CN1148445C - Microbead-shaped porous carrier with skeleton of multi-element copolymer for immobilized enzyme and its preparing process - Google Patents
Microbead-shaped porous carrier with skeleton of multi-element copolymer for immobilized enzyme and its preparing process Download PDFInfo
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- CN1148445C CN1148445C CNB991098366A CN99109836A CN1148445C CN 1148445 C CN1148445 C CN 1148445C CN B991098366 A CNB991098366 A CN B991098366A CN 99109836 A CN99109836 A CN 99109836A CN 1148445 C CN1148445 C CN 1148445C
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Abstract
The present invention relates to a microbead-shaped porous carrier for an immobilized enzyme, which uses a multi-element copolymer as a skeleton, and a preparing method thereof. The preparing method comprises the following steps: four comonomers are used, and 5 to 30 parts by weight of monomer A, 5 to 30 parts by weight of monomer B, 40 to 90 parts by weight of monomer C and 0 to 10 parts by weight of monomer D are fully mixed; the mixture is polymerized in a suspension system containing 1 to 4 wt% of gelatin and 1 wt% of Mg(OH)2, wherein the volume of the system is 3 to 4 times of the total volume of the monomers; temperature slow rises from 40DEGC, and the rate of temperature rise is from 0.45 to 0.65 deg c every minute; the mixture is polymerized at the temperature of 65 to 70DEGC for 5 hours, solidified at the temperature of more than 70DEGC for 6 to 10 hours, sieved, washed by a great amount of water and soaked in acetone; a holing agent is washed off to obtain a porous microbead; the microbead is aired and added to excessive methanol solution containing 3 to 5 wt% of NaOH, the mixture reacts at the temperature of 18 to 25DEGC for 24 to 48 hours, suction filtration is carried out, and the mixture is washed by acetone thrice to obtain a product. The carrier has the diameter of 80 to 400 mum and the wet density of 1.02 to 1.10 g/cm<3>. The quantity of hydroxy which can be activated reaches 9.8 to 11.5 mmol/g(dry weight).
Description
Technical field
The present invention relates to a kind of immobilized enzyme biotechnology, particularly relate to a kind of be skeleton with the multiple copolymer, through multi-hole type microballon shape fixed enzyme vector of surface modification and preparation method thereof.
Background technology
Early sixties, people such as Katchallski-Katzir at first are fixed in some proteolytic ferments on the insoluble carrier or are wrapped in the artificial rust, make immobilized enzyme, as document 1:Annu.Rev.Biochem.35,773-908,1966.People such as the Japanese Tanake Seiyaku Chibata of company successfully were used for enzyme immobilization technology industrial production first in 1967, and as document 2:Biotechnol.Bioeng.9,603-615 describes in 1967.They use immobilization amino acid acylase that the racemize DL-amino acid of synthetic is converted into corresponding L-type enantiomorph.Before and after 1970, trial production during two other immobilized enzyme system drops in succession.One is that Britain produces 6-amino-penicillanic acid with immobilized penicillin acylated enzyme hydrolyzing penicillin G or V, as document 3:Proc.R.Soc.London Ser.B 179, and 321-334,1971 is described; Another is that the U.S. produces fructose with the fixed glucose isomerase transforming glucose, as document 4:Applied Biochemistry and Bioengineering, and Vol.1, pp222-327.Academic Press, 1976 is described.These successful industrial application have promoted the research extensively and profoundly of enzyme immobilization technology, make with the immobilized enzyme stable the increasing of quantity of the commercial run that is catalyzer.
Utilize immobilized enzyme to carry out industrial production, enzyme can be reclaimed, reuse, reduced the catalyzer cost, also improved the stability of enzyme, avoided zymoprotein, simplified aftertreatment the pollution that product causes.Its research and application develop rapidly, obtain widespread use in industrial production and biochemical analysis, become one of most active fields in the modern biotechnology.
Enzyme immobilization method can reduce carrier combined techniques, crosslinking and entrapping method three major types.The carrier combined techniques is that enzyme is incorporated into a class process for fixation on the water insoluble carrier.According to bonded form difference, can be divided into physisorphtion, ionic bond method and covalent attachment method etc. again.Physisorphtion be meant enzyme by physical adsorption on insoluble carrier.Carrier has activated carbon, sintered glass, aluminum oxide, silica gel, starch, synthetic resins etc.This method has enzyme active center and is difficult for advantage destroyed, that the enzymatic structure variation is little, but a little less than enzyme and the carrier interaction force, enzyme easily comes off.The ionic bond method is incorporated into enzyme on the water insoluble carrier with ion-exchange group by ionic linkage.The carrier of this method has polyose ion-exchanger and synthetic macromolecule ion exchange resin, for example DEAE-Mierocrystalline cellulose, CM-Mierocrystalline cellulose etc.This method is simple to operate, mild condition, and the higher structure of enzyme and the amino-acid residue in active centre are difficult for destroyed, can obtain the higher immobilized enzyme of enzyme yield alive.But the bonding force of carrier and enzyme a little less than, be subjected to the influence of damping fluid kind or pH easily; When reacting under the high condition of ionic strength, enzyme easily comes off from carrier.The covalent attachment method be with enzyme with covalent bonds on carrier.This method or with carrier related group activation, relevant with enzyme then group generation linked reaction, or on carrier, connect a bifunctional reagent, then the enzyme coupling is got on.Amino, carboxyl, hydroxyl, phenolic group etc. can be arranged with the functional group of carrier-bound enzyme.Covalent attachment method reaction conditions is relatively harsher, complicated operation, and cause that easily the higher structure of enzyme changes, and destroying the part active centre, enzyme yield alive is generally about 30%, but the enzyme combination is firmly, good stability.It is use in the carrier combined techniques maximum a kind of.Industrial extensive employing covalent attachment legal system is equipped with immobilized enzyme.
The used carrier of carrier combined techniques has membranaceous, fibrous and particulate state, and used substrate material has natural polymer and synthetic polymer two classes.Natural polymer has agarose, gelatin, as document 5: microbiotic, 13 (3), 177-180,1988 is described; And for example document 6: Chinese Journal of Pharmaceuticals, 24 (3), 100-103,1993 and document 7: Chinese microbiotic magazine, 15 (5), 338-341, chitin and the document 8 introduced in 1990: silk, (8), 13-15, the fibroin membrane of introducing in 19,1996 etc.Vinylbenzene-Vinylstyrene particle, document 10 that synthetic polymer has document 9:DE3515252 to introduce: University Of Shanxi's journal, natural science edition, 14 (3), 273-277,1991 macroporous adsorbent resin, document 11 (JP5959191, JP58190399) ion exchange resin of Jie Shaoing, the documents of introducing 12: microorganism journal, 38 (3), 204-207,1998 polyacrylonitrile fibres of introducing etc.When membranaceous and fibrous carrier was used for reactor, liquid-phase mixing was bad, is unfavorable for the regulation and control of acidity in the reaction process, and needed manually carrier to be packed into reactor, and labour intensity is big, the reaction process instability.On the other hand, membranaceous and the used material of fibrous carrier often is not exclusively used in immobilized enzyme, influence the performance of enzymic activity, as polyacrylonitrile fibre former be used for the weaving, ion exchange resin is former to be used for water treatment and other sepn process, chitin then is through chemically treated natural polymer, and batch difficult quality is stable.
Summary of the invention
Purpose of the present invention: in order to overcome the shortcoming of said fixing enzyme carrier, resolved vector combines weak problem with enzyme, reduces the probability that enzyme comes off from carrier; In order to improve the activity of immobilized enzyme; Be difficult to identical shortcoming in order to overcome existing carrier batch different mass; For the industrialization that promotes China's enzyme immobilization technology and the development of related industries, what a kind of excellent property was provided is skeleton with the multiple copolymer, through the multi-hole type microballon shape fixed enzyme vector of surface modification.
The object of the present invention is achieved like this:
Provided by the invention is that the preparation method of the multi-hole type microballon shape fixed enzyme vector of skeleton carries out according to the following step with the multiple copolymer:
(1) microballon preparation: comonomer has four classes (A, B, C, D), and its proportion scale is as follows:
Monomer A 5-25 weight part;
Monomers B 5-25 weight part;
Monomer C50-90 weight part;
Monomer D0-10 weight part;
Wherein monomer A be vinylbenzene, a kind of in Vinyl toluene, a Vinyl toluene and the alpha-methyl styrene, monomers B is a kind of in Vinylstyrene and the triallyl isocyanurate, monomer C is a vinyl-acetic ester, and monomer D is one or both in methyl methacrylate, methyl acrylate, vinylformic acid and the methacrylic acid;
With A, B, C, D four class monomers thorough mixing according to the above ratio.According to the above-mentioned monomer meter that mixes of every 100g, add initiator 0.8-1.3g, pore-creating agent 6-30ml and 200
#Gasoline 0-20ml.Wherein initiator adopts the general initiator of the industry, and as Diisopropyl azodicarboxylate (AlBN) or benzoyl peroxide (BPO), pore-creating agent adopts the general perforating agent of the industry, as methyl acetate, ethyl acetate, butylacetate, ethyl butyrate or butyl butyrate;
Every 100g monomer uses gelatin that contains 2.5-4wt% and the 1wt%Mg (OH) of 350-450ml
2Suspension system in carry out polyreaction.40 ℃ of beginnings slowly heat up, and temperature rise rate is 0.45-0.65 ℃/min, and 65-70 (solidified 6-7 hour more than 70 ℃, sieves, and with a large amount of water washings, soaks with acetone then, and the flush away pore-creating agent obtains the multi-hole type microballon by polymerization 5 hours.
(2) surface modification: above-mentioned microballon is air-dry, add the excessive methanol solution that contains 3-5wt%NaOH, 18-25 ℃ of reaction is after 24-48 hour, and suction filtration is used washing with acetone three times, promptly makes the carrier that immobilized enzyme is used.
The surfaces externally and internally of this carrier have great amount of hydroxy group (OH), be easy to activation, and hardness height, thereby improved the activity of immobilized enzyme.Control the quantity and the density that can activate hydroxyl by regulating each monomeric proportioning and modified condition.
Provided by the invention is the multi-hole type microballon shape fixed enzyme vector of skeleton with the multiple copolymer, and its particle diameter is 80-400 μ m, and wet density is 1.02-1.10g/cm
3, can activate hydroxyl quantity and reach 9.8-11.5mmol/g (dry weight).It can be made through suspension copolymerization by following proportion scale by following four class monomers;
Monomer A 5-25 weight part;
Monomers B 5-25 weight part;
Monomer C50-90 weight part;
Monomer D0-10 weight part.
Effect of the present invention: the fixed enzyme vector particle diameter of the present invention's preparation is 80-400 μ m, and wet density is 1.02-1.10g/cm
3, be suitable for the reactor operation; Be difficult for microbiological contamination, intensity is better than the external agarose 6B that adopts usually; Active group is many, can activate hydroxyl quantity and reach the 9.8-11.5mmol/g dry weight, is higher than German carrier Eupergit C 2-3 doubly; Cost is low, and the preparation method is simple.Carrier of the present invention is activated the back in conjunction with penicillin acylase, the immobilized penicillin acylated enzyme of making is than the high 5-10 of activity of the immobilized enzyme times with the preparation of agarose 6B microballon, than the high 2-3 of activity of the immobilized enzyme for preparing with Eupergit C doubly, enzyme yield average out to 37% alive; In conjunction with saccharifying enzyme or glucose isomerase, the over-all properties of the immobilized enzyme of making is better than using other carrier with carrier activation of the present invention back.
Embodiment
The present invention is described in detail below in conjunction with embodiment.
Embodiment 1:
1 with vinylbenzene 5g, Vinylstyrene 5g, vinyl-acetic ester 90g thorough mixing, adds initiator Diisopropyl azodicarboxylate (AlBN) 1.1g, pore-creating agent butylacetate 10ml and 200
#Gasoline 10ml contains 2.5wt% gelatin and 1wt%Mg (OH) at 400ml
2Suspension system in carry out polyreaction.40 ℃ of beginnings slowly heat up, and temperature rise rate is 0.56 ℃/min, 65 ℃ of polymerizations 5 hours, and 70 ℃ solidified 2 hours, and 75 ℃ solidified 3.5 hours, and 80 ℃ are continued to solidify after 1 hour, and stopped reaction sieves, with a large amount of water washings, then with acetone immersion, flush away pore-creating agent.
2 is air-dry with above-mentioned microballon, adds the excessive methanol solution that contains 3wt%NaOH, and 18 ℃ of reactions are after 24 hours, and suction filtration is used washing with acetone three times, promptly makes the carrier that immobilized enzyme is used.
Embodiment 2:
Preparation process is with embodiment 1, vinylbenzene 25g, and Vinylstyrene 15g, vinyl-acetic ester 60g, pore-creating agent methyl acetate 30ml does not add 200
#Gasoline, gelatin solution 400ml, other is constant.
Embodiment 3:
1 with vinylbenzene 15g, Vinylstyrene 25g, vinyl-acetic ester 50g, methyl methacrylate 10g thorough mixing, adds initiator benzoyl peroxide (BPO) 1.3g, pore-creating agent ethyl acetate 6ml and 200
#Gasoline 6ml contains 2.5wt% gelatin and 1wt%Mg (OH) at 375ml
2Suspension system in carry out polyreaction.40 ℃ of beginnings slowly heat up, and temperature rise rate is 0.45 ℃/min, 65 ℃ of polymerizations 5 hours, and 72 ℃ solidified 2 hours, and 75 ℃ solidified 3.0 hours, and 80 ℃ are continued to solidify after 1 hour, and stopped reaction sieves, with a large amount of water washings, then with acetone immersion, flush away pore-creating agent.
2 is air-dry with above-mentioned microballon, adds the excessive methanol solution that contains 5wt%NaOH, and 22 ℃ of reactions are after 36 hours, and suction filtration is used washing with acetone three times, promptly makes the carrier that immobilized enzyme is used.
Embodiment 4:
1 with vinylbenzene 20g, Vinylstyrene 15g, vinyl-acetic ester 60g, methacrylic acid 5g thorough mixing, adds initiator Diisopropyl azodicarboxylate (AlBN) 1.0g, pore-creating agent ethyl butyrate 15ml and 200
#Gasoline 15ml contains 2.5wt% gelatin and 1wt%Mg (OH) at 400ml
2Suspension system in carry out polyreaction.40 ℃ of beginnings slowly heat up, and temperature rise rate is 0.45 ℃/min, 67 ℃ of polymerizations 5 hours, and 72 ℃ solidified 2 hours, and 75 ℃ solidified 3.0 hours, and 80 ℃ are continued to solidify after 1 hour, and stopped reaction sieves, with a large amount of water washings, then with acetone immersion, flush away pore-creating agent.
2 is air-dry with above-mentioned microballon, adds the excessive methanol solution that contains 4wt%NaOH, and 25 ℃ of reactions are after 24 hours, and suction filtration is used washing with acetone three times, promptly makes the carrier that immobilized enzyme is used.
Embodiment 5:
1 will add initiator benzoyl peroxide (BPO) 1.1g, pore-creating agent butylacetate 30ml and 200 to Vinyl toluene 25g, triallyl isocyanurate 15g, vinyl-acetic ester 60g thorough mixing
#Gasoline 5ml contains 2.5wt% gelatin and 1wt%Mg (OH) at 400ml
2Suspension system in carry out polyreaction.40 ℃ of beginnings slowly heat up, and temperature rise rate is 0.50 ℃/min, 67 ℃ of polymerizations 5 hours, and 70 ℃ solidified 2.5 hours, 75 ℃ solidified 3.0 hours, and 80 ℃ are continued to solidify after 1 hour, and stopped reaction sieves, with a large amount of water washings, soak the flush away pore-creating agent then with acetone.
2 is air-dry with above-mentioned microballon, adds the excessive methanol solution that contains 3wt%NaOH, and 18 ℃ of reactions are after 48 hours, and suction filtration is used washing with acetone three times, promptly makes the carrier that immobilized enzyme is used.
Embodiment 6:
Vinyl toluene 15g, Vinylstyrene 25g, vinyl-acetic ester 50g, methyl methacrylate 5g, methacrylic acid 5g thorough mixing add initiator benzoyl peroxide (BPO) 0.8g, pore-creating agent butylacetate 6ml and 200 between 1 general
#Gasoline 6ml contains 4% gelatin and 1wt%Mg (OH) at 375ml
2Suspension system in carry out polyreaction.40 ℃ of beginnings slowly heat up, and temperature rise rate is 0.50 ℃/min, 70 ℃ of polymerizations 5 hours, and 72 ℃ solidified 2 hours, and 75 ℃ solidified 3 hours, and 80 ℃ are continued to solidify after 1 hour, and stopped reaction sieves, with a large amount of water washings, then with acetone immersion, flush away pore-creating agent.
2 is air-dry with above-mentioned microballon, adds the excessive methanol solution that contains 5wt%NaOH, and 22 ℃ of reactions are after 36 hours, and suction filtration is used washing with acetone three times, promptly makes the carrier that immobilized enzyme is used.
Embodiment 7:
1 with alpha-methyl styrene 20g, triallyl isocyanurate 15g, vinyl-acetic ester 60g, vinylformic acid 5g thorough mixing, adds initiator Diisopropyl azodicarboxylate (AlBN) 0.9g, pore-creating agent methyl acetate 15ml and 200
#Gasoline 10ml contains 3% gelatin and 1wt%Mg (OH) at 350ml
2Suspension system in carry out polyreaction.40 ℃ of beginnings slowly heat up, and temperature rise rate is 0.60 ℃/min, 70 ℃ of polymerizations 5 hours, and 72 ℃ solidified 2 hours, and 75 ℃ solidified 3 hours, and 80 ℃ are continued to solidify after 1 hour, and stopped reaction sieves, with a large amount of water washings, then with acetone immersion, flush away pore-creating agent.
2 is air-dry with above-mentioned microballon, adds the excessive methanol solution that contains 4wt%NaOH, and 25 ℃ of reactions are after 24 hours, and suction filtration is used washing with acetone three times, promptly makes the carrier that immobilized enzyme is used.
Embodiment 8:
1 will add initiator Diisopropyl azodicarboxylate (AlBN) 0.8g to Vinyl toluene 25g, triallyl isocyanurate 15g, vinyl-acetic ester 60g thorough mixing, and pore-creating agent butyl butyrate 30ml contains 2.5wt% gelatin and 1wt%Mg (OH) at 400ml
2Suspension system in carry out polyreaction.40 ℃ of beginnings slowly heat up, and temperature rise rate is 0.60 ℃/min, 70 ℃ of polymerizations 5 hours, and 70 ℃ solidified 2.5 hours, 75 ℃ solidified 3.5 hours, and 80 ℃ are continued to solidify after 1 hour, and stopped reaction sieves, with a large amount of water washings, soak the flush away pore-creating agent then with acetone.
2 is air-dry with above-mentioned microballon, adds the excessive methanol solution that contains 3wt%NaOH, and 18 ℃ of reactions are after 48 hours, and suction filtration is used washing with acetone three times, promptly makes the carrier that immobilized enzyme is used.
Embodiment 9:
Vinyl toluene 15g, Vinylstyrene 25g, vinyl-acetic ester 50g, methyl acrylate 5g, vinylformic acid 5g thorough mixing add initiator benzoyl peroxide (BPO) 1.0g, pore-creating agent butylacetate 6ml and 200 between 1 general
#Gasoline 6ml contains 2.5% gelatin and 1wt%Mg (OH) at 375ml
2Suspension system in carry out polyreaction.40 ℃ of beginnings slowly heat up, and temperature rise rate is 0.65 ℃/min, 68 ℃ of polymerizations 5 hours, and 72 ℃ solidified 2 hours, and 75 ℃ solidified 3.5 hours, and 80 ℃ are continued to solidify after 1 hour, and stopped reaction sieves, with a large amount of water washings, then with acetone immersion, flush away pore-creating agent.
2 is air-dry with above-mentioned microballon, adds the excessive methanol solution that contains 5wt%NaOH, and 22 ℃ of reactions are after 36 hours, and suction filtration is used washing with acetone three times, promptly makes the carrier that immobilized enzyme is used.
Embodiment 10:
1 with alpha-methyl styrene 20g, triallyl isocyanurate 15g, vinyl-acetic ester 60g, methyl acrylate 5g thorough mixing, adds initiator benzoyl peroxide (BPO) 1.0g, pore-creating agent butylacetate 20ml and 200
#Gasoline 10ml contains 2.5wt% gelatin and 1wt%Mg (OH) at 450ml
2Suspension system in carry out polyreaction.40 ℃ of beginnings slowly heat up, and temperature rise rate is 0.65 ℃/min, 68 ℃ of polymerizations 5 hours, and 72 ℃ solidified 2 hours, and 75 ℃ solidified 3.5 hours, and 80 ℃ are continued to solidify after 1 hour, and stopped reaction sieves, with a large amount of water washings, then with acetone immersion, flush away pore-creating agent.
2 is air-dry with above-mentioned microballon, adds the excessive methanol solution that contains 4wt%NaOH, and 25 ℃ of reactions are after 24 hours, and suction filtration is used washing with acetone three times, promptly makes the carrier that immobilized enzyme is used.
Claims (2)
1. one kind is the method for making of the multi-hole type microballon shape fixed enzyme vector of skeleton with the multiple copolymer, it is characterized in that carrying out according to the following step:
(1) microballon preparation: with monomer A 5-25 weight part, monomers B 5-25 weight part, monomer C50-90 weight part, monomer D0-10 weight part thorough mixing;
The above-mentioned monomer that mixes of every 100g adds initiator 0.8-1.3g, pore-creating agent 6-30ml and 200
#Gasoline 0-20ml;
Every 100g monomer uses gelatin that contains 2.5-4wt% and the 1wt%Mg (OH) of 350-450ml
2Suspension system in carry out polyreaction, 40 ℃ of beginnings slowly heat up, temperature rise rate is 0.45-0.65 ℃/min, 65-70 ℃ of polymerization 5 hours, solidified more than 70 ℃ 6-7 hour, and sieved and, soak with acetone then with a large amount of water washings with usual method, the flush away pore-creating agent obtains the multi-hole type microballon;
(2) surface modification: to obtain the multi-hole type microballon air-dry with above-mentioned, adds the excessive methanol solution that contains 3-5wt%NaOH, and 18-25 ℃ of reaction be after 24-48 hour, and suction filtration with washing with acetone three times, promptly makes product,
Above-mentioned monomer A is vinylbenzene, a kind of in Vinyl toluene, a Vinyl toluene and the alpha-methyl styrene;
Above-mentioned monomers B is a kind of in Vinylstyrene and the triallyl isocyanurate;
Above-mentioned monomer C is a vinyl-acetic ester;
Above-mentioned monomer D is one or both in methyl methacrylate, methyl acrylate, vinylformic acid and the methacrylic acid.
2. one kind is the multi-hole type microballon shape fixed enzyme vector of skeleton with the multiple copolymer, and it is characterized in that: this carrier granule diameter is 80-400 μ m, and wet density is 1.02-1.10g/cm
3, can activate hydroxyl quantity and reach the 9.8-11.5mmol/g dry weight; It can be by following monomer according to following proportion scale through method according to claim 1 and get:
Monomer A is vinylbenzene, a kind of in Vinyl toluene, a Vinyl toluene and the alpha-methyl styrene, the 5-25 weight part;
Monomers B is a kind of in Vinylstyrene and the triallyl isocyanurate, the 5-25 weight part;
Monomer C is a vinyl-acetic ester, the 50-90 weight part;
Monomer D is one or both in methyl methacrylate, methyl acrylate, vinylformic acid and the methacrylic acid, the 0-10 weight part.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB991098366A CN1148445C (en) | 1999-07-16 | 1999-07-16 | Microbead-shaped porous carrier with skeleton of multi-element copolymer for immobilized enzyme and its preparing process |
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| CNB991098366A CN1148445C (en) | 1999-07-16 | 1999-07-16 | Microbead-shaped porous carrier with skeleton of multi-element copolymer for immobilized enzyme and its preparing process |
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| CN1148445C true CN1148445C (en) | 2004-05-05 |
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| CN105440197B (en) * | 2016-01-08 | 2017-10-03 | 谱赛科（江西）生物技术有限公司 | A kind of preparation method and application technology for the polymeric adsorbent that steviol glycoside is isolated and purified |
| CN106589202A (en) * | 2016-12-05 | 2017-04-26 | 黄晖 | Lysozyme immobilized carrier and preparation method thereof |
| CN114350647B (en) * | 2021-12-23 | 2024-05-10 | 江苏大学 | Application of UCST type nonionic water-soluble polymer in immobilized glucose isomerase |
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