DE2421650A1 - IMMOBILIZATION OF ENZYMES IN ULTRAFILTRATION MEMBRANES - Google Patents
IMMOBILIZATION OF ENZYMES IN ULTRAFILTRATION MEMBRANESInfo
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- DE2421650A1 DE2421650A1 DE2421650A DE2421650A DE2421650A1 DE 2421650 A1 DE2421650 A1 DE 2421650A1 DE 2421650 A DE2421650 A DE 2421650A DE 2421650 A DE2421650 A DE 2421650A DE 2421650 A1 DE2421650 A1 DE 2421650A1
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- enzyme
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- 108090000790 Enzymes Proteins 0.000 title claims description 58
- 102000004190 Enzymes Human genes 0.000 title claims description 58
- 239000012528 membrane Substances 0.000 title claims description 31
- 238000000108 ultra-filtration Methods 0.000 title description 9
- 229920000642 polymer Polymers 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 10
- 239000003085 diluting agent Substances 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 229920005597 polymer membrane Polymers 0.000 claims description 3
- 239000007970 homogeneous dispersion Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000011148 porous material Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 108010046334 Urease Proteins 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920002466 Dynel Polymers 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000003100 immobilizing effect Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 108010093096 Immobilized Enzymes Proteins 0.000 description 1
- HSGSGNFSUDPBDX-UHFFFAOYSA-N N,N-dimethylacetamide N,N-dimethylformamide Chemical compound C(=O)N(C)C.C(=O)N(C)C.C(C)(=O)N(C)C HSGSGNFSUDPBDX-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229920004890 Triton X-100 Polymers 0.000 description 1
- 108700040099 Xylose isomerases Proteins 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- -1 arches Substances 0.000 description 1
- PPBAJDRXASKAGH-UHFFFAOYSA-N azane;urea Chemical compound N.NC(N)=O PPBAJDRXASKAGH-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 108010051210 beta-Fructofuranosidase Proteins 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000008121 dextrose Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000001760 fusel oil Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000013072 incoming material Substances 0.000 description 1
- 235000011073 invertase Nutrition 0.000 description 1
- 239000001573 invertase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- PMPRVTLEEOMPAR-UHFFFAOYSA-N n,n-dimethylacetamide;n,n-dimethylformamide;1-methylpyrrolidin-2-one Chemical compound CN(C)C=O.CN(C)C(C)=O.CN1CCCC1=O PMPRVTLEEOMPAR-UHFFFAOYSA-N 0.000 description 1
- LDVAUXKTWYGAIY-UHFFFAOYSA-N n,n-dimethylformamide;1-methylpyrrolidin-2-one;methylsulfinylmethane Chemical compound CS(C)=O.CN(C)C=O.CN1CCCC1=O LDVAUXKTWYGAIY-UHFFFAOYSA-N 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011049 pearl Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- XIPFMBOWZXULIA-UHFFFAOYSA-N pivalamide Chemical compound CC(C)(C)C(N)=O XIPFMBOWZXULIA-UHFFFAOYSA-N 0.000 description 1
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 230000007723 transport mechanism Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/142—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes with "carriers"
- B01D69/144—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes with "carriers" containing embedded or bound biomolecules
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/145—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing embedded catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/301—Polyvinylchloride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
- B01D71/421—Polyacrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M21/00—Bioreactors or fermenters specially adapted for specific uses
- C12M21/18—Apparatus specially designed for the use of free, immobilized or carrier-bound enzymes
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M23/00—Constructional details, e.g. recesses, hinges
- C12M23/34—Internal compartments or partitions
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M25/00—Means for supporting, enclosing or fixing the microorganisms, e.g. immunocoatings
- C12M25/02—Membranes; Filters
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M29/00—Means for introduction, extraction or recirculation of materials, e.g. pumps
- C12M29/04—Filters; Permeable or porous membranes or plates, e.g. dialysis
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M47/00—Means for after-treatment of the produced biomass or of the fermentation or metabolic products, e.g. storage of biomass
- C12M47/10—Separation or concentration of fermentation products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Zoology (AREA)
- Biotechnology (AREA)
- Genetics & Genomics (AREA)
- Biochemistry (AREA)
- General Engineering & Computer Science (AREA)
- Biomedical Technology (AREA)
- General Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microbiology (AREA)
- Sustainable Development (AREA)
- Dispersion Chemistry (AREA)
- Molecular Biology (AREA)
- Clinical Laboratory Science (AREA)
- Materials Engineering (AREA)
- Immunology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
- Apparatus Associated With Microorganisms And Enzymes (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Enzymes And Modification Thereof (AREA)
Description
Priorität vom 7. Mai 1973 in USA, Serial No.358.170Priority dated May 7, 1973 in USA, Serial No.358.170
Die Erfindung betrifft ein Verfahren zur Immobilisierung von Enzymen in einer Ultrafiltrationsmembran und eine Membran mit eingeschlossenen Enzymen sowie ein enzymatisch.es Reaktions- und Trennverfahren unter Vewendung einej/solchen Membran. Wegen ihrer zahlreichen Eigenschaften erscheinen Enzyme als ideale Katalysatoren vom Standpunkt der chemischen Verfahrenstechnik. Unter milden pH- und Temperaturbedingungen arbeiten sie gut, sie führen häufig zu hohen Reaktionsraten, und jedes Enzym besitzt eine bemerkenswerte Spezifität hinsichtlich der ausgelösten Reaktionsart. Praktisch ausnahmslos hängen chemische Reaktionen für die Unterhaltung des ZeIl-The invention relates to a method for immobilizing enzymes in an ultrafiltration membrane and a membrane with enclosed enzymes as well as an enzymatic reaction and separation methods using such a membrane. Because of their numerous properties, enzymes appear to be ideal catalysts from the chemical standpoint Process technology. They work well under mild pH and temperature conditions, they often lead to high reaction rates, and each enzyme has a remarkable specificity in terms of the type of response elicited. Virtually without exception chemical reactions for the maintenance of the cell
AO9847/0922AO9847 / 0922
2 A 2 1 6 5 Ü2 A 2 1 6 5 n
lebens von der katalytischen Einschaltung von Enzymen ab, so daß ungewöhnlich verschiedenartige Reaktionen durch diese Katalysatoren kontrolliert werden.depend on the catalytic activation of enzymes, so that unusually diverse reactions result from them Catalysts are controlled.
Die scheinbar ungeheure gewerbliche Anwendungsfähigkeit von Enzymen ist jedoch wegen ihrer hohen Ausgangskosten, ihrer Unbeständigkeit und der Schwierigkeiten, die sich bei der Abtrennung der Enzyme von den Reaktionsprodukten ergeben, nicht verwirklicht worden. Beispielsweise ist es allgemein unwirtschaftlich, die Enzyme nach Beendigung der gewünschten Reaktion als Abfall zu verwerfen; statt dessen hat man versucht , das Reaktionsprodukt von den Enzymen abzutrennen und die Enzyme dann zu Rohmaterial zurückzuleiten. Bei einer derartigen Betriebsweise zeigte sich, daß die Enzyme bei den erforderlichen Pumpgeschwindigkeiten empfindlich gegen Scherkräfte sind und unter solchen Bedingungen zu einer Degenerierung neigen.The seemingly vast commercial utility of enzymes, however, has not been realized because of their high initial cost, inconsistency, and the difficulties involved in separating the enzymes from the reaction products. For example, it is generally uneconomical to discard the enzymes as waste after the desired reaction has ended; instead, attempts have been made to separate the reaction product from the enzymes and then return the enzymes to raw material. In such an operation it was found that the enzymes are sensitive to shear forces at the required pump speeds and tend to degenerate under such conditions.
Wegen dieser Schwierigkeit ist andererseits vorgeschlagen worden, die Enzyme durch Anlagerung an künstlichen Matritzen zu immobilisieren. Tatsächlich sind in den letzten Jahren Enzyme an natürliche Polymere, künstliche Polymere und anorganische Materialien, wie Glas, Metall und Metallsalze in. verschiedenerlei Formen, wie Perlen, Mikrokapseln, Bögen, Membranen, Filterpapier und Mikroröhrchen angelagert worden.Because of this difficulty, on the other hand, it has been proposed to convert the enzymes by attachment to artificial matrices to immobilize. Indeed, in recent years, enzymes are attached to natural polymers, man-made polymers and inorganic ones Materials such as glass, metal and metal salts in various shapes such as pearls, microcapsules, arches, Membranes, filter paper and microtubes have been attached.
409847/0922409847/0922
Zur Immobilisierung von Enzymen sind verschiedene Techniken
angewandt worden. Beim Adsorptionsverfahren werden Enzyme
durch Anziehung entgegengesetzter elektrischer Ladungen an
ihrem Platz gehalten. Beispielsweise wird ein Enzym von
positiver Ladung an einer negativ geladenen Matritze gebunden. Ein Gelgitter kann das Enzym einfangen. Die Poren
des Gelgitters müssen groß genug sein, um das Substrat und
das Endprodukt innerhalb und außerhalb des Gitters umlaufen zu lassen. Eine weitere Methode besteht in einer covalenten
chemischen Bindung, bei der eine unmittelbare chemische Verknüpfung zwischen Enzym und Matritze eintritt.Various techniques have been used to immobilize enzymes. In the adsorption process, enzymes
by attracting opposite electrical charges
held in place. For example, an enzyme is used by
positive charge bound to a negatively charged die. A gel grid can capture the enzyme. The pores of the gel grid must be large enough to accommodate the substrate and
circulating the end product inside and outside the grid. Another method is a covalent chemical bond, in which a direct chemical bond occurs between the enzyme and the die.
Soweit bisher Enzyme an Polymeren angelagert worden sind, besteht der Mechanismus der Anlagerung im allgemeinen in einer gewissen Form vn covalenter Bindunge Diese Anlagerungsmethode hat den Nachteil, daß der Chemismus des Enzyms zwangsläufig verändert wird, und dies hat häufig einen nachteiligen Einfluß auf die Reaktionsfähigkeit des Enzyms.To the extent so far enzymes have been attached to polymers, the mechanism of attachment generally is in a certain shape vn covalent bond e This addition method has the disadvantage that the chemistry of the enzyme is inevitably changed, and this often has an adverse influence on the reactivity of the Enzyme.
Es besteht daher ein echtes Bedürfnis für ein Verfahren zur
Immobilisierung von Enzymen ohne Beeinträchtigung ihrer Reaktionsfähigkeit. Die Erfindung hat sich deshalb die Aufgabe
gestellt, ein neues Verfahren zu schaffen, bei dem die Enzyme in einer Ultrafiltrationsmembran, und zwar durch Einschluß
immobilisiert werden, wodurch sich eine neuartige
Ultrafiltrationsmembran ergibt.There is therefore a real need for a method of immobilizing enzymes without compromising their responsiveness. The invention has therefore set itself the task of creating a new process in which the enzymes are immobilized in an ultrafiltration membrane, specifically by inclusion, whereby a novel
Ultrafiltration membrane results.
4 0 9 8 Λ 7 / 0 ίϊ 2 24 0 9 8 Λ 7/0 ίϊ 2 2
Weitere Vorteile der Erfindung ergeben sich aus der nachstehenden Beschreibung.Further advantages of the invention emerge from the description below.
Die Erfindung ist grundsätzlich auf ein Verfahren zur Herstellung einer polymeren Ultrafiltrationsmembran gerichtet, die eine wirksame Menge eines mechanisch eingeschlossenen Enzyms enthält, indem man die Membran aus einer Lösung des Polymers ausfällt, die einen dispergierten Enzymzusatz enthält. Die auf diese ¥eise gebildete enzymhaltige Ultrafiltrationsmembran hat die Fähigkeit, eine Molekulartrennung zu bewirken und bevorzugt auf das Ultrafiltrat selektiv einzuwirken, wobei die eingeschlossenen biologisch aktiven Enzyme eine spezifische chemische Reaktion auslösen. Da das Enzym seinem Wesen nach ein Katalysator ist, wird es bei der Reaktion nicht zerstört und behält sane Aktivität über ausgedehnte Zeiträume, ist also stabil.The invention is basically directed to a method for producing a polymeric ultrafiltration membrane, which is an effective amount of a mechanically entrapped Contains enzyme by precipitating the membrane from a solution of the polymer that contains a dispersed enzyme additive. The enzyme-containing ultrafiltration membrane formed in this way has the ability to effect molecular separation and is preferably selective for the ultrafiltrate act, the trapped biologically active Enzymes trigger a specific chemical reaction. Since the enzyme is by nature a catalyst, will it is not destroyed in the reaction and retains its activity over extended periods of time, so it is stable.
Im besonderen wird eine polymere, anisotrope, mikroporöse Membran der in der USA-Patentschrift 3 615 024 vom 26. Okt. 1971 beschriebenen Art nach der dort beschriebenen Methode unter Zusatz des Enzyms zu der Polymerlösung vor der Ausfällung hergestellt. Wie in dieser Patentschrift beschrieben, wird eine Lösung eines Polymers in einem organischen Lösungsmittel gebildet und dann zu einem dünnen Film vergossen. Die eine Seite des Films wird bevorzugt mit einem Lösungsmittel in Berührung gebracht, das mit dem organischen Lösungsmittel weitgehend mischbar und ausreichend unverträglich mit dem Polymer ist, so daß eine rasche Aus-In particular, it becomes a polymeric, anisotropic, microporous Membrane of the type described in U.S. Patent 3,615,024 dated Oct. 26. 1971 described type according to the method described there with the addition of the enzyme to the polymer solution prior to precipitation. As described in this patent specification, a solution of a polymer is formed in an organic solvent and then into a thin Film shed. One side of the film is preferably brought into contact with a solvent which is compatible with the organic solvent is largely miscible and sufficiently incompatible with the polymer, so that a rapid
4 0 9 8 4 7/09224 0 9 8 4 7/0922
-dünn fällung der Polymembran erfolgt. Das Vei/ungsmittel v±tü mit der Membran in Kontakt gehalten, bis praktisch das ganze Lösungsmittel durch Verdünnungsmittel verdrängt worden ist. Die auf diese Weise hergestellte Membran, die gewöhnlich eine Dicke von mehr als etwa 0,05 n™ (0,002 Zoll) und weniger als etwa 1,25 mm (0,050 Zoll) hat, ist dadurch gekennzeichnet, daß angrenzend an die Filmoberfläche eine sehr dünne, relativ dichte Haut vorhanden ist, die eine Sperrschicht von etwa 0,1 bis 5»0 Mikron Dicke aus porösem Polymer darstellt, worin der mittlere Porendurchmesser im Millimikronbereich beispielsweise bei 1 bis 1000 Millimikron oder etwa 1/10 bis 1/1OO der Hautdicke liegt. Der Rest der Filmstruktur stellt eine selbsttragende Trägerschicht von grobporösem Polymer dar, die dem Strömungsmittel nur geringen hydraulischen Widerstand entgegensetzt. Gemäß der Erfindung wird das Enzym in fein verteilter Form und wirksamer Menge in die Polymerlösung eingeführt und darin z.Bo durch Vermischung gut dispergiert. Die enzymhaltige Polymerlösung wird dann, wie oben angegeben, zu einem Film vergossen. An Kontakt mit dem Lösungsmittel, das gewöhnlich aus Wasser, ggf. mit einem Zusatz von 1 bia 3 Ί» eines oberflächenaktiven Mittels, z.B. eines unter dem Namen Triton-X100 bekannten Polyäthoxyäthanols besteht, wird das Polymer ausgefällt und liefert in der vorstehend angegebenen Weise die anisotrope Membran, jedoch umschließt in diesem Fall die Membran das Enzym, insbesondere längs der Porenkanälβ. - Thin precipitation of the polymer membrane takes place. Until virtually all the solvent has been displaced by the diluent Vei / ungsmittel v t ± ü held with the membrane in contact. The membrane made in this manner, which usually has a thickness of greater than about 0.05 n ™ (0.002 inches) and less than about 1.25 mm (0.050 inches), is characterized by having a very thin thickness adjacent the film surface There is a relatively dense skin which is a barrier layer of about 0.1 to 5 »0 microns thick of porous polymer, wherein the mean pore diameter in the millimicron range is, for example, 1 to 1000 millimicrons or about 1/10 to 1/100 of the skin thickness . The remainder of the film structure is a self-supporting carrier layer made of coarse-pored polymer, which offers little hydraulic resistance to the fluid. According to the invention the enzyme is introduced in finely divided form and effective amount in the polymer solution and is dispersed by mixing for example o good. The enzyme-containing polymer solution is then cast into a film, as indicated above. On contact with the solvent, which usually consists of water, optionally with the addition of 1 bia 3 »of a surface-active agent, for example a polyethoxyethanol known under the name Triton-X100, the polymer is precipitated and provides the in the manner indicated above anisotropic membrane, but in this case the membrane encloses the enzyme, in particular along the pore channels.
409847/0922 . 6 -409847/0922. 6 -
Zur Durchführung der Erfindung geeignete Polymer-Lösungsmittelsysteme sind nachstehend aufgeführt.Polymer solvent systems suitable for practicing the invention are listed below.
Polymerpolymer
Acrilonitril-vinylchloridcopolymer (Dynel)Acrilonitrile-vinyl chloride copolymer (Dynel)
Lösungsmittelsolvent
Dimethylformamid Dimethylsulfoxid Methyl-pyrrolidon Dirnethylacetamid Dimethylformamid Dimethy1acetamid Methyl-pyrrolidon Dimethylpropionamid Dime thylfοrmamid Dimethylacetamid DimethylformamidDimethylformamide dimethyl sulfoxide Methyl pyrrolidone dirnethylacetamide Dimethylformamide dimethyl acetamide Methyl-pyrrolidone, dimethylpropionamide, dimethylformamide Dimethylacetamide dimethylformamide
Cyc1ohexanonCyclohexanone
Diese Polymer-Lösungsmittelsysteme sind keineswegs erschöpfend, denn das Schrifttum ist reich an anderen PoIymer-Lösungsmittelsystemen, und seine jeweilige Wahl ist in erster Linie eine Sache des Fachmannes. Xm allgemeinen liegt der Gehalt an Polymerfeststoffen in der Gießlösung bei etwaThese polymer-solvent systems are by no means exhaustive, since the literature is rich in other polymer-solvent systems and its particular choice is primarily a matter for the person skilled in the art. Generally, the polymer solids content of the casting solution will be about
409847/0922 - 7 -409847/0922 - 7 -
5 bis 4o Gew. -$ des Polymer-Lösungsmittelgemisches.5 to 40% by weight of the polymer-solvent mixture.
Enzyme, die sich zum Einschluß in Ultrafiltrationsmembranen eignen, sind beispielsweise Glucamylase für Stärke-Verzuckerung, Glucoseisomerase zur Umwandlung von Dextrose in Fructose, Invertase zur Sucroseumwandlung bei der Zuckerinversion und Urease zur Umwandlung von Harnstoffen Ammoniak,Enzymes that lead to inclusion in ultrafiltration membranes are suitable, for example, glucamylase for starch saccharification, glucose isomerase for converting dextrose into Fructose, invertase to convert sucrose during sugar inversion and urease to convert urea ammonia,
Abgesehen von Wasser, das normalerweise in allen System verwendet wird, in denen es brauchbar ist, sind organische Lösungsmittel, wie Methanol, Benzin, Fuselöl u.dgl. als Verdünnungsmittel in gewissen Sonderfällen verwendbar. Wo jedoch die Verwendung eines solchen Verdünnungsmittels angegeben ist, muß zunächst seine Verträglichkeit mit dem Enzym ermittelt werden.Aside from water, which is normally used in any system in which it is useful, organic solvents are such as methanol, gasoline, fusel oil and the like as diluents can be used in certain special cases. However, where indicated the use of such a diluent its compatibility with the enzyme must first be determined.
Das Gießen des Films und die Ausfällung der enzymhaltigen Membran erfolgen bei relativ mäßiger Temperatur, gewöhnlich im Bereich von etwa O bis 90 C.The casting of the film and the precipitation of the enzyme-containing Membrane take place at a relatively moderate temperature, usually in the range of about 0 to 90 C.
Die folgenden Beispiele dienen zur weiteren Erläuterung der Erfindung und ihrer Vorteile.The following examples serve to further explain the Invention and its advantages.
Eine Polymerlösung wird zubereitet, indem man 15 g eines ^O-eO-Acrylnitrilvinylchloridcopolymers (Dynel) mit 85 ml Dimethylformamid zu einer klaren Lösung vermischt. Die Enzymurease erhält man in Pulverform von einer TeilchengrößeA polymer solution is prepared by adding 15 g of a ^ O-eO-acrylonitrile vinyl chloride copolymer (Dynel) to 85 ml Dimethylformamide mixed to a clear solution. The enzyme urease is obtained in powder form of one particle size
U09847/0 922 _8_ U 09847/0 922 _ 8 _
von 0,1 ,XL» 1,0 g feinteiliges Enzym wird dann der Lösung zugesetzt und der Behälter fünf Minuten auf Walzen bewegt, um eine homogene Dispersion zu erhalten. Die enzymhaltige Mischung wird auf einem porösen Papierträger als dünner Film aufgetragen und dann das Papier mit dem darauf liegenden Film 20 Minuten in einem Wasserbad von einer Temperatur von 25 C eingetaucht, um die anisotrope Membran auszufällen« Die erhaltene Membran hat eine Dicke von etwa 0,125 mm (0,005 Zoll) und unterscheidet sich in ihrem Aussehen nicht von ehzymfreien anisotropen Membranen. Reehnungsmäß^ig sind 0,1215 S Urease mit je etwa 155 cm (2h Quadratzoll) Membran zu diesem Zeitpunkt vereinigt. Die Membran wird dann zu einer Scheibe von etwa 75 mm (3 Zoll) Durchmesser geschnitten und in einer Amicon Batch Zelle Nr. ^Ol montiert. Destilliertes Wasser wird hindurchgeleitet, um wässrige Lösungsmittel und freies Enzym zu eluieren.from 0.1 , XL » 1.0 g of finely divided enzyme is then added to the solution and the container is moved on rollers for five minutes in order to obtain a homogeneous dispersion. The enzyme-containing mixture is applied as a thin film to a porous paper support and then the paper with the film on it is immersed for 20 minutes in a water bath at a temperature of 25 C to precipitate the anisotropic membrane. The membrane obtained has a thickness of about 0.125 mm (0.005 inch) and is no different in appearance from enzyme-free anisotropic membranes. As a rule, 0.1215 S urease are combined with each approximately 155 cm (2h square inch) membrane at this point in time. The membrane is then cut into a disk about 75 mm (3 inches) in diameter and mounted in an Amicon batch cell # ^ oil. Distilled water is passed through to elute aqueous solvents and free enzyme.
Die Aktivität des unbeweglichen Enzyms wird durch Harnstoffhydrolyse untersucht. Der Harnstoff (HgNCONH2) wird durch die Membran mit Fließraten schwankend von etwa 19 bis I90 l/ 0,09 m /Tag 4eaiie»B-pe*-e^as>e-fee*-peJ?-iä.ay4 (5 bis 5° Gallonen/Quadratfuß/Tag) geleitet. Infolge der eintretenden katalytischen Reaktion verwandelt sich der Harnstoff in CO2 und NH„. Die Wirksamkeit des Enzyms wird durch die im Penaeat gelöste Ammoniakmai ge gemessen,und diese Ammoniakanalyse wird gegenüber der Nessler-Reagensreaktion am zulaufenden Material verglichen. Die Analyse erfolgt colometriech an einem elektronischen Bausch & £,omb Colorimeter Nr,2O,The activity of the immobile enzyme is examined by urea hydrolysis. The urea (HgNCONH 2 ) is passed through the membrane with flow rates fluctuating from about 19 to 190 l / 0.09 m / day 4e a ii e »B-pe * - e ^ as> e-fee * -peJ? -Iä. ay4 (5 to 5 gallons / square foot / day). As a result of the catalytic reaction that occurs, the urea is converted into CO 2 and NH 2. The effectiveness of the enzyme is measured by the amount of ammonia dissolved in the penaeate, and this ammonia analysis is compared with the Nessler reagent reaction on the incoming material. The analysis is carried out colometrically on an electronic Bausch & £, omb colorimeter No. 2O,
409847/0922409847/0922
Die bei mäßigen Fließraten erzielte Umwandlung ist umgekehrt proportional dem Durchfluß; beispielsweise beträgt sie k9 <$> bei einer Fließrate von etwa 19 1/0,09 m /Tag (5 Gallonen/Quadratfuß/Tag) und 32 # bei einer Fließrate von etwa 80 1/0,09 m /Tag (21 Gallonen/Quadratfuß/Tag). Bei höheren Fließratei ist die Umwandlung linear, was besagt, daß die begrenzenden Faktoren die Enzymkonzentration in Kontakt mit den Porenkanälen und die Kontaktzeiten sind. Bei niedrigen Fließraten ist die Umwandlung höher als vorauszuberechnen ist. Dies beruht auf dem zusätzlichen Mechanismus der Diffusion.The conversion achieved at moderate flow rates is inversely proportional to the flow; for example, it is k9 <$> at a flow rate of about 19 1 / 0.09 m / day (5 gallons / square foot / day) and 32 # at a flow rate of about 80 1 / 0.09 m / day (21 gallons / day) Square feet / day). At higher flow rates the conversion is linear, indicating that the limiting factors are the enzyme concentration in contact with the pore channels and the contact times. At low flow rates, the conversion is higher than can be calculated in advance. This is due to the additional mechanism of diffusion.
Eine gemäß Beispiel 1 hergestellte Ultrafiltrationsmembran mit immobilisiertem Enzym wird länger als 3 Monate bed. etwa + ^0C (40° F) aufbewahrt. Zu diesem Zeitpunkt wird die Enzymaktivität durch Harnstoffhydrolyse ermittelt. Nach dieser Zeitspanne ist keine Herabsetzung in der Enzymaktivität vorhanden. Hauptsächlich hat die Aktivität etwas zugenommen. Dies beruht anscheinend auf einer Stabilisierung oder Kristallisierung des Polymers, die bekanntlich die Eigenschaften des Membranträgers steigert, ohne die Membranhaut oder die Molekülarstruktur zu beeinträchtigen.An ultrafiltration membrane with immobilized enzyme produced according to Example 1 is used for more than 3 months. Stored at about + ^ 0 C (40 ° F). At this point the enzyme activity is determined by urea hydrolysis. After this period there is no decrease in enzyme activity. Mainly the activity has increased a bit. This is apparently based on a stabilization or crystallization of the polymer, which is known to increase the properties of the membrane support without impairing the membrane skin or the molecular structure.
Der Einschluß des Enzyms in der Ultrafiltrationsmembran hat gewisse Vorteile, die mit den vorbekannten Methoden von Enzymimmobilisierungen nicht erreichbar sind. Wenn z.B. früherThe inclusion of the enzyme in the ultrafiltration membrane has certain advantages with the previously known methods of enzyme immobilization are not reachable. If e.g. earlier
409847/0922 "409847/0922 "
Enzyme eingekapselt worden sind, bedeutete die Diffusion durch das Einkapselungsmittel eine kinetische Begrenzung für enzymatisch Umwandlungen„ Gemäß der Erfindung ist das Enzym längs der Porenkanäle lokalisiert, durch die Permeat leicht fließen kann, und deshalb sind beträchtlich höhere Reaktionsgeschwindigkeiten erzielbar. Außerdem ist hier das Enzym in einem Flüssigkeit-Peststoffseparator mobilisiert, und infolgedessen kann das Enzym nur mit dem Permeat reagieren. Da die Membran nach der Erfindung ein großes Porenvolumen hat und anisotropisch ist, sowie infolge der Natur des Transportmechanismus tritt ein sehr kleines Permeatvolumen während einer kurzen Zeitperiode mit einer hohen Enzymkonzentration in Kontakt. In Verbindung mit der kontinuierlichen Natur des Porenflusses, bei dem umgesetzte Produkte ständig mit Reaktionsmittel verdrängt werden, betrachtet sind die kinetischen Eigenschaften des Systems eindeutig gegenüber denjenigen verbessert, die mit vorbekannten eingekapselten Enzymsystemen erzielbar sind.Since enzymes had been encapsulated, diffusion through the encapsulant was a kinetic limitation for enzymatic conversions “According to the invention this is Enzyme localized along the pore channels through which permeate can easily flow and therefore are considerably higher Response speeds achievable. In addition, here the enzyme is mobilized in a liquid-pesticide separator, and as a result the enzyme can only react with the permeate. Since the membrane according to the invention is a large Has pore volume and is anisotropic, and due to the nature of the transport mechanism, there is a very small volume of permeate in contact with a high concentration of enzyme for a short period of time. In conjunction with the continuous The nature of the pore flow, in which the converted products are constantly displaced by the reactant, is considered the kinetic properties of the system are clearly improved compared to those with previously known encapsulated enzyme systems are achievable.
- 11- 11
409847/.0 922409847 / .0 922
Claims (1)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US35817073A | 1973-05-07 | 1973-05-07 |
Publications (1)
Publication Number | Publication Date |
---|---|
DE2421650A1 true DE2421650A1 (en) | 1974-11-21 |
Family
ID=23408567
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE2421650A Ceased DE2421650A1 (en) | 1973-05-07 | 1974-05-04 | IMMOBILIZATION OF ENZYMES IN ULTRAFILTRATION MEMBRANES |
Country Status (4)
Country | Link |
---|---|
JP (2) | JPS5844401B2 (en) |
DE (1) | DE2421650A1 (en) |
FR (1) | FR2228785B3 (en) |
GB (1) | GB1474594A (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5548392A (en) | 1978-02-17 | 1980-04-07 | Toyo Jozo Co Ltd | Novel immobilizing material combined with biologically active substance, its preparation, device comprising it, method, and preparation of support |
IT1207172B (en) * | 1979-02-15 | 1989-05-17 | Anic Spa | PROCESS FOR THE PREPARATION OF GLOBAL MICROPOROUS BODIES ONE OR MORE ACTIVE AGENTS. |
JPH0646947B2 (en) * | 1984-12-17 | 1994-06-22 | 祥一 清水 | Biochemical reaction method |
JPS63207395A (en) * | 1987-02-20 | 1988-08-26 | Natl Food Res Inst | Production of inverted sugar from molasses |
JPH02150281A (en) * | 1988-11-30 | 1990-06-08 | Central Glass Co Ltd | Enzyme-containing membrane and production thereof |
FR2667874B1 (en) * | 1990-10-16 | 1992-12-31 | Rhone Alpes Futur Fondation | BIO-CATALYSIS REACTOR, AND CORRESPONDING TREATMENT METHOD, PARTICULARLY APPLICABLE TO MALOLACTIC WINE TRANSFORMATION. |
WO2018230330A1 (en) | 2017-06-15 | 2018-12-20 | 株式会社カネカ | Porous membrane for water treatment use |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3615024A (en) * | 1968-08-26 | 1971-10-26 | Amicon Corp | High flow membrane |
-
1974
- 1974-05-02 JP JP49049647A patent/JPS5844401B2/en not_active Expired
- 1974-05-04 DE DE2421650A patent/DE2421650A1/en not_active Ceased
- 1974-05-07 FR FR7415787A patent/FR2228785B3/fr not_active Expired
- 1974-05-07 GB GB2008674A patent/GB1474594A/en not_active Expired
-
1982
- 1982-10-01 JP JP57173069A patent/JPS58187190A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
FR2228785A1 (en) | 1974-12-06 |
JPS5844401B2 (en) | 1983-10-03 |
FR2228785B3 (en) | 1977-03-11 |
JPS58187190A (en) | 1983-11-01 |
GB1474594A (en) | 1977-05-25 |
JPS5014580A (en) | 1975-02-15 |
JPS6253151B2 (en) | 1987-11-09 |
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