DE2333834A1 - CARRIER MATERIAL FOR PROTEINS - Google Patents

CARRIER MATERIAL FOR PROTEINS

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Publication number
DE2333834A1
DE2333834A1 DE19732333834 DE2333834A DE2333834A1 DE 2333834 A1 DE2333834 A1 DE 2333834A1 DE 19732333834 DE19732333834 DE 19732333834 DE 2333834 A DE2333834 A DE 2333834A DE 2333834 A1 DE2333834 A1 DE 2333834A1
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Germany
Prior art keywords
water
proteins
carrier material
carrier
protein
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Pending
Application number
DE19732333834
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German (de)
Inventor
Victor Dr Krasnobajew
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Givaudan SA
Original Assignee
L Givaudan and Co SA
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Filing date
Publication date
Application filed by L Givaudan and Co SA filed Critical L Givaudan and Co SA
Publication of DE2333834A1 publication Critical patent/DE2333834A1/en
Pending legal-status Critical Current

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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
    • C12N11/08—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer
    • C12N11/089—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C12N11/096—Polyesters; Polyamides
    • 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
    • C12N11/14—Enzymes or microbial cells immobilised on or in an inorganic carrier
    • 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
    • C12N11/08—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer
    • C12N11/089—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C12N11/10—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a carbohydrate
    • C12N11/12—Cellulose or derivatives thereof

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Zoology (AREA)
  • Engineering & Computer Science (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Organic Chemistry (AREA)
  • Genetics & Genomics (AREA)
  • Wood Science & Technology (AREA)
  • Biotechnology (AREA)
  • Microbiology (AREA)
  • Biochemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Molecular Biology (AREA)
  • Inorganic Chemistry (AREA)
  • Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
  • Peptides Or Proteins (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)

Description

L. Givaudan & Cie Societe Anonyme, Vernier-Geneve (Schweiz)L. Givaudan & Cie Societe Anonyme, Vernier-Geneve (Switzerland) Trägermaterial für ProteineCarrier material for proteins

Die Erfindung betrifft ein Trägermaterial für Proteine sowie wasserunlösliche Proteinpräparate und ein Verfahren zu deren Herstellung.The invention relates to a carrier material for proteins and water-insoluble protein preparations and a method for their manufacture.

Bs wurde gefunden, dass man Träger zur Bereitung wasserunlöslicher Protein-, insbesondere Enzympräparate,dadurch erhalten kann, dass man ein wasserunlösliches Polymer oder, vorzugsweise, ein wasserunlösliches anorganisches, reaktive Säuerst of funkt ionen enthaltendes Material mit einem aromatischen Diamin behandelt und das Reaktionsprodukt diazotiert. Durch diesen Prozess werden die Trägerpartikel mit einer unablösbaren Ochicht, die aktive Diazoniumgruppen enthält, versehen. Die so erhaltenen Träger liefern bei der Behandlung mit Proteinlösungen wasserunlösliche Proteinpräparate.It has been found that carriers can be used to prepare water-insoluble Protein preparations, in particular enzyme preparations, can be obtained by mixing a water-insoluble polymer or, preferably, a water-insoluble inorganic, reactive acid-containing material with an aromatic Treated diamine and diazotized the reaction product. Through this process, the carrier particles become indelible Ochicht, which contains active diazonium groups, provided. The so The carriers obtained give water-insoluble protein preparations on treatment with protein solutions.

309885/1268309885/1268

Beispiele vcn anorganischen Materialien, die für die Herstellung des erfindungsgemässen Trägers in Betracht kommen sind Silikate und silikathaltige Materialien, z.B. Sand, Steine, Silicagel oder Kieselgur; Bentonit, Vollastonit oder Glas; aber auch Metalloxide wie Aluminiumoxid und Hydroxylapatit.Examples of inorganic materials used for the Preparation of the carrier according to the invention come into consideration are silicates and materials containing silicate, e.g. sand, stones, silica gel or kieselguhr; Bentonite, solid astonite or Glass; but also metal oxides such as aluminum oxide and hydroxyapatite.

Als Beispiele geeigneter Polymerer seien Polyamide genannt. Auch Cellulose, insbesondere Baumwolle, z.B. in Form von Watte ist geeignet. Examples of suitable polymers are polyamides. Cellulose, in particular cotton, e.g. in the form of wadding, is also suitable.

Beispiele von aromatischen Diaminen sind 1,2-Phenylen— diamin, 4,4'-Diamino-diphenylinethant Benzidin, und 4-,4'-DiSnJiHO-stilben. Grundsätzlich ist für die Herstellung der erfindungsgemässen Träger jedes aromatische Diamin geeignet.Examples of aromatic diamines are 1,2-phenylenediamine, 4,4'-diamino-diphenylinethane t benzidine, and 4-, 4'-DiSnJiHO-stilbene. In principle, any aromatic diamine is suitable for the production of the carriers according to the invention.

Zur Herstellung des erfindungsgemässen Trägenaaterials werden die als Ausgangsstoff verwendeten Partikel zunächst mit einer Lösung des Amins, zweckmässig unter leichtem Erwärmen, behandelt. Danach diazotiert man die so erhaltenen Produkte in an sich bekannter Weise, z.B. mit Nitrit und Säure, wie Salz— oder Essigsäure, zweckmässig bei Temperaturen zwischen 0° und Zimmertemperatur.For the production of the carrier material according to the invention the particles used as the starting material are first treated with a solution of the amine, expediently with gentle heating, treated. The products thus obtained are then diazotized in a manner known per se, e.g. with nitrite and acid, such as salt. or acetic acid, expediently at temperatures between 0 ° and room temperature.

Zur Kupplung des Proteins an den Träger behandelt man den letzteren mit einer Lösung des Proteins, wobei man das Verhältnis Protein:Träger zweckmässig auf etwa 1-50 Milligramm pro Gramm bemisst. Die Behandlung wird zweckmässig in einer Pufferlösung, z.B. in Phosphatpuffer, bei pH 5-7,8, vorzugsweise bei pH 7,5 vorgenommen.To couple the protein to the carrier, the latter is treated with a solution of the protein, the ratio of protein: carrier being expediently measured at about 1-50 milligrams per gram. The treatment is expediently carried out in a buffer solution, for example in phosphate buffer, at pH 5-7.8, preferably at pH 7.5.

Als Proteine kommen für die Kupplung an den erfindungsgemässen Träger Antigene, Antikörper, Inhibitoren, wie Tryptininhibitoren und insbesondere Enzyme in Betracht. Beispiele von Enzymen, von denen erfindungsgemäss unlösliche Enzympräparate hergestellt werden können, sind Naringinase, Hesperidinase, ß-Galactosidase, ß-Glucosidase, Trypsin, Bromalin, Ficin, Papain, oc-Amylase, Amyloglucosidaae und Urease.The proteins used for coupling to the carrier according to the invention are antigens, antibodies, inhibitors, such as Tryptin inhibitors and especially enzymes into consideration. Examples of enzymes, of which according to the invention insoluble Enzyme preparations that can be made are naringinase, hesperidinase, ß-galactosidase, ß-glucosidase, trypsin, bromaline, Ficin, papain, oc-amylase, amyloglucosidaae and urease.

309885/1268309885/1268

Die nachstehenden Beispiele erläutern die Erfindung:The following examples illustrate the invention:

Beispiel 1example 1

1 g Silicagel (zur Chromatographie) wurde zu einer Lösung von 200 mg 4,4'-Diaminodiphenylmethan in 10 ml trockenem Benzol gegeben. Das Gemisch wurde 5 Minuten unter gelegentlichem Schütteln auf dem Wasserbad (80°) erwärmt, sodann abgenutscht, bis alles Benzol entfernt war. Der Rückstand wurde in 20 ml eiskaltes Wasser gegeben, unter Rühren mit 300 mg Natriumnitrit und sodann mit verdünnter Salzsäure (20 Vol-$) versetzt, bis das pH 1-2 betrug. Danach wurde 10 Minuten bei 0° gerührt, das pH durch Zusatz von 1 N Natronlauge auf pH 5 eingestellt und der Ueberstand abdekantiert. Der Rückstand wurde mehrmals mit eiskaltem Wasser, das durch Zusatz von Salzsäure auf pH 4-5 gebracht worden war, gewaschen, bis der Ueberstand beim Dekantieren farblos war. Die so erhaltenen Partikel wurden unmittelbar für die Enzymkupplung verwendet. Tüne· Lagerung in Pliosphatpuffer pH 6,5 bei 4° während 24 Stunden zeigte keinen merklichen Verlust an Kupplungskapazität.1 g of silica gel (for chromatography) was added to a solution of 200 mg of 4,4'-diaminodiphenylmethane in 10 ml of dry benzene. The mixture was heated on the water bath (80 °) for 5 minutes with occasional shaking, then suction filtered until all of the benzene was removed. The residue was poured into 20 ml of ice-cold water, 300 mg of sodium nitrite and then dilute hydrochloric acid (20% by volume) were added with stirring until the pH was 1-2. The mixture was then stirred at 0 ° for 10 minutes, the pH was adjusted to 5 by adding 1N sodium hydroxide solution and the supernatant was decanted off. The residue was washed several times with ice-cold water, which had been brought to pH 4-5 by adding hydrochloric acid, until the supernatant was colorless on decanting. The particles obtained in this way were used directly for the enzyme coupling. T TSOW · Storage in Pliosphatpuffer pH 6.5 at 4 ° for 24 hours showed no significant loss of coupling capacitance.

In der gleichen Weise wurden Trägermaterialien auf der Basis von porösem Glas (Partikelgrösse 40-200 mesh US Standard, Porengrösse 10-200 nir) Aluminiumoxid, Cellulose und Polyamid hergestellt .In the same way, support materials based on porous glass (particle size 40-200 mesh US standard, Pore size 10-200 nir) made of aluminum oxide, cellulose and polyamide .

Beispiel 2Example 2

1 g des gemäss Beispiel 1 hergestellten Trägermaterials wurden zu 25 ml einer eiskalten Enzymlösung (-siehe Tabelle) in 0,05 M Phosphatpuffer pH 6,5-7,8 (Proteingehalt 1-8 mg), gegeben und bei 4° 30 Minuten bis 20 Stunden leicht geschüttelt. Danach wurde filtriert, die Partikel wurden dreimal mit j>e 50 ml 1 H Kaliumchloridlosung gewaschen, in 20 ml 0,05 M Citrat- oder Phosphatpuffer pH 6,5 suspendiert und bei 4° aufbewahrt. Die1 g of the carrier material prepared according to Example 1 were added to 25 ml of an ice-cold enzyme solution (see table) in 0.05 M phosphate buffer pH 6.5-7.8 (protein content 1-8 mg), given and gently shaken at 4 ° for 30 minutes to 20 hours. Thereafter was filtered, the particles were washed three times with 50 ml of 1 H Washed potassium chloride solution in 20 ml of 0.05 M citrate or Phosphate buffer pH 6.5 suspended and stored at 4 °. the

309885/1263309885/1263

Aktivität der so erhaltenen Enzympräparate ist der nachstehenden Tabelle zu entnehmen:Activity of the enzyme preparations thus obtained is as follows See table:

309885/1263309885/1263

TabelleTabel

O CDO CD 0000 co tnco tn

KJ CD 00KJ CD 00

Trägerbasis: poröses GlasSupport base: porous glass Enzymenzyme Eingesetzte
Enzymmenge
[mg Protein] [Einheiten]Deployed
Amount of enzyme
[mg protein] [units] 3,4
8
192
384
10,4
1,2
5,5
1,1
8,83.4
8th
192
384
10.4
1.2
5.5
1.1
8.8 Aktivität
pro g Träger
Einheitenactivity
per g of carrier
units 1,8
9,4
2,1
0,44
0,35
1,761.8
9.4
2.1
0.44
0.35
1.76 SubstratSubstrate Naringinase
Amyloglucosidase
Hesperidinase
Ficin
Trypsin
Bromalin
ß-GlucosidaseNaringinase
Amyloglucosidase
Hesperidinase
Ficin
Trypsin
Bromaline
β-glucosidase 1
2,3
4
8
2
2
2,5
2
21
2.3
4th
8th
2
2
2.5
2
2 1,9
2,4
50
90
4,6
0,38
1,9
0,32
2,31.9
2.4
50
90
4.6
0.38
1.9
0.32
2.3 Naringin
Stärke
Hesperidin-dihydrochalcon
Casein
N-Benzoy1-dl-arginin -4-nitro-anilid
Casein
N-Nitrophenyl-glyqopyranosidNaringin
strength
Hesperidin dihydrochalcone
Casein
N-Benzoy1-dl-arginine -4-nitro-anilide
Casein
N-nitrophenyl glyqopyranoside Trägerbasis: SilicagelCarrier base: silica gel wie oben
OO
OO
OO
CO
OOas above
OO
OO
OO
CO
OO Naringinase
Amyloglucosidase
Trypsin
Ficin
Bromalin
ß-CHucosidaseNaringinase
Amyloglucosidase
Trypsin
Ficin
Bromaline
β-CHucosidase 3
2
2,5
2
2
23
2
2.5
2
2
2 10
90
5,5
1,2
1,1
8,810
90
5.5
1.2
1.1
8.8

in ι in ι

Claims (1)

PatentansprücheClaims \l\ Verfahren zur Herstellung eines Trägermaterials für Proteine, dadurch gekennzeichnet, dass man ein wasserunlösliches Polymer oder ein wasserunlösliches anorganisches, reaktive Sauerstoffunktionen enthaltendes Material r;;it einem aromatischen Diamin behandelt und das Reaktionsprodukt diazotiert. A method for producing a carrier material for proteins, characterized in that a water-insoluble polymer or a water-insoluble inorganic material containing reactive oxygen functions is treated with an aromatic diamine and the reaction product is diazotized. 2. Verfahren nach Patentanspruch 1, dadurch gekennzeichnet, dass man als Ausgangsmaterial ein Silikat verwendet.2. The method according to claim 1, characterized in that a silicate is used as the starting material. 3· Verfahren nach Patentanspruch 2, dadurch gekennzeichnet, dass man Silicagel oder poröses Glaspulver verv/endet,3 · Method according to claim 2, characterized in that that one uses silica gel or porous glass powder, 4. Verfahren nach den PatentansprUcnen 1-?, dadurch gekennzeichnet, dass man als aromatisches Diarr.in 1,3-Phenylendiamin, 4,4'-Diamino-diphenylmethan, Benzidin oder 4,4'-Diaminostilben verwendet.4. The method according to claims 1- ?, characterized in that that the aromatic diarrhea in 1,3-phenylenediamine, 4,4'-diamino-diphenylmethane, benzidine or 4,4'-diaminostilbene used. ^. Verfahren zur Herstellung eines Proteinr-ränarates, aadurch gekennzeichnet, dass man einen gerräss der. Patentansprücnen 1-4 erhaltenen Träger mit einer Proteinlösung oehandelt. ^. Process for the production of a protein ränarates, acharacterized in that one gears the. Claims 1-4 obtained carrier with a protein solution treated. 309885/ 1 268309885/1 268 ORIGINAL INSPECTEDORIGINAL INSPECTED -1T-- 1 T- 233383A233383A 6. Trägermaterial flir Proteine, bestehend aus einem wasserunlöslichen Polymer oder einem anorganischen, reaktive Sauerstoffunktionen enthaltendem Material, auf dem eine Schicht von diazotierten! Diamin aufgebracht ist.6. Carrier material for proteins, consisting of a water-insoluble polymer or an inorganic material containing reactive oxygen functions, on which a Layer of diazotized! Diamine is applied. 7. Trägermaterial gemäss Anspruch 6, dadurch gekennzeichnet, dass es aus einem Silikat aufgebaut ist.7. Carrier material according to claim 6, characterized in that that it is composed of a silicate. ■/ 309885/1263■ / 309885/1263
DE19732333834 1972-07-12 1973-07-03 CARRIER MATERIAL FOR PROTEINS Pending DE2333834A1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH1042272A CH579533A5 (en) 1972-07-12 1972-07-12

Publications (1)

Publication Number Publication Date
DE2333834A1 true DE2333834A1 (en) 1974-01-31

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ID=4363063

Family Applications (1)

Application Number Title Priority Date Filing Date
DE19732333834 Pending DE2333834A1 (en) 1972-07-12 1973-07-03 CARRIER MATERIAL FOR PROTEINS

Country Status (14)

Country Link
JP (1) JPS4959697A (en)
AT (1) AT326813B (en)
AU (1) AU5578973A (en)
BE (1) BE802236A (en)
CH (1) CH579533A5 (en)
DE (1) DE2333834A1 (en)
FR (1) FR2192113B1 (en)
GB (1) GB1444395A (en)
HU (2) HU167605B (en)
IL (1) IL42259A (en)
IT (1) IT990560B (en)
NL (1) NL7309663A (en)
SE (1) SE7309771L (en)
ZA (1) ZA733252B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH579098A5 (en) * 1973-02-22 1976-08-31 Givaudan & Cie Sa
FR2417514A1 (en) * 1978-02-16 1979-09-14 Rhone Poulenc Ind Enzymes immobilised on inorganic supports - by attaching to bridging molecule bonded to support by an ester linkage
DE2963866D1 (en) * 1978-02-16 1982-11-25 Rhone Poulenc Spec Chim Support-enzyme complexes and method for preparing them
DE3311889A1 (en) * 1983-03-31 1984-10-11 Byk-Mallinckrodt Chemische Produkte Gmbh, 6057 Dietzenbach METHOD FOR IRREVERSIBLE BINDING OF PROTEIN TO POLYSTYROL SURFACES WITH THE PRESERVATION OF BIOLOGICAL ACTIVITY, POLYSTYROL SURFACES OBTAINED AND THEIR USE
IL83451A (en) * 1987-08-06 1991-06-10 Univ Ramot Stabilized water soluble enzymes and a method for their preparation

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Publication number Publication date
IL42259A0 (en) 1973-07-30
BE802236A (en) 1974-01-14
ZA733252B (en) 1974-03-27
ATA420673A (en) 1975-03-15
JPS4959697A (en) 1974-06-10
HU167605B (en) 1975-11-28
NL7309663A (en) 1974-01-15
AU5578973A (en) 1974-11-21
AT326813B (en) 1975-12-29
IT990560B (en) 1975-07-10
FR2192113A1 (en) 1974-02-08
HU168032B (en) 1976-02-28
CH579533A5 (en) 1976-09-15
IL42259A (en) 1976-09-30
FR2192113B1 (en) 1976-11-12
GB1444395A (en) 1976-07-28
SE7309771L (en) 1974-01-14

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