WO2005095626A1 - Biocatalyseur immobilisé et procédé servant à produire un sel d'acide organique avec celui-ci - Google Patents

Biocatalyseur immobilisé et procédé servant à produire un sel d'acide organique avec celui-ci Download PDF

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Publication number
WO2005095626A1
WO2005095626A1 PCT/JP2005/005799 JP2005005799W WO2005095626A1 WO 2005095626 A1 WO2005095626 A1 WO 2005095626A1 JP 2005005799 W JP2005005799 W JP 2005005799W WO 2005095626 A1 WO2005095626 A1 WO 2005095626A1
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organic acid
biocatalyst
producing
acid salt
aqueous solution
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PCT/JP2005/005799
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English (en)
Japanese (ja)
Inventor
Youichi Kobayashi
Masahiro Yokoyama
Ryosuke Mizui
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Nippon Soda Co., Ltd.
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Publication of WO2005095626A1 publication Critical patent/WO2005095626A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
    • C12P7/42—Hydroxy-carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
    • C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
    • C12N11/04—Enzymes or microbial cells immobilised on or in an organic carrier entrapped within the carrier, e.g. gel or hollow fibres
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P11/00—Preparation of sulfur-containing organic compounds
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P13/00—Preparation of nitrogen-containing organic compounds
    • C12P13/04—Alpha- or beta- amino acids
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P13/00—Preparation of nitrogen-containing organic compounds
    • C12P13/04—Alpha- or beta- amino acids
    • C12P13/12—Methionine; Cysteine; Cystine

Definitions

  • the present invention relates to a method for producing an organic acid salt by using a hydrolysis action of an immobilized biocatalyst.
  • the organic acid salt produced according to the present invention is used as it is or, if necessary, converted into the corresponding organic acid for use in industrial raw materials, agricultural and pharmaceutical raw materials, feed additives and the like.
  • the present invention also provides a method for preparing an immobilized biocatalyst.
  • the immobilized biocatalyst produced by the present invention is used for applications such as production of various useful substances, wastewater treatment and environmental purification.
  • Patent Document 1 Japanese Patent Publication No. 58-15120
  • Patent Document 2 JP-A-04-40898
  • Patent Document 3 JP-A-03-62391
  • Patent document 4 International publication 00-27809 pamphlet
  • Non-Patent Document 1 Methods in ENZYMOLOGY 135, 175-189
  • the present inventors have found that when converting nitrile or amide to the corresponding organic acid ammonium, As a result of intensive studies on the preparation method of the immobilized biocatalyst that can be used, when the biocatalyst is entrapped and immobilized with an alginate gel, a cationic amine such as a primary amine or a secondary amamine is contained in its constituent unit.
  • the method of contacting the polymer simultaneously with the polyvalent metal ion or after contacting the polymer with the polyvalent metal ion does not cause a decrease in the activity of the biocatalyst at the time of preparation and prevents the catalyst from being used and washed.
  • the present invention has been completed by finding an industrially advantageous method for preparing a biocatalyst which does not require the occasional addition of polyvalent metal ions such as Ca ions irrespective of the concentration of the organic acid ammonium.
  • the biocatalyst is mixed with an aqueous alginate solution, and the mixed solution is contacted with an aqueous solution containing a cationic polymer having a primary amine or a secondary amine in a constituent unit and a polyvalent metal ion to form a gel.
  • an immobilized biocatalyst or by contacting the mixture with an aqueous solution containing a polyvalent metal ion to form a gel and then contacting with a cationic polymer having a primary or secondary amine in the constituent unit
  • a process for producing an organic acid salt which comprises recovering the organic acid ammonium.
  • the present invention provides a gel catalyst by mixing a biocatalyst with an aqueous alginate solution and bringing the mixed solution into contact with an aqueous solution containing a cationic polymer having a primary amine or a secondary amine as a constituent unit and a polyvalent metal ion.
  • a gel catalyst by mixing a biocatalyst with an aqueous alginate solution and bringing the mixed solution into contact with an aqueous solution containing a cationic polymer having a primary amine or a secondary amine as a constituent unit and a polyvalent metal ion.
  • the immobilized biocatalyst is prepared, and then, in a solvent containing the immobilized biocatalyst, the tolyl or amide is converted to the corresponding organic acid ammonium without supplying the polyvalent metal ion. And recovering the organic acid ammonium salt.
  • X- represents a monovalent anion, and n represents an integer of 10 to 4000
  • X- represents a monovalent anion
  • k and m are integers of 1 to 10
  • n is an integer of 10 to 4000.
  • X- represents a monovalent anion
  • n represents an integer of 10 to 4000
  • a cationic polymer having a secondary amine or a secondary amine is a mixture of the polymer represented by the above formula 1, 2, or 3 and polyethyleneimine. Method for producing acid salt.
  • the biocatalyst is derived from a microorganism belonging to the genus Arthrobacter, the genus Variovorax, the genus Pseudonocardia, or the genus Rhodococcus.
  • the method for producing an organic acid salt according to (4) is derived from a microorganism belonging to the genus Arthrobacter, the genus Variovorax, the genus Pseudonocardia, or the genus Rhodococcus.
  • the biocatalyst is characterized by being Arthrobacter sp. NS (Arthrobacter sp.) NSSC104, earth mouth Bacter sp. NS (Arthrobacter sp.) NSSC204 or Pseudonocardia thermophila JCM3095 ( (1) The method for producing an organic acid salt according to (8)
  • an organic acid ammonium - ⁇ concentration arm is characterized in that 5 wt 0/0 above (1) to a manufacturing method of an organic acid salt according to (6).
  • a method for preparing an immobilized biocatalyst comprising the steps of:
  • aqueous solutions of alginate used in the present invention include aqueous solutions of sodium alginate, potassium alginate, and ammonium alginate.
  • the cationic polymer used in the present invention may be any polymer that contains a primary amine or a secondary amine in its constituent unit. Homopolymers represented by the formula, copolymers represented by the above formula 2, polyethylenimine and chitosan can be mentioned. These cationic polymers can be used in combination of two or more kinds. More specifically, Nittobo's PAS series, PAA series, etc. can be exemplified.
  • the monovalent anion used in the present invention includes, but is not limited to, Cl-, OH- and the like.
  • Polyvalent metal ions used in the present invention include calcium ions, strontium ions, norium ions, aluminum ions and the like.
  • alginate gel used in the present invention examples include hydrogels formed by calcium alginate, strontium alginate, barium alginate, aluminum alginate and the like.
  • the -tolyl used in the present invention includes ratato-tolyl, mandero-tolyl, 2-hydroxy
  • Examples of the amide used in the present invention include lactamide, mandelamide, 2-hydroxy-1-methylthiobutyramide, and 2-amino-4-methylthiobutyramide.
  • the organic acid salt produced in the present invention includes ammonium salts such as lactic acid, mandelic acid, 2-hydroxy-4-methylthiobutanoic acid and methionine, sodium salts, potassium salts, calcium salts, magnesium salts and the like. Is mentioned.
  • the biocatalyst used in the present invention is not particularly limited as long as it is a cell having an activity of converting a -tolyl or amide compound into a corresponding organic acid ammonium or a treated product thereof.
  • Genus and among these, in particular, earth bacterium _ _ ⁇ sp (Arthrobacter sp.) NSSC104 (FERM BP-5829), earth port pacta ⁇ _ ⁇ sp (Arthrobacter sp.) NSSC204 (FERM BP) — 7662), Variovorax paradoxus IAM12374, Pseudonocardia thermoph ila) JCM3095 can be suitably exemplified. Further, there may be mentioned cells of a recombinant organism obtained by introducing a gene sequence encoding -tolylase, amidase or -tolylhydratase contained in these cells into another kind of cell. Examples of the processed product include a cell extract or -tolylase, nitrile hydratase or amidase purified from the extract.
  • the immobilization of the biocatalyst is performed as follows. First, cells collected from a culture solution obtained by culturing the above microorganisms by centrifugation or membrane separation are suspended in an aqueous solution containing a water-soluble alginate such as sodium alginate. Is continuously dropped into an aqueous solution containing a polyvalent metal ion such as a calcium ion, a strontium ion, a barium ion or an aluminum ion, and the above-mentioned cationic polymer to obtain a bead-shaped molded product.
  • a polyvalent metal ion such as a calcium ion, a strontium ion, a barium ion or an aluminum ion
  • the molded article may be obtained in an aqueous solution containing only the polyvalent metal ion and then immersed in an aqueous solution containing the cationic polymer.
  • a valent metal ion may be contained.
  • it can be formed into a plate, rod, thread, or the like, and then cut and used as necessary.
  • the thus obtained immobilized biocatalyst was treated with nitrile or acetonitrile as it was or after being washed with an aqueous solvent. It can be subjected to a conversion reaction to the corresponding organic acid ammonium by contacting with the midi conjugate.
  • Alginates used in preparing the immobilized biocatalyst include sodium alginate, potassium alginate, and alginate alginate, which have a concentration of 0.1 to 0.1% before gelling. Can be used in the range of 10% by weight. The cell concentration before gelation can be used in the range of 0.01 to 15% by weight as the dry weight of the cells.
  • the inner diameter of the injection needle, pores, etc. for forming the droplets should be within the range of 0.05 to 5 mm.
  • An industrial method such as flow, mechanical vibration or mechanical shear may be used.
  • the polyvalent metal used for geli-dani is selected from the group consisting of canoleshmi-d, strontium-d, norium-d, aluminum ion, and the like. Used as an aqueous solution.
  • Gel is a force generated simultaneously with contact with polyvalent metal ions. In order to increase the strength of the gel, it is better to contact these polyvalent metal ions for at least 30 minutes, preferably 2 hours to 5 days.
  • a higher temperature during gel formation has the effect of shortening the contact time, but is usually selected in the range of 4 to 60 ° C in consideration of the stability of the biocatalyst.
  • the pH at the time of gel formation should be determined in consideration of the stability of the biocatalyst.
  • Normal pH3 ⁇ Power selected in the range of L1 Avoid chitosan aggregation only when chitosan is used as the cationic polymer
  • the pH is preferably adjusted to 7 or less.
  • the amount of the aqueous solution of the polyvalent metal salt used when the gel is formed into beads is sufficient as long as the droplets to be dropped do not come into contact with each other before being formed into beads.
  • 0.5-: LOO double capacity is used.
  • the concentration of the cationic polymer at the time of forming the gel can be generally used in the range of 10 ppm to 10% by weight, preferably 20 ppm to 1% by weight.
  • the concentration of the cationic polymer can be generally used in the range of 10 ppm to 10% by weight, preferably 20 ppm to 1% by weight, and the immersion time is A force in the range of 30 minutes or more, preferably 2 hours to 5 days, a treatment temperature of 4 to 60 ° C. and a pH of 3 to 11 is also selected.
  • the pH is preferably adjusted to 7 or less in order to avoid aggregation of chitosan.
  • the size of the prepared beads changes depending on the salt concentration, pH, temperature conditions, etc.
  • the thus obtained immobilized biocatalysts are physically stable even at a polyvalent metal ion concentration of less than 10 mM, and have an alginate gel force.
  • a force capable of depriving polyvalent metal ions. Rubonate, phosphate and sulfate. Force that can be used even in the presence of a salt When using a method of simultaneously contacting a polyvalent metal ion and a cationic polymer to perform gelling, contacting the cationic polymer after gelling with a polyvalent metal ion An immobilized biocatalyst having better physical stability than the method can be obtained.
  • the production of an organic acid salt using the immobilized biocatalyst prepared as described above is performed as follows.
  • the immobilized biocatalyst is added to water or an aqueous solution of an organic acid corresponding to the desired organic acid salt, and the pH is adjusted as necessary.
  • the addition of the compound causes the accumulation of the ammonium salt.
  • the reaction can be stopped and the batch reaction for separating the immobilized biocatalyst from the product can be repeated, but the organic reaction can be continued while adding the substrate.
  • the recovery of the reaction solution and the supply of water are performed in parallel, so that the aqueous solution of the organic acid ammonium in a certain range can be continuously produced.
  • the resulting continuous reaction may be carried out using a column reactor or a stirred tank reactor.
  • the reaction temperature may be kept constant, but the biocatalyst may be changed within a stable range for the purpose of maintaining a constant production rate.
  • the substrate concentration may be changed so that the substrate supply rate is maintained at a constant value.However, it is sufficient to maintain the substrate supply rate at a constant value. To avoid this, an additional biocatalyst can be added.
  • Organic acid ammonium - ⁇ amount of fixed I ⁇ member catalyst in the production of beam can be performed in the range of the reaction solution to 50 by weight at a ratio of wet weight for weight 0/0.
  • the reaction is carried out at a pH of 3 to 12, preferably 5 to L1.
  • the temperature of the reaction may be selected in the range from 4 to 70 ° C.
  • the concentration of the substrate can be in the range of 0.001% by weight to the saturation concentration, and the concentration of the formed organic acid ammonium salt can be in the range of 1% by weight to the saturation concentration, preferably 5% by weight to the saturation concentration. You can do it.
  • the reaction solution may contain salts such as carboxylate, phosphate, sulfate, etc., in addition to the produced organic acid ammonium salt.
  • the desired organic acid salt can be prepared from the obtained aqueous solution of organic acid ammonium by adding a corresponding base and distilling off ammonia. At this time, the aqueous solution of organic acid ammonium may be concentrated in advance.
  • the base to be added may be selected according to the target organic acid salt, and examples thereof include sodium hydroxide, potassium hydroxide, calcium hydroxide, and magnesium hydroxide. In addition, Sidani calcium, calcium carbonate, Sidani magnesium or magnesium carbonate may be used.
  • the target organic acid salt can be obtained under industrially advantageous conditions by virtue of the nitrile or amido ligating properties.
  • Yeast extract 0.5%, glucose 0.5%, dipotassium hydrogen phosphate 0.1%, potassium dihydrogen phosphate 0.1%, salt 0.1%, magnesium sulfate heptahydrate 0.02%, and 3 ml of a medium containing 0.001% of ferrous sulfate was placed in a test tube and sterilized at 121 ° C for 20 minutes.
  • 200 ml of a medium having the following composition was placed in a 1000 ml baffled Erlenmeyer flask.
  • One platinum loop of Arthrobacter NSSC204 strain was inoculated into the above-mentioned test tube, and cultured at 33 ° C. with shaking. Then, 2 ml of the culture was inoculated into the above-mentioned Erlenmeyer flask with a baffle, and then transferred. Shaking culture was performed at 33 ° C for days.
  • the cells were collected as a pellet by centrifuging the obtained culture solution, and suspended in ion-exchange water to obtain a 20-ml cell suspension.
  • 0.357 g of sodium alginate was dissolved in 50 ml of water and mixed with 20 ml of the cell suspension to obtain a cell-sodium alginate mixed solution.
  • the piping was connected so that this mixed solution could be dropped from the tip of the injection needle (22G) using a tubing pump.
  • Calcium chloride dihydrate 5 5.
  • the fixed immobilized cell body catalyst (equivalent to 3.3 g in terms of dry weight) obtained in Example 1 was placed in a ⁇ four-necked flask, and water was added to make 55.5 ml.
  • the four-necked flask was equipped with a stirring blade, a pH sensor, a raw material supply pipe, a reaction liquid recovery pipe with a filter, a pH adjustment liquid supply pipe, a replenishment water supply pipe, and a water level sensor.
  • the flask was placed in a constant temperature water bath at 25 ° C., and stirring was performed at a speed of 60 rpm.
  • the pH sensor is connected to a pH controller, and the pH is automatically adjusted to 7.0 to 7.5 by supplying 0.5% ammonia water from the pH adjustment liquid supply pipe with a pump controlled by the pH controller.
  • the raw material 2-hydroxy-4-methylthiop-mouth-tolyl
  • the reaction solution was continuously collected through a reaction solution collection tube by a metering pump.
  • the water level sensor is installed so that it can detect that the liquid volume in the flask has changed from the initial liquid volume (65 ml), and the replenishing water is supplied by a pump linked to the water level sensor, so that the reaction solution is removed from the flask.
  • the liquid level was set so as to maintain a constant height even when the liquid was discharged.
  • the continuous reaction was performed as follows. As a first step, the water level and pH controls were not activated, and the raw material-tolyl was continuously added at a rate of 4 gZh. When the water level sensor-detects the liquid level, the raw material - tolyl are 12. 5 g feed, 2-hydroxy-4-methylthiobutanoate ammoxidation reaction liquid - ⁇ beam concentration had reached 20 weight 0/0. Then, control of the water level and pH was started, and a continuous reaction was started in which the reaction solution was continuously withdrawn at a rate of 15 gZh while adding the starting material-tolyl at a rate of 3 gZh.
  • reaction solution components The analysis of the reaction solution components is as follows It went to. After sampling 0.1 ml of the reaction solution and diluting 100 times with water, high performance liquid chromatography (column: Tosoh ODS-80TS 4.6 mm XI 50 mm, eluent: 0.1% (V / V) TFA- 20% (VZV) acetonitrile aqueous solution, flow rate: lmlZmin, column temperature: 40 ° C). A calibration curve was prepared using known concentrations of 2-hydroxy-4-methylthiobutyrate-tolyl and ammonium 2-hydroxy-1-methylthiobutanoate, and the peak area force of each diluted sample was analyzed. Calculated.
  • FIG. 1 shows the results of a continuous reaction for 46 days. During this time, the immobilized cell catalyst beads were physically stable, and beads collapsed and cell leakage was not observed.
  • Example 2 As in Example 2, except that the addition of polyallylamine hydrochloride was omitted, the immobilized Idani germ cell catalyst (equivalent to 3.3 g in terms of dry weight) prepared in the same manner as in Example 1 was used. Continuous production of ammonium 2-hydroxy-4-methylthiobutanoate was attempted by the method described above. As a first step of continuous reaction, a state that does not actuate the control of the water level and P H, the raw material - was continuously added tri Le at a rate of 4GZh. Approximately one hour later, the leakage of cells from the immobilized cell catalyst began to be observed, and after one hour, the shape of the immobilized cell catalyst began to collapse. The sol was turned into sol and the viscosity of the reaction solution increased, making it impossible to continue the continuous reaction.
  • the activity of the biocatalyst is not reduced at the time of its preparation, and at the time of its use or washing.
  • the desired organic acid salt can be obtained under industrially advantageous conditions by using an immobilized biocatalyst that does not require the addition of polyvalent metal ions such as Ca ions, regardless of the presence or absence of the organic acid ammonium. be able to.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Zoology (AREA)
  • Wood Science & Technology (AREA)
  • Genetics & Genomics (AREA)
  • Health & Medical Sciences (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
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  • General Health & Medical Sciences (AREA)
  • Biotechnology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Biomedical Technology (AREA)
  • Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)

Abstract

[PROBLÈMES] Fournir un procédé servant à produire un sel d'acide organique lequel comprend d'hydrolyser un nitrile ou un amide dans des conditions telles que la concentration en sels d'ions métalliques polyvalents tels qu'un ion calcium soit faible et qu'un sel d'ammonium de l'acide organique soit présent en grande quantité, grâce à l'hydrolyse avec un biocatalyseur recouvert et immobilisé avec un gel d'acide alginique. [MOYENS POUR RÉSOUDRE LES PROBLÈMES] Le procédé servant à produire un sel d'acide organique est caractérisé en ce qu'on utilise l'activité hydrolytique d'un biocatalyseur recouvert et immobilisé avec un polymère cationique ayant une amine primaire ou une amine secondaire comme motifs de structure et avec un sel de l'acide alginique pour convertir un nitrile ou un amide en sel d'ammonium de l'acide organique correspondant sans apporter d'ions métalliques polyvalents.
PCT/JP2005/005799 2004-03-31 2005-03-29 Biocatalyseur immobilisé et procédé servant à produire un sel d'acide organique avec celui-ci WO2005095626A1 (fr)

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Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5053586A (fr) * 1973-09-19 1975-05-12
JPS6088018A (ja) * 1983-10-21 1985-05-17 Nitto Boseki Co Ltd モノアリルアミンとジアリルアミン誘導体との共重合体の製造方法
JPS60160885A (ja) * 1984-01-30 1985-08-22 Asama Kasei Kk 固定化した微生物、植物細胞および／または酵素
JPS61162191A (ja) * 1985-01-11 1986-07-22 Nitto Chem Ind Co Ltd 微生物による有機酸類の製造法
JPH0440898A (ja) * 1990-06-08 1992-02-12 Nitto Chem Ind Co Ltd α―ヒドロキシ―４―メチルチオ酪酸の生物学的製造法
JPH04193308A (ja) * 1990-11-27 1992-07-13 Nitto Boseki Co Ltd 凝集剤
WO1997032030A1 (fr) * 1996-02-29 1997-09-04 Nippon Soda Co., Ltd. PROCESSUS DE PREPARATION D'ACIDES α-HYDROXY A L'AIDE D'UN MICRO-ORGANISME ET NOUVEAU MICRO-ORGANISME
JPH10286087A (ja) * 1997-02-14 1998-10-27 Nippon Shokubai Co Ltd 固定化生体触媒
JP2000125831A (ja) * 1998-10-26 2000-05-09 Frontier Engineering:Kk 筒状食品の連続通電加熱装置用串状電極
JP2001017195A (ja) * 1999-07-02 2001-01-23 Nippon Soda Co Ltd 微生物触媒を用いた物質生産方法
WO2002008439A1 (fr) * 2000-07-21 2002-01-31 Nippon Soda Co., Ltd. Procede d'elaboration d'acides 2-amino
JP2002034584A (ja) * 2000-07-21 2002-02-05 Nippon Soda Co Ltd α−ヒドロキシ酸アンモニウム塩の製造法
JP2003524608A (ja) * 1998-11-06 2003-08-19 アベンテイス・アニマル・ニユートリシヨン・エス・エー メチオニンの製造方法

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5053586A (fr) * 1973-09-19 1975-05-12
JPS6088018A (ja) * 1983-10-21 1985-05-17 Nitto Boseki Co Ltd モノアリルアミンとジアリルアミン誘導体との共重合体の製造方法
JPS60160885A (ja) * 1984-01-30 1985-08-22 Asama Kasei Kk 固定化した微生物、植物細胞および／または酵素
JPS61162191A (ja) * 1985-01-11 1986-07-22 Nitto Chem Ind Co Ltd 微生物による有機酸類の製造法
JPH0440898A (ja) * 1990-06-08 1992-02-12 Nitto Chem Ind Co Ltd α―ヒドロキシ―４―メチルチオ酪酸の生物学的製造法
JPH04193308A (ja) * 1990-11-27 1992-07-13 Nitto Boseki Co Ltd 凝集剤
WO1997032030A1 (fr) * 1996-02-29 1997-09-04 Nippon Soda Co., Ltd. PROCESSUS DE PREPARATION D'ACIDES α-HYDROXY A L'AIDE D'UN MICRO-ORGANISME ET NOUVEAU MICRO-ORGANISME
JPH10286087A (ja) * 1997-02-14 1998-10-27 Nippon Shokubai Co Ltd 固定化生体触媒
JP2000125831A (ja) * 1998-10-26 2000-05-09 Frontier Engineering:Kk 筒状食品の連続通電加熱装置用串状電極
JP2003524608A (ja) * 1998-11-06 2003-08-19 アベンテイス・アニマル・ニユートリシヨン・エス・エー メチオニンの製造方法
JP2001017195A (ja) * 1999-07-02 2001-01-23 Nippon Soda Co Ltd 微生物触媒を用いた物質生産方法
WO2002008439A1 (fr) * 2000-07-21 2002-01-31 Nippon Soda Co., Ltd. Procede d'elaboration d'acides 2-amino
JP2002034584A (ja) * 2000-07-21 2002-02-05 Nippon Soda Co Ltd α−ヒドロキシ酸アンモニウム塩の製造法

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Title
WANG Y.J. ET AL: "Development of new polycations for cell encapsulation with alginate.", MATERIALS SCIENCE & ENGINEERING C., vol. 13, no. 1-2, 2000, pages 59 - 63, XP002989846 *

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