JPH064029B2 - Inorganic carrier for enzyme immobilization - Google Patents
Inorganic carrier for enzyme immobilizationInfo
- Publication number
- JPH064029B2 JPH064029B2 JP2067961A JP6796190A JPH064029B2 JP H064029 B2 JPH064029 B2 JP H064029B2 JP 2067961 A JP2067961 A JP 2067961A JP 6796190 A JP6796190 A JP 6796190A JP H064029 B2 JPH064029 B2 JP H064029B2
- Authority
- JP
- Japan
- Prior art keywords
- enzyme
- sio
- enzyme immobilization
- carrier
- porous body
- 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
- 108090000790 Enzymes Proteins 0.000 title description 23
- 102000004190 Enzymes Human genes 0.000 title description 23
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 13
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 8
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052863 mullite Inorganic materials 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 2
- 239000012188 paraffin wax Substances 0.000 claims 1
- 230000003100 immobilizing effect Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 108010093096 Immobilized Enzymes Proteins 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 229940057995 liquid paraffin Drugs 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 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
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000005373 porous glass Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- -1 allyl amides Chemical class 0.000 description 1
- 102000016679 alpha-Glucosidases Human genes 0.000 description 1
- 108010028144 alpha-Glucosidases Proteins 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 239000011942 biocatalyst Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Catalysts (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 生体触媒を利用したバイオリアクターシステムは、省資
源、省エネルギー、低環境負荷であるために新しい化学
物質生産技術として注目されている。そのようなバイオ
リアクターシステムを構築する上で酵素固定化担体の開
発は、重要な基盤技術である。無機材料は、機械的強度
や化学的耐久性が高く、加熱滅菌もたやすいために、酵
素固定化担体として優れた資質を持つ材料である。一般
に酵素の固定化は、担体表面の水酸基を利用して、有機
官能基を導入し、導入有機官能基と酵素とを共有結合さ
せる方法がとられる。すでに、共有結合法による酵素固
定化担体として高シリカ質の多孔性ガラスが開発されて
いるが、高価な上アルカリ性環境下での耐久性に欠ける
ことからその使用が限定されていた。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) A bioreactor system using a biocatalyst is attracting attention as a new chemical substance production technology because of its resource saving, energy saving, and low environmental load. Development of an enzyme-immobilized carrier is an important basic technology for constructing such a bioreactor system. An inorganic material is a material having excellent properties as an enzyme-immobilized carrier because it has high mechanical strength and chemical durability and is easily heat-sterilized. In general, for immobilizing an enzyme, a method of introducing an organic functional group using a hydroxyl group on the surface of a carrier and covalently bonding the introduced organic functional group and the enzyme is used. Highly siliceous porous glass has already been developed as an enzyme-immobilized carrier by the covalent bond method, but its use was limited because it was expensive and lacked in durability in an alkaline environment.
本発明は、酵素固定化に適した表面水酸基に富む無機多
孔体及びその製造法に関するものである。The present invention relates to an inorganic porous material rich in surface hydroxyl groups suitable for enzyme immobilization and a method for producing the same.
（従来の技術） 従来、酵素固定化用担体として多糖類やアルリルアミド
等の高分子ゲル、イオン交換樹脂、ナイロン等の合成樹
脂が研究用として多用されてきた。しかしこれは、高分
子系材料は、加熱滅菌が困難な上に、材料高度が低いた
めにスケールアップや汚染対策がむずかしく工業規模で
のバイオリアクター用酵素固定化担体として用いられる
ことが少なかった。また、分相化反応を利用して作られ
る多孔質ガラスは、機械的強度は高いものの価格が高
く、対アルカリ性にも欠けるために、その利用が限定さ
れてきた。(Prior Art) Conventionally, polymer gels such as polysaccharides and allyl amides, ion exchange resins, and synthetic resins such as nylon have been widely used for research as carriers for immobilizing enzymes. However, this is because it is difficult to sterilize the polymer material by heat and the scale of the material is low, and it is difficult to prevent contamination and it is rarely used as an enzyme-immobilized carrier for a bioreactor on an industrial scale. Further, the porous glass produced by utilizing the phase-separation reaction has high mechanical strength but is expensive, and lacks alkali resistance, so that its use has been limited.
（発明が解決しようとする問題点） 前述したように、工業的に利用可能なバイオリアクター
に用いることのできる酵素固定化担体は、いまだ開発さ
れていない。(Problems to be Solved by the Invention) As described above, the enzyme-immobilized carrier that can be used in the industrially applicable bioreactor has not been developed yet.
本発明の目的は、機械的強度が高く、容易な加熱滅菌に
耐えうる耐熱性を有し、かつ経済性に優れた酵素固定化
用無機担体及びその製造法を提供することにある。An object of the present invention is to provide an inorganic carrier for enzyme immobilization which has high mechanical strength, has heat resistance capable of withstanding easy heat sterilization, and is excellent in economic efficiency, and a method for producing the same.
（問題を解決するための手段） 本発明者らは、前記の目的を達成すべく、酵素固定化能
に優れた無機材料の検討を行い、さらに酵素固定化担体
としての効率向上をはかる多孔体化について鋭意研究を
重ねた結果、Al2O3−SiO2系セラミックスが優れた酵素
固定化能を有すること、さらにその原料をアルミナゾル
とシリカゾルから合成し、成形助材として流動パラフィ
ンを用いることによって多孔体化できることを見出し本
発明を完成するに至った。(Means for Solving the Problem) In order to achieve the above-mentioned object, the present inventors have examined an inorganic material having an excellent enzyme immobilization ability, and further have a porous body for improving the efficiency as an enzyme immobilization carrier. As a result of earnestly researching the chemical conversion, Al 2 O 3 -SiO 2 ceramics have excellent enzyme immobilization ability, and by synthesizing the raw material from alumina sol and silica sol and using liquid paraffin as a molding aid. They have found that they can be made porous and have completed the present invention.
すなわち、本発明は、水系アルミナゾルと水系シリカゾ
ルをAl2O3：SiO2のモル比が３：２を最適とする割合で
混合し、乾燥・固化した原料粉末に重量比で３０％の流
動パラフィンを加え、粒状、管状、板状等の所定の形状
に成形し、1200℃〜1500℃で焼成することによって、Al
2O3−SiO2系の多孔体を製造する方法のおよびその結果
得られた酵素固定化用無機担体を提供するものである。That is, according to the present invention, an aqueous alumina sol and an aqueous silica sol are mixed at an optimal ratio of Al 2 O 3 : SiO 2 in a molar ratio of 3: 2, and the dried and solidified raw material powder is mixed with 30% by weight of liquid paraffin. Is added to form a predetermined shape such as a granular shape, a tubular shape, or a plate shape, and baked at 1200 ° C to 1500 ° C to obtain Al.
The present invention provides a method for producing a 2 O 3 —SiO 2 -based porous body and the resulting inorganic carrier for enzyme immobilization.
本発明において、担体製造原料としてアルミナゾルとシ
リカゾルを用いたことによって、共有結合法による酵素
固定化反応の反応基となる水酸基濃度が任意に制御で
き、さらに比表面積が多きな担体が製造できた。In the present invention, by using alumina sol and silica sol as the raw material for producing the carrier, the concentration of the hydroxyl group serving as the reaction group of the enzyme immobilization reaction by the covalent bond method can be arbitrarily controlled, and a carrier having a large specific surface area can be produced.
（発明の効果） 本発明によって得られた酵素固定化用無機担体は、機械
的強度が高く、耐熱性に優れているためにバイオリアク
ター用の担体として用いた場合、装置のスケールアップ
がたやすく、加熱滅菌や担体の再利用性に優れ、従って
工業規模でのバイオリアクターの利用に道を開くもので
ある。(Effects of the Invention) The inorganic carrier for enzyme immobilization obtained by the present invention has high mechanical strength and excellent heat resistance, and therefore when used as a carrier for a bioreactor, the scale-up of the device is easy. It is excellent in heat sterilization and reusability of carriers, and thus opens the way to the use of bioreactors on an industrial scale.
さらに、本発明の方法は、アルミナゾルとシリカゾルを
原料として用い、流動パラフィンを成形助材として、任
意の形状に成形したのち、焼結するだけで高効率の酵素
固定化担体が得られるために、従来のセラミックス製造
設備により実施できるので、工業的にきわめて価値の高
い方法である。Furthermore, the method of the present invention uses alumina sol and silica sol as raw materials, and uses liquid paraffin as a molding aid to form an arbitrary shape after molding into an arbitrary shape, so that a highly efficient enzyme-immobilized carrier can be obtained. This method is industrially extremely valuable because it can be carried out using conventional ceramics manufacturing equipment.
実施例 次に実施例により本発明をさらに詳細に説明する。EXAMPLES Next, the present invention will be described in more detail with reference to Examples.
（実施例１） 無機材料の酵素固定化担体能の比較 ジルコニア、チタニア、アルミナ、ケイ酸ジルコニウ
ム、チタン酸バリウム、チタン酸アルミニウム、アルミ
ノシリケイト（Al2O3−SiO2）、フォルステライト、コ
ーディエライト以上９種のち密質焼結体を合成し、グル
タルアルデヒド法でマルターゼを固定化し、酵素固定化
能および固定化酵素の安定性を調べた。その結果、表１
に示すようにその構成成分にSiO2を含む材料が高い酵素
固定化能を示した。中でもコーディエライトは最も高い
酵素固定化能を示したが、溶液中での安定性が低いため
に固定化酵素の安定性が低かった。それに対してアルミ
ノシリケイト（Al2O3−SiO2）は、酵素固定化能および
固定化酵素の安定性共に高い値を示した。(Example 1) Comparison zirconia enzyme immobilization carrier capacity of the inorganic material, titania, alumina, zirconium silicate, barium titanate, aluminum titanate, aluminosilicate (Al 2 O 3 -SiO 2) , forsterite, Kodie Light 9 or more kinds of dense sintered bodies were synthesized, maltase was immobilized by the glutaraldehyde method, and the enzyme immobilizing ability and the stability of the immobilized enzyme were examined. As a result, Table 1
As shown in Fig. 3 , the material containing SiO 2 as its constituent showed high enzyme immobilization ability. Among them, cordierite showed the highest enzyme immobilization ability, but the stability of the immobilized enzyme was low due to its low stability in solution. On the other hand, aluminosilicate (Al 2 O 3 —SiO 2 ) showed a high value in both the enzyme immobilization ability and the stability of the immobilized enzyme.
（実施例２） 水系アルミナゾルと水系シリカゾルをAl2O3：SiO2のモ
ル比が３：２を最適とする割合で混合し、乾燥・固化し
た原料粉末に重量比で３０％の流動パラフィンを加え、
粒状に成形し、１２００℃で焼成し、Al2O3−SiO2系多
孔体を合成した。 (Example 2) Aqueous alumina sol and aqueous silica sol were mixed at an optimal ratio of Al 2 O 3 : SiO 2 molar ratio of 3: 2, and 30% by weight of liquid paraffin was added to the dried and solidified raw material powder. In addition,
It was formed into granules and fired at 1200 ° C. to synthesize an Al 2 O 3 —SiO 2 type porous body.
このものは、圧縮強度７３kgf/cm2、比表面積４７m2の
クリストバライト、ムライト、Al2O3−SiO2スピネルか
らなる多孔体で、良好な酵素固定化能、固定化酵素安定
性を示した。This was a porous body composed of cristobalite, mullite, and Al 2 O 3 —SiO 2 spinel having a compressive strength of 73 kgf / cm 2 and a specific surface area of 47 m 2 , and exhibited good enzyme immobilizing ability and immobilized enzyme stability.
（実施例３） 実施例１において、焼成温度を１３００℃に変えた以外
は、実施例１と全く同様にした。(Example 3) The same procedure as in Example 1 was carried out except that the firing temperature was changed to 1300 ° C.
このものは、圧縮強度４３０kgf/cm2、比表面積１０ｍ2
のクリストバライトとムライトからなる多孔体で、良好
な酵素固定化能を示した。This product has a compressive strength of 430 kgf / cm 2 and a specific surface area of 10 m 2.
The porous body consisting of cristobalite and mullite showed good enzyme immobilization ability.
（実施例４） 実施例１において、焼成温度を１５００℃に変えた以外
は、実施例１と全く同様にした。(Example 4) The same procedure as in Example 1 was carried out except that the firing temperature was changed to 1500 ° C.
このものは、圧縮強度７８０kgf/cm2、比表面積２ｍ2の
ムライトからなる多孔体で、良好な酵素固定化能を示し
た。This product was a porous body composed of mullite having a compressive strength of 780 kgf / cm 2 and a specific surface area of 2 m 2 , and showed a good enzyme immobilizing ability.
（参考例１） 実施例２において、水系アルミナゾルと水系シリカゾル
をAl2O3：SiO2のモル比が１：１に変えた以外は、実施
例１と全く同様にした。In Reference Example 1 Example 2, the aqueous alumina sol and an aqueous silica sol Al 2 O 3: SiO 2 molar ratio is 1: except for changing 1, and in the same manner as in Example 1.
このものは、圧縮強度９６０kgf/cm2、比表面積１０ｍ2
のクリストバライトとムライトからなる多孔体であった
が、実施例１で合成した担体と比較して約１1/2の酵素
固定化能しか示さなかった。This product has a compressive strength of 960 kgf / cm 2 and a specific surface area of 10 m 2.
Although it was a porous body composed of cristobalite and mullite, it exhibited only about 11/2 of the enzyme immobilizing ability as compared with the carrier synthesized in Example 1.
（参考例２） 実施例２において、水系アルミナゾルと水系シリカゾル
をAl2O3：SiO2のモル比が４：３に変えた以外は、実施
例１と全く同様にした。In Reference Example 2 Example 2, the aqueous alumina sol and an aqueous silica sol Al 2 O 3: SiO 2 molar ratio is 4: except for changing the 3 and in the same manner as in Example 1.
このものは、圧縮強度４３０kgf/cm2、比表面積１７ｍ2
のクリストバライト、ムライト、アルミナからなる多孔
体であったが、実施例１で合成した担体と比較して約１
／２の酵素固定変能しか示さなかった。This product has a compressive strength of 430 kgf / cm 2 and a specific surface area of 17 m 2.
Although it was a porous body composed of cristobalite, mullite, and alumina, it was about 1 in comparison with the carrier synthesized in Example 1.
It only showed an enzyme immobilization capacity of / 2.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 鈴木 高広 愛知県名古屋市北区八代町２丁目109番地 八代寮101号 (56)参考文献 特開 平１−275480（ＪＰ，Ａ) 特開 昭60−98985（ＪＰ，Ａ) ─────────────────────────────────────────────────── --- Continuation of the front page (72) Inventor Takahiro Suzuki 2-109, Yatsushiro-cho, Kita-ku, Nagoya-shi, Aichi No. 101 Yatsushiro Dormitory (56) References JP-A-1-275480 (JP, A) JP-A-60 -98985 (JP, A)
Claims (2)
2Ｏ3：ＳｉＯ2のモル比が３：１を最適とする３：１．
８〜２．２の割合で混合し、乾燥・固化した粉末に重量
比で３０％の流動パラフインを加え、粒状、管状、板状
等の所定の形状に成形し、１２００℃〜１５００℃で焼
成し、Ａｌ2Ｏ3−ＳｉＯ2系ムライト質多孔体を製造す
る方法。1. A water-based alumina sol and a water-based silica sol are mixed with Al.
Optimum molar ratio of 2 O 3 : SiO 2 is 3: 1 3: 1.
Mixing in a ratio of 8 to 2.2, adding 30% by weight of fluidized paraffin to the dried and solidified powder, molding into a predetermined shape such as granular, tubular, plate-like, and firing at 1200 ° C to 1500 ° C. And a method for producing an Al 2 O 3 —SiO 2 -based mullite porous body.
た酵素固定化用担体。2. An enzyme-immobilized carrier produced by the method according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2067961A JPH064029B2 (en) | 1990-03-16 | 1990-03-16 | Inorganic carrier for enzyme immobilization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2067961A JPH064029B2 (en) | 1990-03-16 | 1990-03-16 | Inorganic carrier for enzyme immobilization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03266985A JPH03266985A (en) | 1991-11-27 |
| JPH064029B2 true JPH064029B2 (en) | 1994-01-19 |
Family
ID=13360071
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2067961A Expired - Lifetime JPH064029B2 (en) | 1990-03-16 | 1990-03-16 | Inorganic carrier for enzyme immobilization |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH064029B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5614401A (en) * | 1993-06-23 | 1997-03-25 | Toyo Denka Kogyo Co., Ltd. | Enzyme immobilizing carrier containing kaolin |
| JPH0818814B2 (en) * | 1993-06-23 | 1996-02-28 | 東洋電化工業株式会社 | Porous powder and method for producing the same |
| JP3371531B2 (en) * | 1994-04-20 | 2003-01-27 | 株式会社豊田中央研究所 | Catalyst production method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6098985A (en) * | 1983-11-02 | 1985-06-01 | Kikkoman Corp | Preparation of immobilized mold of microorganism for enzyme |
| GB8803413D0 (en) * | 1988-02-15 | 1988-03-16 | Ecc Int Ltd | Biological support |
-
1990
- 1990-03-16 JP JP2067961A patent/JPH064029B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03266985A (en) | 1991-11-27 |
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| EXPY | Cancellation because of completion of term |