混合し、その混合
物のシリカ原料を加水分解することにより得た、キトサ
ンに対し１重量％〜80重量％のシリカを含むキトサン・
シリカ系複合体。1. Obtained by mixing chitosan with a silica raw material whose main component is a silicon alkoxide or a multimeric silicon alkoxide produced by partially hydrolyzing it, and hydrolyzing the silica raw material of the mixture. Chitosan containing 1% to 80% by weight of silica based on chitosan
Silica-based composite.
に加水分解して生成した多量体シリコンアルコキシドを
主成分とするシリカ原料にキトサンを混合し、その混合
物のシリカ原料を加水分解することを特徴とするキトサ
ンに対し１重量％〜80重量％のシリカを含むキトサン・
シリカ系複合体の製造方法。2. A silica raw material mainly composed of a silicon alkoxide or a multimeric silicon alkoxide produced by partially hydrolyzing it, and chitosan are mixed, and the silica raw material of the mixture is hydrolyzed. Chitosan containing 1% to 80% by weight of silica based on chitosan
Method for producing silica-based composite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2269642A JPH0764953B2 (en) | 1990-10-09 | 1990-10-09 | Chitosan-silica composite and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2269642A JPH0764953B2 (en) | 1990-10-09 | 1990-10-09 | Chitosan-silica composite and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04146942A JPH04146942A (en) | 1992-05-20 |
| JPH0764953B2 true JPH0764953B2 (en) | 1995-07-12 |
Family
ID=17475194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2269642A Expired - Lifetime JPH0764953B2 (en) | 1990-10-09 | 1990-10-09 | Chitosan-silica composite and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0764953B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020078175A (en) * | 2001-04-06 | 2002-10-18 | 학교법인 문화교육원 | Preparation of silica-chitosan composite materials by sol-gel techniques |
| JP4559764B2 (en) * | 2004-03-29 | 2010-10-13 | ピアス株式会社 | Chitosan-based composite, method for producing the chitosan-based composite, and external preparation for skin and cosmetics containing the chitosan-based composite |
| CN101948574B (en) * | 2010-10-15 | 2012-05-30 | 上海交通大学 | Hydrophobic chitosan film containing hydrophobic nano silicon dioxide particles and preparation method thereof |
| US9894895B2 (en) * | 2014-05-15 | 2018-02-20 | University Of Central Florida Research Foundation, Inc. | Non-phytotoxic composite polymer film barrier as a repellent for controlling infection |
| JP6636881B2 (en) * | 2016-09-02 | 2020-01-29 | 大日精化工業株式会社 | Method for producing siloxane-modified chitosan, siloxane-modified chitosan, emulsifier, and emulsion composition |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59213390A (en) * | 1983-05-19 | 1984-12-03 | Asahi Denka Kogyo Kk | Immobilized enzyme and its preparation |
| JPS6440501A (en) * | 1987-08-07 | 1989-02-10 | Asahi Glass Co Ltd | Chitosan carrying material |
-
1990
- 1990-10-09 JP JP2269642A patent/JPH0764953B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04146942A (en) | 1992-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0272300B1 (en) | Material of polysaccharides containing carboxyl groups, and a process for producing such polysaccharides | |
| Coradin et al. | Sol-gel biopolymer/silica nanocomposites in biotechnology | |
| CN109053928A (en) | A kind of large biological molecule and its preparation method and application based on modification of chitosan | |
| JPH0764953B2 (en) | Chitosan-silica composite and method for producing the same | |
| JP2580537B2 (en) | Three-dimensional network composed of silica spherical particles | |
| CN116139331A (en) | Multifunctional wound repair dressing loaded with bioactive glass and preparation method thereof | |
| JPH03212451A (en) | Transparent uniform material of organic-inorganic complex and its production | |
| JPH0669485B2 (en) | Molded product containing silk fibroin | |
| US4785049A (en) | Forming clear gel and transparent film by reacting alumina hydrate with vinyl alcohol-vinyl acetate copolymer | |
| Bogush et al. | The development of bioadhesives based on recombinant analogues of spider web proteins | |
| JP3086851B2 (en) | Method for producing polyhydroxycarboxylic acid resin | |
| Mizushima | Preparation of alkoxide-derived chitosan-silica complex membrane | |
| JP2750306B2 (en) | Method for producing immobilized low molecular protein A | |
| JPH05271549A (en) | Production of polysiloxane composite polymer and coating composition therefrom | |
| RU2807591C1 (en) | Magnetically separable catalyst for oxidation of organic compounds and method of its preparation | |
| JP4092070B2 (en) | Organic-inorganic composite using sugar derivative and method for producing metal oxide | |
| CN120285265B (en) | Preparation method and application of antibacterial material | |
| Duarte et al. | Chitin/chitosan based aerogels: Processing and morphology | |
| JP2002294014A (en) | Polyvinyl alcohol-based gel forming composition | |
| CN121652068A (en) | A dual-aldehyde functional crosslinking agent, its preparation method, and the collagen antibacterial hydrogel prepared using the same agent and its applications. | |
| RU2170590C1 (en) | Method of preparing alginate material showing wound-healing action | |
| KR100902040B1 (en) | Method for producing palmitoyl chitosan and chitosan film containing same | |
| CN102911928A (en) | Immobilized method of creatine kinase | |
| CN101934090A (en) | A kind of injectable bone repair material and preparation method thereof | |
| JPH04330936A (en) | Porous chitosan molded body and its manufacturing method |