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EP1556427A2 - Materiau macroporeux se presentant sous la forme de perles de matieres plastiques - Google Patents

Materiau macroporeux se presentant sous la forme de perles de matieres plastiques

Info

Publication number
EP1556427A2
EP1556427A2 EP03750435A EP03750435A EP1556427A2 EP 1556427 A2 EP1556427 A2 EP 1556427A2 EP 03750435 A EP03750435 A EP 03750435A EP 03750435 A EP03750435 A EP 03750435A EP 1556427 A2 EP1556427 A2 EP 1556427A2
Authority
EP
European Patent Office
Prior art keywords
monomers
material according
perien
macroporous plastic
macroporous
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03750435A
Other languages
German (de)
English (en)
Inventor
Stefan Menzler
Hans-Ulrich Petereit
Christian Meier
Thomas Boller
Thomas Süfke
Klaus Schultes
Roger Recktenwald
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Roehm GmbH Darmstadt
Original Assignee
Roehm GmbH Darmstadt
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Roehm GmbH Darmstadt filed Critical Roehm GmbH Darmstadt
Publication of EP1556427A2 publication Critical patent/EP1556427A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F246/00—Copolymers in which the nature of only the monomers in minority is defined
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/18—Suspension polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S530/00—Chemistry: natural resins or derivatives; peptides or proteins; lignins or reaction products thereof
    • Y10S530/81—Carrier - bound or immobilized peptides or proteins and the preparation thereof, e.g. biological cell or cell fragment as carrier
    • Y10S530/812—Peptides or proteins is immobilized on, or in, an organic carrier
    • Y10S530/815—Carrier is a synthetic polymer

Definitions

  • the invention relates to the field of polymer carrier systems and, in particular, to a macroporous plastic bead material containing a copolymer of crosslinked (meth) acrylate plastic.
  • Polymer carrier systems containing copolymers of crosslinked (meth) acrylate plastic are known, for. B. from EP-A 0 328767, EP-A 424 130, EP-A 579 928 or from WO 99/33964.
  • WO 99/40122 (DE-A 19804518) relates to a process for the preparation of a bead-shaped, crosslinked hydrophilic copolymer which is active against ligands with nucleophilic groups by inverse suspension polymerization of a monomer phase.
  • the invention further relates to the carrier polymer materials obtainable therefrom with a high binding capacity for penicillin amidase and a low swelling number and the use thereof.
  • copolymer of crosslinked (meth) acrylate plastic is obtained by inverse suspension polymerization of the following monomers:
  • the copolymer is suitable as a carrier material for various types of enzymes.
  • macroporous plastic bead materials should be provided which are suitable as efficient carrier materials, in particular for enzymes which are able to convert relatively hydrophobic substrates, preferably for lipases.
  • macroporous plastic bead materials should be provided which, after binding lipases, show comparatively high activities in test systems such as tributyrin hydrolysis, triacetin hydrolysis, phenylethyl acetate hydrolysis and / or phenylethyl acetate synthesis.
  • the object is achieved by a macroporous plastic bead material with an average particle diameter in the range from 10 to 1000 ⁇ m, containing a copolymer
  • the macroporous plastic bead material has an average particle diameter V 50 of 10 to 1000, preferably from 50 to 600, particularly preferably from 100 to 500, in particular from 200 to 400 ⁇ m.
  • the determination of the average particle diameter V 50 can, for. B. with a particle analyzer.
  • a sample with a particle concentration in the range of 10 3 -10 6 particles is mixed with some detergent as a wetting aid and additionally treated with ultrasound before the measurement to separate the particles.
  • the macroporous plastic bead material can have a porosity which can be measured by a Kp S ⁇ o value of 0.3 to 0.9, in particular from 0.35 to 0.6.
  • B. characterizes by inverse size exclusion chromatography in tetrahydrofuran.
  • the macroporous plastic bead material can have a swelling number in water from 1 to 1.5, in particular from 1.05 to 1.2.
  • the copolymer consists of the free-radically polymerized units of the monomer types a) to d) which are present in the proportions given and generally add up to 100% by weight.
  • the properties for the implementation of hydrophobic substrates are essentially determined by the selection of the monomers in detail and their quantitative proportions. In particular, the balance of the more hydrophilic monomer types a) and the more hydrophobic monomer types d) seem to have an important influence on the implementation of hydrophobic substrates.
  • the binding properties for enzymes are influenced in particular by the selection and the proportion of the monomer type b).
  • the monomer type c) influences the size and porosity of the plastic beads. Size and porosity in turn influence the binding capacity for enzymes and their catalysis behavior in the bound state.
  • the copolymers can also contain small amounts of further vinyl-polymerizable monomers without their essential properties having to be significantly impaired in individual cases.
  • the copolymers consist of 100% radical-polymerized units, the monomers a) to d).
  • Monomers a) contain 5-60, preferably 10 to 50% by weight of vinylically polymerizable monomers with a water solubility of at least 1% at 20 ° C. in the copolymer.
  • Particularly suitable monomers a) are acrylamide and / or methacrylamide, hydroxyalkyl esters of unsaturated polymerizable carboxylic acids, such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate.
  • z. B N-vinyl pyrrolidone, methyl methacrylate or 3-allyloxy-1, 2-propanediol.
  • Methyl methacrylate and methoxypolyethylene glycol methacrylate are preferred.
  • MPEGMA methoxypolyethylene glycol methacrylate
  • PEGMA polyethylene glycol methacrylate
  • MPEGMA350 methoxypolyethylene glycol methacrylate 350
  • PEGMA polyethylene glycol methacrylate
  • Monomers b) contain 1-40, preferably 10 to 30% by weight of vinylically polymerizable monomers which have an additional functional group, preferably an oxirane group (epoxy group) which can form covalent bonds in a reaction with nucleophilic groups of ligands, are provided.
  • an additional functional group preferably an oxirane group (epoxy group) which can form covalent bonds in a reaction with nucleophilic groups of ligands
  • ligands are preferably biologically active molecules, especially macromolecules, e.g. B. amino acids, peptides, proteins, especially enzymes such as. B. lipases, but also nucleic acids or polysaccharides. Oxirane groups in particular are suitable for binding ligands while maintaining their biological activity.
  • Suitable monomers b) are glycidyl methacrylate and / or allyl glycidyl ether and / or vinyl azlactone.
  • Glycidyl methacrylate is preferred, particularly preferably in an amount of 15 to 25% by weight.
  • Monomers c) contain 10-40, preferably 20 to 35% by weight of hydrophilic, crosslinking, radically polymerizable monomers with two or more ethylenically unsaturated polymerizable groups.
  • B. hydrophilic di (meth) acrylates such as. B. ethylene glycol di (meth) acrylate and polyethylene oxide di (meth) acrylates.
  • Suitable monomers c) are also N, N ' -methylene-bis-acrylamide or N, N ' -methylene-bis-methacrylamide.
  • Preferred monomer c) is 1,4-butanediol dimethacrylate.
  • Monomers d) contain 10-60, preferably 10-30% by weight of vinylically polymerizable monomers with a water solubility of at most 1% at 20 ° C.
  • Suitable monomers d) are, for. B. isobutyl methacrylate, n-butyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate and 2-ethylhexyl methacrylate. production method
  • the macroporous plastic bead material consisting of the copolymers can be prepared in a manner known per se by means of suspension polymerization (bead polymerization).
  • An aqueous phase, which in particular distributors, for. B. contains precipitated aluminum hydroxide, placed in a stirred reactor.
  • the monomers are then used together with a polymerization initiator, e.g. B. dilauryl peroxide, in an organic phase, e.g. B. cyclohexane added.
  • the phases are dispersed with stirring, the polymerization of the monomers z. B. can be done in a temperature range of 60 to 80 ° C.
  • the macroporous plastic bead material can be obtained from the batch by filtration and drying.
  • Variants of the copolymers on which the enzyme lipase from Candida antarctica was immobilized are said to have good results in the following test systems.
  • the enzyme immobilization can e.g. B. by incubating the macroporous plastic bead material with a commercially available enzyme solution (z. B. Novozym® 525F) in aqueous solution for 1 to 2 days at room temperature. The plastic bead material coupled with the enzyme is then washed and dried. The immobilizates obtained in this way can be tested in the following test systems.
  • tributyrin hydrolysis activity of have at least 150 [U / g], preferably at least 300 [U / g], in particular at least 500 [U / g].
  • the immobilizate of macroporous plastic bead material and lipase from Candida antarctica can e.g. B. have a triacetin hydrolysis activity of at least 50 [U / g], preferably at least 100 [U / g], in particular at least 150 [U / g].
  • the immobilizate of macroporous plastic bead material and lipase from Candida antarctica can e.g. B. have a phenylethyl acetate hydrolysis activity of at least 80 [U / g], preferably at least 100 [U / g], in particular at least 150 [U / g].
  • Racemate resolution of 1-phenylethanol by transesterification (non-aqueous system).
  • the immobilizate of copolymer and lipase from Candida antarctica can, for. B. have a phenylethanol racemate cleavage activity of at least 100 [U / g], preferably at least 120 [U / g], in particular at least 180 [U / g].
  • the macroporous plastic bead material can be used for the immobilization of peptides, proteins, nucleic acids or polysaccharides, preferably for the immobilization of lipases from Rhizopus, Aspergillus, Mucor, Alcaligenes, Candida, Pseudomonas, Thermomyces, Chromobacterium, porcine pancreas, and for the immobilization of phospholipases Streptomyces and Actinomadura, as well as for the immobilization of esterases from pig liver and orange peel.
  • the macroporous plastic bead materials according to the invention can be used as carrier materials for the covalent binding of ligands by means of the oxirane groups present in stirred or flow reactors.
  • This can e.g. B. by addition of proteins, in particular enzymes, from concentrated solutions via covalent binding while maintaining their biological activity.
  • proteins, in particular enzymes from concentrated solutions via covalent binding while maintaining their biological activity.
  • peptides, amino acids, lipids, nucleotides, polynucleotides, low molecular weight nucleophilic compounds or organometallic compounds can also be reacted with the oxirane groups of the carrier beads.
  • the polymer beads loaded with ligands can be used in a manner known per se for the stereospecific synthesis of chiral substances, such as amino acids (d-phenylalamine, p-hydroxy-d-phenylalanine, l-tert.-leucine) or drugs, e.g. B. ß-lactam antibiotics, ibuprofen can be used.
  • amino acids d-phenylalamine, p-hydroxy-d-phenylalanine, l-tert.-leucine
  • drugs e.g. B. ß-lactam antibiotics, ibuprofen can be used.
  • the polymer beads can also be used in the separation technique for adsorption chromatography or gel permeation chromatography. For specific adsorption, the polymer beads can be loaded with immunoglobulin fractions from antisera or with monoclonal antibodies.
  • Another area of application is the use of the carrier polymer material loaded with enzymes or antibodies as an adsorbent in extracorporeal therapy, in which pathogenic or toxic substances are removed from whole blood.
  • MPEGMA350 methoxypolyethylene glycol methacrylate 350
  • Example 1 Manufacturing instructions for mixed polymer variant 13
  • the total amount of water [810g] and the aluminum sulfate [5.4g] are placed in a 2L stirred reactor comprising a thermocouple, bath thermostat, reflux condenser, nitrogen inlet tube with stirring and nitrogen inlet and heated to 70 ° C.
  • the soda solution [24g] is added in one go to precipitate the aluminum hydroxide.
  • the auxiliary distributors C15 paraffin sulfonate, Na salt and polyethylene glycol 5000/6000 [0.05 g each] are then added.
  • the pH of the water phase is approximately 5.5. After that:
  • the total amount of water [810g] and the aluminum sulfate [5.4g] are placed in a 2L stirred reactor, comprising a thermocouple, bath thermostat, reflux condenser, nitrogen inlet tube with stirring and nitrogen inlet and heated to 70 ° C.
  • a 2L stirred reactor comprising a thermocouple, bath thermostat, reflux condenser, nitrogen inlet tube with stirring and nitrogen inlet and heated to 70 ° C.
  • the soda solution [24g] is added in one go to precipitate the aluminum hydroxide.
  • the auxiliary distributors C15 paraffin sulfonate, Na salt and polyethylene glycol 5000/6000 [0.05 g each] are then added.
  • the pH of the water phase is approximately 5.5. After that:
  • the average particle diameter is measured with a CIS1 particle analyzer from LOT GmbH.
  • Sample preparation Place enough sample in a 400 ml beaker to reach a concentration of 10 3 -10 6 particles. Then a few drops of detergent are added to the sample as a wetting aid. Then it is filled up with 350 ml deionized water. The suspension obtained is treated with ultrasound for about 1 minute and then measured in the CIS1 device, measuring range 5-600 ⁇ m.
  • the proportion of the pore volume which is accessible to the probe molecule used is determined by inverse size exclusion chromatography (SEC).
  • SEC inverse size exclusion chromatography
  • the distribution coefficient obtained in this way is a measure of the porosity of the sample.
  • a Merck Superformance glass column 300x10 mm is filled with the bead polymer using THF and tetrachlorethylene according to the balanced density principle. The column is then packed and equilibrated by delivering 150 ml of THF at a flow rate of 15 ml / min. The column is then closed and a further 150 ml of tetrahydrofuran (THF) are pumped at a flow rate of 10 ml / min.
  • THF tetrahydrofuran
  • probe molecules are placed one after the other on the column and eluted at a flow rate of 0.2 ml / min.
  • the exclusion limits are determined with o-dichlorobenzene and polystyrene 6770000 (molecular weight 6770000 daltons), polystyrene 10200 (molecular weight 10200 daltons) is used as the probe molecule.
  • the distribution coefficient is calculated from the elution volumes as follows:
  • KpsiO VE (PS10200) - VE (PS6770000) / VE (o-dichlorobenzene) - VE (PS6770000)
  • KPSIO distribution coefficient for polystyrene 10200
  • VE (PS ⁇ 77 OO OO ) elution volume of the exclusion marker polystyrene 6770000
  • VE (o-dichlorobenzene) elution volume of the exclusion marker o-dichlorobenzene.
  • pH stat titrator e.g. B. Mettler DL 50
  • pH stat titrator e.g. B. Schott Titroline Alpha 100 ml double-walled glass vessel Thermostatic water bath stirring station Radiometer TTA 80 pH electrode Schott Blue Line 10 ml burette
  • the reaction vessel is thermostatted to 25 ° C. 16 ml of 0.05M potassium phosphate buffer pH 7.0 are introduced, 100 mg of the investigating immobilisates are added. Then the stirring is started. The reaction is started by adding 400 ⁇ l triacetin. The connected titrator registers the alkali consumption depending on the hydrolysis time. The activity of the enzyme is determined from the linear slope of the curve. The activity in U / g immobilizate can be calculated directly from the value obtained therefrom in ml NaOH / min per amount of enzyme used.
  • pH stat titrator e.g. B. Mettler DL 50
  • Table A Examples of polymer supports produced according to the invention, immobilization method M3-aMEK.
  • Table B Examples of polymer supports produced according to the invention, immobilization method M2.
  • Polymer A Commercially available, macroporous, crosslinked plastic bead material
  • Polymer B Commercially available, macroporous, crosslinked plastic bead material
  • polymer C corresponds to polymer A, but has a lower swelling number ( ⁇ 1.5) (preparation according to DE-A 19804518).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne un matériau macroporeux se présentant sous la forme de perles de matières plastiques, possédant un diamètre moyen de particules compris entre 10 et 1000 ñm, contenant un copolymère constitué de : a) 5 - 60 % en poids de monomères pouvant être soumis à une polymérisation vinylique, présentant une solubilité dans l'eau d'au moins 1 % à 20 DEG C, b) 1 - 40 % en poids de monomères pouvant être soumis à une polymérisation vinylique, comportant un groupe fonctionnel supplémentaire pouvant se lier par covalence aux groupes nucléophiles des ligands, au cours d'une réaction analogue à une polymérisation, c) 10 - 40 % en poids de monomères hydrophiles pouvant être soumis à une polymérisation radicalaire réticulante, comportant au moins deux groupes polymérisables, éthyléniquement insaturés et d) 10 - 60 % en poids de monomères pouvant être soumis à une polymérisation vinylique, présentant une solubilité dans l'eau d'au maximum 1 % à 20 DEG C, la somme des monomères a) à d) étant généralement égale à 100 %.
EP03750435A 2002-10-31 2003-08-25 Materiau macroporeux se presentant sous la forme de perles de matieres plastiques Withdrawn EP1556427A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10251144 2002-10-31
DE10251144A DE10251144A1 (de) 2002-10-31 2002-10-31 Makroporöses Kunststoffperlenmaterial
PCT/EP2003/009378 WO2004039854A2 (fr) 2002-10-31 2003-08-25 Materiau macroporeux se presentant sous la forme de perles de matieres plastiques

Publications (1)

Publication Number Publication Date
EP1556427A2 true EP1556427A2 (fr) 2005-07-27

Family

ID=32115155

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03750435A Withdrawn EP1556427A2 (fr) 2002-10-31 2003-08-25 Materiau macroporeux se presentant sous la forme de perles de matieres plastiques

Country Status (9)

Country Link
US (1) US7381552B2 (fr)
EP (1) EP1556427A2 (fr)
JP (1) JP2006504816A (fr)
KR (1) KR20050084753A (fr)
CN (1) CN1283680C (fr)
AU (1) AU2003270100A1 (fr)
DE (1) DE10251144A1 (fr)
IL (2) IL162081A0 (fr)
WO (1) WO2004039854A2 (fr)

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WO2004039854A2 (fr) 2004-05-13
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JP2006504816A (ja) 2006-02-09
US7381552B2 (en) 2008-06-03
US20050065224A1 (en) 2005-03-24
IL162081A (en) 2008-07-08
KR20050084753A (ko) 2005-08-29
IL162081A0 (en) 2005-11-20
DE10251144A1 (de) 2004-05-19
CN1283680C (zh) 2006-11-08
AU2003270100A1 (en) 2004-05-25

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