IE49394B1 - Microporous polymer bodies having agents occluded therein - Google Patents
Microporous polymer bodies having agents occluded thereinInfo
- Publication number
- IE49394B1 IE49394B1 IE282/80A IE28280A IE49394B1 IE 49394 B1 IE49394 B1 IE 49394B1 IE 282/80 A IE282/80 A IE 282/80A IE 28280 A IE28280 A IE 28280A IE 49394 B1 IE49394 B1 IE 49394B1
- Authority
- IE
- Ireland
- Prior art keywords
- process according
- polymeric matrix
- agents
- solution
- mixture
- Prior art date
Links
Classifications
-
- 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
Abstract
To form microporous bodies having occluded in their interior active agents such as enzymes, a polymer solution is mixed with the active agent dissolved or dispersed in a liquid phase compatible and miscible with the solvent used for dissolving the polymer. The final form of the microporous bodies can be imparted by extrusion, dripping or otherwise.
Description
This invention relates to a process for the preparation of microporous bodies wherein one or more agents, more particularly those agents which display a biological activity, are occluded.
It is known from Italian Patent Specification No. 836,482 { Patent
Specification No. 33536 ) that it is possible to immobilize enzymes and preparations containing them in the interior of filamentary polymeric structures. The process is carried out by preparing an emulsion of an aqueous solution of the enzyme and of a solution of the polymer dissolved in a solvent which is immiscible with water, the emulsion being subsequently extruded through a spinneret into a coagulation bath to produce a filament which occludes, in its interior, the enzymatic solution present in the emulsion. Thus, there are obtained biological catalysts which have a high activity. However, their practical use is often limited by the shape imparted thereto by the above process and by the comparative intricacy of the process.
According to the present invention, there is provided a process for the
- 2 49384 preparation of a microporous body wherein one or more agents selected from biologically active agents, sequestering agents and dyestuffs are occluded, which process comprises (a) forming a solution of a polymeric matrix in an organic solvent; (b) forming a dispersion or solution of said agent or agents in a medium compatible therewith and miscible with the organic solvent for the polymeric matrix; (c) if desired, adding to the dispersion or solution obtained by step (b), an additive selected from (i) at least one polymer which has a molecular weight different from that of the polymeric matrix and which is not soluble in the solvent for the polymeric matrix and (ii) at least one polyfunctional reagent selected from aliphatic aldehydes, isocyanates and thioisocyanates; (d) mixing the solution obtained by step (a) with the dispersion or solution obtained by step (b) with or without the additive added in step (c); and (e) carrying out a shaping stage by (i) coagulating the mixture in a medium which is a non-solvent for the polymeric matrix, or by (ii) extrusion of the mixture in a dry condition, or by (iii) ejecting the mixture from a pressurised enclosure.
This invention relates to an improved process for the preparation of microporous bodies which occlude the above agents, especially those which display a biological activity, and whose practical use, i.e. their use in commercial reactions in which such agents are involved, is by no means restricted. Thus, there are obtained, for example, biological catalysts with a high efficiency, the exploitation of which is not restricted by practical arrangements they must undergo, by virtue of the different shapes in which they can be obtained.
The biologically active agents which can be occluded according to the present invention, include enzymes, enzymic cells, antigens, antibodies, antisera, hormones, and coenzymes which are bound to macromolecular matrices.
49384
It is to be added that it is also possible to occlude once more bodies in which agents have already occluded, either by the process of this invention or otherwise. It is also possible to occlude other substances deriving from the physical or chemical union of the agents with appropriate substrates.
Thus, for example, it is possible to give the agent a high degree of protection. The agent can be occluded as such, or after having been mixed With appropriate inert fillers. The process of this invention has proven to be especially efficient for the preparation of biological catalysts, particularly in view of the possibility of obtaining such catalysts in a great variety of shapes. It is thus possible to obtain fibres, fibrids, cylindrical bodies or various sizes, ellipsoids, spherical bodies and powders of various grit sizes, since the shape depends upon the steps used in the shaping treatment.
As indicated above, one way in which the latter treatment is performed by causing the mixture of the solution of the polymeric matrix and the agent, or of its dispersion, to coagulate in a medium which is a non-solvent for the polymeric matrix. The coagulation can take place, for example, by dripping the mixture into the medium (whereby there are obtained, for example, bodies having a spherical or spheroidal shape) or by causing the mixture to flow directly into the interior of the medium (whereby fibres, for example, are obtained).
As indicated above, an alternative shaping procedure is the dry extrusion with evaporation of the solvent of the mixture. Thus, there is obtained a continuous filament which can be severed to obtain cylindrical bodies with various cross-sectional outlines.
As indicated above, another shaping procedure is to eject the mixture from a pressurised enclose, with or without the aid of a propellent, so that fibrids or powders of various grit sizes are formed.
- 4 49384
The polymeric matrices which can be used according to the method of this invention include cellulose polymers; esterified and etherified cellulose polymers; polyamides; and polymers and copolymers of acrylonitrile, butadiene, isoprene, acrylates, methacrylates, vinyl butyrate or other vinyl esters, vinyl chloride, vinylidene chloride, vinylidene chloride, styrene or y -methyl glutamate. Cellulose esters have proven to be especially suitable for the purposes of the present invention.
The media in which the active agents are dissolved or dispersed include water; alcohols (e.g. methanol, ethanol, n-propanol, n-butanol, t-butanol, ethylene glycol and glycerol); ketones (e.g. acetone and methylethylketone); ethers (e.g. dioxan, tetrahydrofuran and ethoxyethanol); esters (e.g. ethyl and methyl acetates, n-propyl acetate and ethyl formate); acids (e.g. acetic acid, propionic acid and formic acid); pyridine; acetonitrile; cyclohexane; and dimethylformamide.
The solvents for the polymeric matrix can be selected from a wide range of compounds, depending upon the nature of the polymeric matrix, and include acetone, methyl isobutyl ketone, cyclohexanone and other ketones; methyl acetate, ethyl lactate and other esters; ethylene glycol monoacetate monomethyl ether; ethylene glycol monomethyl ether; methylene chloride; propylene chloride; tetrachloroethanes; nitromethane; chlorophenols; m-cresol; acetic acid; formic acid; dimethylformamide; dimethylsulphoxide; alcohols (e.g. ethanol); dioxan; hydrocarbons (e.g. benzene and toluene); pyridine; chloroform; mixtures of ethanol and water; mixtures of ethanol and carbon tetrachloride; and mixtures of Isopropanol and methylethylketone.
The additives mentioned above have the task of aggregating or cross-linking the active agent during admixture of the latter with the polymeric matrix. The additives which can be used include (a) polymers with different molecular
- 5 43394 weight and which are not soluble in the solvent for the polymeric matrix, for example polyamines (such as polyethyleneimine, cationic polyacrylamides and anionic polyacrylamides), polyamino acids (such as polyisines), sulphonated polystyrene, polycarboxylic acids, polyvinyl alcohols and polyvinyl5 pyrolidone; and (b) polyfunctional reagents such a aliphatic aldehydes, isocyanates and thioisocyanates.
The invention will now be illustrated by the following Examples. In the Examples, the cellulose acetate used was obtained from Fluka, the acetone from Carlo Erba, the polyethyleneimine and the polyethyleneimine hydrochloride from
Polysciences Inc., the penicillina G from Squibb, the glutaraldehyde from Merck, the glucose!somerase powder from Godo Shusei, and the invertase from B.D.H.
EXAMPLE 1.
This Example describes the preparation of spherules of beta-galaceto15 oxidase obtained by occluding Saccharomyces lactis cells.
A 10% by weight solution of cellulose acetate in acetone was prepared, and, to 375 grams of this polymeric solution, there were added, with stirring,
154 g of cellular paste (35.8 g dry weight) from 2 litres of Saccharomyces lactis fermentation broth.
The cellular dispersion thus obtained was introduced into a steel container, and was extruded through a capillary tube having a diameter of 0.4 mm, by the pressure of nitrogen. The thin extruded filament, by being allowed to fall for a distance of about 20 centimetres, was converted into a rosary of beads which, upon dropping into a water bath, coagulated to form spherules.
There were collected about 800 g of moist spherules, which, when dried in an
- 6 49384 air stream, weighed 73 g in total. One gram of these spherules was incubated at 25“C with 200 ml of a 4.75% by weight solution of anhydrous lactose in a 0.1 molar phosphate buffer having a pH of 7, which solution contained 2 millimol of MgS04.7H20 and 1 millimol of EDTA, After a two5 hour reaction, 80% of the lactose had been converted into glucose and galactose, as shown by the analysis of glucose performed by the glucose test (Boehringer).
The hydrolysis of lactose with these spherules was repeated for 20 consecutive times without any noticeable loss of activity.
EXAMPLE 2.
This Example describes the preparation of spherules of penicillin-acylase obtained by occluding Escherichia coli cells previously treated with polyethyleneimine.
Escherichia coli cells (20 g dry weight) containing 10® units were slurried in
875 g of water and treated for 10 minutes with stirring with 25 g of a 3,3% by weight solution of polyethyleneimine. The formation of cell aggregates took place. These aggregates readily settled.
The cellular paste was then reslurried in a small volume of water (overall weight 127 g) and vigorously stirred with 157 g of a 10% by weight solution
2o of cellulose acetate in acetone. By the procedure described in Example 1, there were prepared 35 g (dry weight) of spherules. A portion of these spherules (5 g) was incubated at 37°C in 400 ml of a 6% by weight solution of penicillina G in a 0.02 molar phosphate buffer having a pH of 8. The initial activity was as great as 60,000 units (micromol an hour of hydrolysed penicillin G), and total hydrolysis was achieved within about 4 hours.
The same spherules,when used repeatedly for 20 consecutive hydrolyses, retained 60% of their initial activity.
- 7 49394
EXAMPLE 3.
This Example describes the preparation of spherules of penicillin-acylase obtained by occluding Escherichia coli cells previously treated with polyethyleneimine and glutaraldehyde.
Escherichia coli cells (20 g dry weight) containing 10® units were slurried in 400 g of water and stirred for 10 minutes with 25 g of a 3.3% by weight solution of polyethyleneimine and 5 g of a 25% by weight solution of glutaraldehyde.
The cells which collected upon settling were vigorously stirred with 157 g of a 10% by weight solution of cellulose acetate in acetone.
Preparation of spherules was performed by the procedure described in the previous Examples. There were obtained 40 g of dry spherules, 5 g of which were used for checking the activity under the conditions of Example 2. The activity was 50,000 units, and the hydrolysis was completed in just over 4 hours. In contrast to the spherules prepared without glutaraldehyde, the spherules of this Example retain their activity unaltered relative to the initial activity.
EXAMPLE 4.
This Example describes the preparation of spherules of glucose-isomerase obtained by occluding Arthrobacter sp. cells previously treated with polyacrylamide (Prodefloc A/15).
To 10 litres of a broth culture of Arthrobacter sp. cells containing glucoseisomerase enzyme, there were added, on completion of the fermentation, 500 g of a 0.3% by weight solution of Prodefloc A/1S. The cellular slurry was stirred for 20 minutes, whereafter the cells settled. The cellular paste (150 g dry weight) was collected and reslurried with water until an overall
- 8 48384 weight of 600 g was attained, and then admixed vigorously with 1,500 g of a 10% by weight solution of cellulose acetate in acetone. By the procedure disclosed in the previous Examples, spherules were prepared. One gram of these spherules was incubated at 60°C in 100 ml of a 50% (weight/weight) .3 _4 solution of glucose containing 5 x 10 mol of MgSO^HgO, 10 mol of CoCl2 and 0.1 mol of Na2S03, and having a pH of 7. By polarimetric measurements, the activity was determined as 100 international units (micromol of fructose produced in one minute) with a yield (unfolded activity/occluded activity) of 56% by weight. These spherules, used continuously for 20 consecutive days, did not lose their activity.
EXAMPLE 5.
This Example describes the preparation of spherules of glucose-isomerase obtained by occluding the enzyme in solution upon treatment with polyethyleneimine and glutaraldehyde.
An enzyme solution was prepared by dissolving 2 g of glucose-isomerase powder in 8 g of water. To this solution, there were added, with stirring, g of a 3.3% solution of polyethyleneimine and 4 g of a 2.5% solution of glutaraldehyde. This enzymic preparation was admixed with 100 g of a 10% by weight solution of cellulose acetate in acetone at room temperature. By the procedure described in the previous Examples, spherules were prepared.
The weight of the spherules, upon drying in air, was 12 g, A portion of these spherules (2 g) was incubated at 60°C with 100 ml of a 50% (weight/weight) solution of glucose containing 5 x 10 mol of MgS04.7H2Q,10 mol of CoCl2 and 0.1 mol of Na2SO3 and having a pH of 7, for determining the activity.
This activity was 500 international units, and the yield was 30%-40% by weight.
EXAMPLE 6.
This Example describes the preparation of cylindrical bodies of cellulose acetate occluding polyethyleneimine as a sequestering agent.
g of cellulose acetate were dissolved 1n 85 g of acetone (pure reagent).
To the polymeric solution, there were added, slowly and with stirring, g of a 33% (weight/weight) aqueous solution polyethyleneimine hydrochloride and 5 g of a 1% by weight solution of glutaraldehyde. The mixture was transferred to a steel cylinder having connected thereto, at the top, a nitrogen bottle, and, at the bottom, a spinneret immersed in a water bath.
By nitrogen pressure, the mixture was extruded from the spinneret, The mixture coagulated so that a continuous filament was obtained. This filament was severed by a cutting device in samples 1 - 2 cm long. One gram of these cylindrical bodies was contacted for 4 hours with a cupric solution having a content of 18.3 ppm, obtained by dissolving CuS04.5H20 in distilled water.
By the use of an atomic-absorption spectrophotometer (Varian-Techtron 1200), the copper content of the solution treated with the cylinders was measured. This content was 1.1 ppm. Upon washing of the cylinders with 50 ml of normal hydrochloric acid, the copper content was 17 ppm.
The cylinders were contacted for 4 hours with the copper solution. The copper content of the solution was measured once more, and was found to be 1.2 ppm. This sequence of operation was repeated 10 times, and it was found that the cylinders do not lose their copper sequestering ability.
EXAMPLE 7.
This Example describes the preparation of fibrids of invertase obtained by occluding the enzyme in a solution to which polyvinylpyrrolidone has been added.
- 10 49384
A solution of 50 g of invertase, after the addition thereto of 10 g of polyvinylpyrolidone (K30), was vigorously stirred with 333 g of a 15% by weight solution of cellulose acetate in acetone. The solution was introduced into an autoclave and was then extruded by nitrogen pressure (50 atmospheres) through a 500 micron nozzle to form a dry powder of the fibrid type, the particle size of which is in the range of 160-1600 microns. The activity of the invertase enzyme occluded in the fibrids was measured on a solution of 20% by weight sucrose in a 0.1 molar phosphate buffer having a pH of 4 and a temperature of 25°C. The activity, in terms of milligrams of inverted sucrose per minute and per gram of fibrid, lies in the range of 8-50, depending upon the fibrid size.
EXAMPLE 8.
This Example describes the preparation of fibres of hydroxypyrimidine hydrolase and N-carbamoyl-D-aminoacid hydrolase obtained by occluding Agrobacterium radiobacter cells to which polyethyleneimine has been added.
Agrobacterium radiobacter cells (4 g dry weight) were slurried in 100 g of water and treated, with stirring, with 2 g of a 3% by weight solution of polyethyleneimine. After 10 minutes, stirring was discontinued and the cells which had settled were collected and slurried in 25g of water.
The slurry was vigorously stirred with 20 g of a 20% by weight solution of cellulose acetate in acetone. The resulting preparation was introduced into a steel cylinder having connected thereto, at its top, a nitrogen bottle and, at the bottom, a monofilament spinneret having a diameter of 1 mm. By means of a metering pump, the preparation was extruded through the spinneret in the form of a continuous filament which was allowed to dry in air by evaporation of the acetone during a drop of 4 metres. The entire thread (8 g dry weight) was incubated at 40°C under a nitrogen blanket in a 0.1 molar phosphate buffer having a pH of 8 and containing 4 g of DL-phenylhydantoin, for determining the activity of the two enzymes. After 20 hours of reaction,
- 11 49384 the conversion of the hydantoin to D(-)phenylglycine was complete, as shown by an analysis made by the use of an aminoacid analyser. The same thread, when used 10 times for successive hydrolyses, lost 30% of its initial activity.
Claims (9)
- CLAIMS 5 1. A process for the preparation of a microporous body wherein one or more agents selected from biologically active agents, sequestering agents and dyestuffs are occluded, which process comprises (a) forming a solution of a polymeric matrix in an organic solvent; (b) forming a dispersion or 10 solution of said agent or agents in a medium compatible therewith and miscible with the organic solvent for the polymeric matrix; (c) if desired, adding to the dispersion or solution obtained by step (b), and additive selected from (i) at least one polymer which has a molecular weight different from that of the polymeric matrix and which is not soluble in the solvent 15 for the polymeric matrix and (ii) at least one polyfunctional reagent selected from aliphatic aldehydes, isocyanates and thioisocyanates; (d) mixing the solution obtained by step (a) with the dispersion or solution obtained by step (b) with or without the additive added in step (c); and (e) carrying out a shaping stage by (i) coagulating the mixture in a medium which is a non-solvent for the 20 polymeric matrix, or by (ii) extrusion of the mixture in a dry condition, or by (iii) ejecting the mixture from a pressurised enclosure.
- 2. A process according to Claim 1, wherein the coagulation is effected by dripping the mixture into the medium.
- 3. A process according to Claim 1, wherein the coagulation is effected 25 by causing the mixture to flow directly into the medium.
- 4. A process according to any of Claims 1 to 3, wherein said biologically active agent(s) is (are) selected from enzymes, enzymic cells, antigens, - 12 4-8394 antibodies, antisers, hormones, and coenzymes bound to macromolecular matrices.
- 5. A process according to any of Claims 1 to 4, wherein the polymeric matrix is selected from cellulose polymers; esterified and etherified 5 cellulose polymers; polyamides; and polymers or copolymers of acrylonitrile, butadiene, isoprene, acrylates, methacrylates, vinyl butyrate or other vinyl esters, vinyl chloride, vinylidene chloride, styrene or y-methyl glutamate.
- 6. A process according to any of Claims 1 to 5, wherein the solvent for the polymeric matrix is selected from acetone, methyl isobutyl ketone, 10 cyclohexanone or other ketones; methyl acetate, ethyl lactate or other esters; ethylene glycol monoacetate monomethyl ether; ethylene glycol monomethyl ether: methylene chloride; propylene chloride; tetrachloroethanes; nitromethane; chlorophenols; m-cresol; acetic acid; formic acid; dimethylformamide; dimethylsulphoxide; alcohols; dioxan, hydrocarbons; pyridine; 15 chloroform; mixtures of ethanol and water; mixtures of ethanol and carbon tetrachloride; and mixtures of isopropanol and methylethyl ketone.
- 7. A process according to any of Claims 1 to 6, wherein the medium used in step (b) is selected from water, alcohols, ketones, ethers, esters, acids, pyridine, acetonitrile, cyclohexane and dimethylformamide. 2o
- 8. A process according to Claim 1, substantially as described in any of the foregoing Examples.
- 9. A microporous body wherein one or more of said agents are occluded, when prepared by a process according to any of Claims 1 to 8.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IT7920213A IT1207172B (en) | 1979-02-15 | 1979-02-15 | PROCESS FOR THE PREPARATION OF GLOBAL MICROPOROUS BODIES ONE OR MORE ACTIVE AGENTS. |
Publications (2)
Publication Number | Publication Date |
---|---|
IE800282L IE800282L (en) | 1980-08-15 |
IE49394B1 true IE49394B1 (en) | 1985-10-02 |
Family
ID=11164802
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
IE282/80A IE49394B1 (en) | 1979-02-15 | 1980-02-14 | Microporous polymer bodies having agents occluded therein |
Country Status (35)
Country | Link |
---|---|
JP (1) | JPS55115827A (en) |
KR (1) | KR850000252B1 (en) |
AR (1) | AR228027A1 (en) |
AT (1) | AT380487B (en) |
BE (1) | BE881755A (en) |
BG (1) | BG40485A3 (en) |
BR (1) | BR8000975A (en) |
CA (1) | CA1148312A (en) |
CH (1) | CH644387A5 (en) |
CS (1) | CS268652B2 (en) |
DD (1) | DD149075A5 (en) |
DE (1) | DE3005771A1 (en) |
DK (1) | DK167286B1 (en) |
EG (1) | EG14977A (en) |
ES (1) | ES8102803A1 (en) |
FR (1) | FR2448971A1 (en) |
GB (1) | GB2041941B (en) |
GR (1) | GR73888B (en) |
HU (1) | HU186733B (en) |
IE (1) | IE49394B1 (en) |
IL (1) | IL59278A (en) |
IN (1) | IN152453B (en) |
IT (1) | IT1207172B (en) |
LU (1) | LU82166A1 (en) |
MW (1) | MW1080A1 (en) |
NL (1) | NL189007C (en) |
NO (1) | NO161077C (en) |
PH (1) | PH20814A (en) |
PL (1) | PL133437B1 (en) |
PT (1) | PT70829A (en) |
RO (1) | RO81372B (en) |
SE (1) | SE452160B (en) |
YU (1) | YU44312B (en) |
ZA (1) | ZA80644B (en) |
ZM (1) | ZM1780A1 (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2584552A (en) * | 1948-04-12 | 1952-02-05 | Delman Corp | Diaphragm pump |
DE3130606C2 (en) * | 1981-08-01 | 1985-03-21 | Rolf Dr. 8700 Würzburg Siegel | Method for the isolation of cells involved in antibody formation |
US4732851A (en) * | 1982-03-16 | 1988-03-22 | Purification Engineering, Inc. | Immobilization of cells with a polyazetidine prepolymer |
DE3215211A1 (en) * | 1982-04-23 | 1983-10-27 | Akzo Gmbh | MICROPOROISIS POWDER LOADED WITH ACTIVE SUBSTANCES |
IE56509B1 (en) * | 1982-11-04 | 1991-08-28 | Univ California | Methods for oncogenic detection |
GB2189809A (en) * | 1986-05-03 | 1987-11-04 | Michael Storey Otterburn | Immobilized biological material |
DE3735397A1 (en) * | 1987-10-20 | 1989-05-03 | Hoechst Ag | MAGNETIC MEMBRANE CAPSULES AND THEIR USE |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1227855B (en) * | 1960-07-12 | 1966-11-03 | Ichthyol Ges | Process for the production of enzyme bodies for the implementation of enzymatic reactions |
US3672955A (en) * | 1970-05-20 | 1972-06-27 | Us Agriculture | Preparation of an insoluble active enzyme |
IT987038B (en) * | 1973-03-22 | 1975-02-20 | Snam Progetti | HIGH PER MEABILITY CELLULOSE FIBERS CONTAINING ENZINES AND PROCEDURE FOR THEIR PREPA RATION |
FR2222080A1 (en) * | 1973-03-22 | 1974-10-18 | Viejo Jacques | Stabilisation of pepsin - by salt formation with a carboxy polymethylene |
JPS5844401B2 (en) * | 1973-05-07 | 1983-10-03 | ドル オリバ− インコ−ポレイテツド | Naizousurukousoobunsansitenaru Jiyugoutaimaku Narabini Sonoseizouhouhou |
JPS50121485A (en) * | 1974-03-08 | 1975-09-23 | ||
IT1039756B (en) * | 1975-07-10 | 1979-12-10 | Snam Progetti | PROCEDURE TO IMPROVE THE ACTIVITY OF OXIDOREDUCTASE ENZYMES ENCLOSED IN FILAMENT STRUCTURES |
JPS52145592A (en) * | 1976-05-27 | 1977-12-03 | Kansai Paint Co Ltd | Immobilization of enzymes of microbial cells |
-
1979
- 1979-02-15 IT IT7920213A patent/IT1207172B/en active
-
1980
- 1980-01-25 GR GR61038A patent/GR73888B/el unknown
- 1980-01-31 IL IL59278A patent/IL59278A/en unknown
- 1980-02-04 ZA ZA00800644A patent/ZA80644B/en unknown
- 1980-02-04 MW MW10/80A patent/MW1080A1/en unknown
- 1980-02-04 GB GB8003622A patent/GB2041941B/en not_active Expired
- 1980-02-07 ZM ZM17/80A patent/ZM1780A1/en unknown
- 1980-02-08 YU YU333/80A patent/YU44312B/en unknown
- 1980-02-11 PH PH23629A patent/PH20814A/en unknown
- 1980-02-11 NO NO800351A patent/NO161077C/en unknown
- 1980-02-12 ES ES489196A patent/ES8102803A1/en not_active Expired
- 1980-02-12 DK DK060380A patent/DK167286B1/en active
- 1980-02-13 BG BG8046606A patent/BG40485A3/en unknown
- 1980-02-13 EG EG86/80A patent/EG14977A/en active
- 1980-02-13 PT PT70829A patent/PT70829A/en not_active IP Right Cessation
- 1980-02-13 SE SE8001137A patent/SE452160B/en not_active IP Right Cessation
- 1980-02-13 CA CA000345588A patent/CA1148312A/en not_active Expired
- 1980-02-13 BR BR8000975A patent/BR8000975A/en not_active IP Right Cessation
- 1980-02-14 FR FR8003301A patent/FR2448971A1/en active Granted
- 1980-02-14 LU LU82166A patent/LU82166A1/en unknown
- 1980-02-14 HU HU80335A patent/HU186733B/en not_active IP Right Cessation
- 1980-02-14 IE IE282/80A patent/IE49394B1/en not_active IP Right Cessation
- 1980-02-14 DD DD80219059A patent/DD149075A5/en not_active IP Right Cessation
- 1980-02-14 PL PL1980222024A patent/PL133437B1/en unknown
- 1980-02-14 CS CS801017A patent/CS268652B2/en unknown
- 1980-02-14 KR KR1019800000587A patent/KR850000252B1/en active
- 1980-02-14 AT AT0080480A patent/AT380487B/en not_active IP Right Cessation
- 1980-02-14 CH CH123180A patent/CH644387A5/en not_active IP Right Cessation
- 1980-02-15 DE DE19803005771 patent/DE3005771A1/en active Granted
- 1980-02-15 IN IN173/CAL/80A patent/IN152453B/en unknown
- 1980-02-15 BE BE0/199424A patent/BE881755A/en not_active IP Right Cessation
- 1980-02-15 RO RO100196A patent/RO81372B/en unknown
- 1980-02-15 NL NLAANVRAGE8000962,A patent/NL189007C/en not_active IP Right Cessation
- 1980-02-15 AR AR279986A patent/AR228027A1/en active
- 1980-02-15 JP JP1676280A patent/JPS55115827A/en active Pending
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