CN1580233A - Immobilized enzyme mesoporous reactor and its preparing method - Google Patents
Immobilized enzyme mesoporous reactor and its preparing method Download PDFInfo
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- CN1580233A CN1580233A CN 03150039 CN03150039A CN1580233A CN 1580233 A CN1580233 A CN 1580233A CN 03150039 CN03150039 CN 03150039 CN 03150039 A CN03150039 A CN 03150039A CN 1580233 A CN1580233 A CN 1580233A
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Abstract
The invention gives a kind of reactor with aperture for enzyme immobilization and the preparation. This reactor with aperture is used for immobilizing enzyme in the aperture that immobilize enzyme molecule in the aperture under the condition of reaction of surface hydroxy group and enzyme molecule carboxy oxo atomy in the aperture because the aperture is fair sized. And then graft silane coupler at orifice of material with aperture by method of grafting. At late, use the double bonded polymerization at the end of silane coupler to form mesh structure. In this method, the orifice can be lessened and can not produce mass transfer resistance to the substrate and the putcome when it check running of enzyme molecule. Thus, the immobilized enzyme with high catalytic activity and high stability can be get.
Description
Technical field: the present invention relates to the immobilization technology of biomacromolecule proteolytic enzyme, relate generally to mesoporous reactor of a kind of immobilized enzyme and preparation method thereof.
Background technology: enzyme immobilization is that enzyme is fixed on the carrier, to solve problems such as reacted enzyme-to-substrate separation, recovery and repeated use.The method of immobilized enzyme can be divided into two big classes substantially, and a class is the physics method, and another kind of is chemical method.The physics method is meant that enzyme and carrier interact with more weak reactive force, this weak interaction can not make the three-dimensional conformation conversion of enzyme be restricted, thereby can not influence the vigor of enzyme, but this weak interaction can cause the loss of enzyme inevitably in catalyzed reaction, enzyme is lived reduce.Chemical method is meant that enzyme and carrier are with stronger reactive force interactions such as covalent linkage, though strong interaction can reduce the loss of enzyme, but cause the 3-d modelling degree of freedom of enzyme to reduce simultaneously, cause enzyme-to-substrate to do the time spent, suitably conversion can not take place to adapt to the configuration of substrate in the conformation of enzyme, be that the active sites of enzyme and the point of application of substrate can not take place effectively to agree with, reduce thereby cause enzyme to be lived.All the time, people are seeking effective immobilized enzyme method.
Since mesoporous material in 1992 comes out, caused showing great attention to of people.Mesoporous material has the high and equal first-class characteristics of pore size distribution of specific surface area, as carrier, can increase substantially the charge capacity of enzyme on carrier with mesoporous material; In addition, hydroxyl is rich on the mesoporous material surface more, can improve the stability of enzyme on carrier by certain interaction, so mesoporous material has obtained attention as the immobilized excellent carrier of class of enzymes.
Document 1:Humphrey H.P.Yiu, Paul A.Wright, Nigel P.Botting, Microporous and Mersoporous Materials 44-45,763,2001 have introduced in the mesoporous material that directly Regular Insulin is fixed on MCM-41, MCM-48, SBA-15 difference pore sizes, and experimental result shows that the immobilization efficiency of enzyme in mesoporous material can reach 90%.Illustrate that mesoporous material is well suited for the carrier as enzyme immobilization.But when the mesoporous material of this immobilized enzyme still has a large amount of enzymes to run off after long-time reaction, the degree of its loss is directly related with the aperture of mesoporous material.For the mesoporous material of small-bore, if the enzyme molecule greater than the aperture of this mesoporous material, then the enzyme molecule can't enter the outside surface that can only be attached to the hole in mesoporous, so cause a large amount of loss of enzyme; For big-pore mesoporous material, though the enzyme molecule is easy to enter in the hole, enzyme also is easy to run off from the aperture of opening wide during reaction.
The loss of enzyme when reducing big-pore mesoporous material immobilized enzyme reaction, document 2:Diaz J.F., Balkus K.J., J.Mol.Catal.B:Enzymatic 2,115,1996 have proposed to carry out with silane coupling agent the aperture modification of mesoporous material, to reach the purpose of dwindling the mesoporous material aperture.It is fixed on cell C on the mesoporous material MCM-41 (aperture 4nm) earlier, carries out grafting with γ-An Jibingjisanyiyangjiguiwan in its aperture again the aperture is dwindled.This grafted method has effectively reduced the loss of enzyme, has kept alive the stablizing of enzyme.But this method only is suitable for adopting the aperture less than the mesoporous material immobilized enzyme molecular dimension of the 4nm small molecules enzyme less than 4nm, as cell C, papoid, Regular Insulin and subtilisin etc.When the aperture of mesoporous material greater than 4nm, because that this grafting method makes the aperture dwindle degree is little, so still have a large amount of phenomenons that run off of enzyme on fixing.
Summary of the invention: the objective of the invention is, in order to make the mesoporous material immobilized enzyme be applicable to various enzymes, and make more effectively immobilized enzyme of mesoporous material, avoid the loss of enzyme in the reaction process, proposition utilizes grafting, polymerization means that netted sealing carried out in the aperture of immobilized enzyme mesoporous material, makes up a kind of mesoporous reactor.
The present invention earlier is added to mesoporous material the mesoporous material (IME-MMM) of being fixed enzyme in the solution of resolvase; Again silane coupling agent is grafted to around the aperture of immobilized enzyme mesoporous material, make the contained two keys of silane coupling agent carry out polymerization with thermal initiator then, the netted chain that forms is sealed the aperture of immobilized enzyme mesoporous material or is dwindled, and this aperture is called mesoporous reactor by the netted immobilized enzyme mesoporous material of sealing or dwindling.
It is as follows that this mesoporous reacting appliance system is equipped with step:
A. be that the ratio of 1: 5～7 (g/l) is added in the there-necked flask with enzyme, damping fluid according to the mass/volume ratio, add deionized water, mix by the amount of 3～4 times of volume of buffer solution; Again mesoporous material (or carrier) is pressed enzyme: the mass ratio of carrier=1: 1～2 adds Erlenmeyer flask, seal the bottleneck of Erlenmeyer flask after shaking all, place 0～30 ℃ shaking table, keep shaking table concussion speed 100～200r/min concussion 6h～24h, being fixed enzyme carrier (IME-MMM).
B. silane coupling agent is dissolved in organic solvent in the ratio of 10～20ml/g, the preparation silane coupler solution.
C. the IME-MMM that steps A is obtained uses the cold acetone thorough washing to remove moisture wherein; place four-hole bottle then; four-hole bottle placed in 50 ℃～90 ℃ the water-bath; under the condition of logical N2 gas shiled; add silane coupler solution; the add-on of silane coupler solution is determined in the ratio of silane coupling agent: IME-MMM=4～6: 1; carry out induction stirring while adding; the solvent that condenser makes evaporation is housed above four-hole bottle to be got back in the four-hole bottle; 2～8h is carried out in reaction, obtains the immobilized enzyme mesoporous material of aperture grafted silane coupling agent.
D. the four-hole bottle to step C adds thermal initiator again, keeping the water-bath temperature is 50 ℃～90 ℃, two keys that silane coupling agent is contained carry out polymerization, the consumption of thermal initiator is that 1～3wt%. polyreaction of silane coupling agent consumption carries out stopping, cooling off behind 6～16h, product is removed wherein moisture with cold acetone solution thorough washing, obtain mesoporous reactor.
The used mesoporous material of steps A should be the one dimension or the three-dimensional clear opening structured material of pore size distribution homogeneous, can select a kind of among SBA-15, MCM-41, MCM-48 or the FSM for use; Preferred SBA-15.
Used enzyme is to have sphere or oval outer shape, the water-soluble and enzyme of molecular dimension more than 3.7nm, a kind of in optional porcine pancreatic lipase, horseradish peroxidase, sphaeroprotein enzyme, the Regular Insulin.
Used buffered soln is phosphate buffer solution, and the buffer value scope is in PH=7～8, and each enzyme all has its best buffer value.The adding of damping fluid is in order to make enzyme bring into play catalytic effect better.
The used silane coupling agent of step B is the silane that contains long alkyl chain and contain two keys in the termination of alkyl chain, optional r-(methacryloxy) propyl trimethoxy silicane (trade(brand)name: KH-570), 7-octyl group Trimethoxy silane, vinyltrimethoxy silane (trade(brand)name: A-171) or vinyltriethoxysilane (trade(brand)name: a kind of A-151).Preferred KH-570 or 7-octyl group Trimethoxy silane;
Used organic solvent is the non-polar solvent that can dissolve used silane coupling agent, one of optional heptane, octane, benzene, toluene, methylene dichloride.
The used thermal initiator of step C can be a kind of in Diisopropyl azodicarboxylate (AIBN), dibenzoyl peroxide (BPO), dilauroyl peroxide, isopropyl benzene hydroperoxide, the peroxide tert pivalate ester, preferred AIBN and BPO.
The product that step C and step D are obtained carries out low temperature N2 suction-desorption isotherm and measures respectively, obtains Fig. 2, thermoisopleth shown in Figure 3.By pattern as can be seen, the mesoporous material that step C obtains is still the unidimensional cavernous structure, and step D has obtained tripe big young shape, i.e. bottleneck shape structure.
By mesoporous reactor structures of samples signature analysis is shown: mesoporous reactor still has good long range ordered structure, its orifice diameter is much smaller than the enzyme bulk of molecule, therefore the enzyme molecule is fixed in the mesoporous material with being stabilized, is difficult for carrying out and run off with reaction.
In order to the microtexture of the mesoporous reactor of top method preparation as shown in Figure 1, the enzyme molecule is fixed in the mesoporous material, the aperture of mesoporous material is reduced owing to the chain web frame of silane coupling agent polymerization formation, make the orifice diameter of mesoporous material much smaller than the enzyme bulk of molecule, this method can be carried out the immobilization of various size enzyme molecule according to the size of carrier aperture.Chain length by the modulation silane coupling agent reaches the purpose of dwindling the aperture effectively, so this method is more suitable for the immobilization of numerous macromole enzyme.
Prepare immobilized enzyme mesoporous material IME-MMM (sample 1) with the method for document 1, prepare aperture grafted IME-MMM (sample 2), prepare the comparative determination that mesoporous reactor carries out enzyme stability alive with the embodiment of the invention 1～3 with the method for document 2.With above-mentioned three samples respectively at normal temperatures, be put in and stir the mensuration of carrying out enzyme work behind 3～5h in the phosphoric acid buffer, the concrete grammar of measuring is: under 37 ℃ of homothermic conditions, vanay with concentration 6.8% is a substrate, take out sample behind the reaction 10min and carry out centrifugation, the filtrate that obtains after the separation as indicator, is carried out titration with NaOH with phenolphthalein, thereby the enzyme that calculates first set reaction is lived; The solid that obtains after the separation repeats above-mentioned measuring method, and the enzyme that obtains reaction is for the second time lived, and so replication is 5 times, and what record the results are shown in Table 1.This measuring method is called as intermittent process.
Table 1. enzyme stable comparative determination alive
| Number of operations | Sample 1 | Sample 2 | Embodiment 1 | Embodiment 2 | Embodiment 3 | |||||
| Enzyme (IU/g) alive | Relative vigor (%) | Enzyme (IU/g) alive | Relative vigor (%) | Enzyme (IU/g) alive | Relative vigor (%) | Enzyme (IU/g) alive | Relative vigor (%) | Enzyme (IU/g) alive | Relative vigor (%) | |
| 1 | ??198 | ??52 | ??200 | ??52 | ??224 | ??58 | ??200 | ??52 | ??150 | ??39 |
| 2 | ??182 | ??47 | ??198 | ??52 | ??226 | ??59 | ??201 | ??52 | ??150 | ??39 |
| 3 | ??162 | ??42 | ??190 | ??50 | ??220 | ??57 | ??195 | ??50 | ??146 | ??38 |
| 4 | ??160 | ??42 | ??180 | ??47 | ??220 | ??57 | ??196 | ??51 | ??145 | ??38 |
| 5 | ??142 | ??37 | ??175 | ??45 | ??220 | ??57 | ??196 | ??51 | ??145 | ??38 |
The present invention has following remarkable benefit:
The mesoporous reactor of the present invention's preparation still orifice diameter is fixed in the mesoporous material enzyme molecule much smaller than the enzyme bulk of molecule with being stabilized, the loss of inhibitory enzyme effectively, the operational stability that keeps enzyme to live.The present invention has enlarged the range of application of mesoporous material as enzyme immobilization carrier, has further utilized the advantage of mesoporous material as enzyme immobilization carrier; Simultaneously also enlarged bio protease and be fixed on quantity in the mesoporous material, made the immobilization that expands to by original only small molecules enzyme immobilization than the high molecular weight protein enzyme.
Description of drawings:
Fig. 1 is mesoporous reactor microstructure models synoptic diagram.
Fig. 2 is the mesoporous material low temperature N in the straight-through duct of one dimension
2Suction-desorption isotherm
The mesoporous reactor of Fig. 3 forms back low temperature N
2Suction-desorption isotherm
Embodiment:
Embodiment 1
A. (the mean molecule diameter is 4～5nm) fully to be dissolved in the 1.25ml phosphoric acid buffer of pH=7.7 to take by weighing the 0.25g porcine pancreatic lipase, add the 49ml deionized water again, mix the back and add 0.5g SBA-15 carrier (mean pore size is 6.6nm), be put in 30 ℃ the shaking table fixedly 12h after sealing, shaking table concussion speed keeps 150r/min.Obtain SBA-15 immobilized enzyme IME-SBA.
B. 3g KH-570 silane coupling agent is joined in the 30ml toluene solvant and thorough mixing.
C. the immobilized enzyme IME-SBA that steps A is obtained, to doing, all adding has in the four-hole bottle of condenser, at N with the cold acetone thorough washing
2Under the gas shiled, in the silane coupler solution adding four-hole bottle with step B, stir while adding, continue 3 hours, obtain the immobilized enzyme mesoporous material of silane coupling agent in the grafting of aperture, be called for short IME-SBA-MA;
D. in above-mentioned reaction solution, add 0.03g initiator A IBN again, keep 70 ℃ constant temperature to make polyreaction carry out 8h, the mesoporous reactor that obtains with cold acetone solution thorough washing, is put at normal temperatures in the 15ml phosphoric acid buffer of pH=7.7 and stirs 3h to keep its enzymic activity.
The mesoporous reactor that obtains is carried out the enzyme stability of living measure, the enzyme work of continuous this mesoporous reactor that records for 5 times sees Table 1 with the relative vigor of immobilized enzyme.
By structures of samples signature analysis, show that mesoporous reactor still has good long range ordered structure to mesoporous reactor; By C=O functional group on the KH-570 silane coupling agent at 1702cm
-1Wave number moves to high wave number, illustrates that polymerization has taken place the two keys of C=C among the KH-570.After forming by mesoporous reactor, thermoisopleth changes tangible H2 type hysteresis loop into by original H1 type hysteresis loop, shows that mesoporous material has formed and has the big young shape (being bottleneck shape structure) of tripe.And its orifice diameter is 3.7nm.
Embodiment 2
KH-570 among the step B is replaced with octyl group Trimethoxy silane coupling agent, and other is with embodiment 1.
The mesoporous reactor that obtains is carried out the enzyme stability of living measure, the enzyme work of continuous this mesoporous reactor that records for 5 times sees Table 1 with the relative vigor of immobilized enzyme.
Embodiment 3
Toluene solvant in the B step is replaced with dichloromethane solvent, and other is with embodiment 1.
The mesoporous reactor that obtains is carried out the enzyme stability of living measure, the enzyme work of continuous this mesoporous reactor that records for 5 times sees Table 1 with the relative vigor of immobilized enzyme.
Claims (6)
1. the preparation method of the mesoporous reactor of immobilized enzyme, concrete preparation process is as follows:
A. be that the ratio of 1: 5～7 (g/l) is added in the there-necked flask with enzyme, damping fluid according to the mass/volume ratio, add deionized water, mix by the amount of 3～4 times of volume of buffer solution; Again mesoporous material is pressed enzyme: the mass ratio of mesoporous material=1: 1～2 adds Erlenmeyer flask, seal the bottleneck of Erlenmeyer flask after shaking all, place 0～30 ℃ shaking table, keep shaking table concussion speed 100～200r/min concussion 6h～24h, being fixed enzyme carrier IME-MMM;
B. silane coupling agent is dissolved in organic solvent in the ratio of 10～20ml/g, the preparation silane coupler solution;
C. the IME-MMM that steps A obtained to remove moisture wherein, places four-hole bottle with the cold acetone thorough washing then, four-hole bottle is placed in 50 ℃～90 ℃ the water-bath, at logical N
2Under the condition of gas shiled, add silane coupler solution, the add-on of silane coupler solution is determined in the ratio of silane coupling agent: IME-MMM=4～6: 1, carry out induction stirring while adding, the solvent that condenser makes evaporation is housed above four-hole bottle to be got back in the four-hole bottle, 2～8h is carried out in reaction, obtains the immobilized enzyme mesoporous material of aperture grafted silane coupling agent;
D. the four-hole bottle to step C adds thermal initiator again, keeping the water-bath temperature is 50 ℃～90 ℃, two keys that silane coupling agent is contained carry out polymerization, the consumption of thermal initiator is 1～3wt% of silane coupling agent consumption, polyreaction is carried out 6～16h and is stopped, cools off, product is removed wherein moisture, the mesoporous reactor of being fixed enzyme with cold acetone solution thorough washing.
2. the preparation method of the mesoporous reactor of immobilized enzyme according to claim 1 is characterized in that:
The described mesoporous material of steps A should be the one dimension or the three-dimensional clear opening structured material of pore size distribution homogeneous; Enzyme is to have sphere or oval outer shape, the water-soluble and enzyme of molecular dimension more than 3.7nm; Buffered soln is phosphate buffer solution, and the buffer value scope is in PH=7～8;
The described silane coupling agent of step B is the silane that contains long alkyl chain and contain two keys in the termination of alkyl chain; Organic solvent is the non-polar solvent that can dissolve used silane coupling agent.
3. the preparation method of the mesoporous reactor of immobilized enzyme according to claim 2 is characterized in that:
The described mesoporous material of steps A can be selected a kind of among SBA-15, MCM-41, MCM-48, the FSM for use; Enzyme can be selected a kind of in porcine pancreatic lipase, horseradish peroxidase, sphaeroprotein enzyme, the Regular Insulin for use;
The described silane coupling agent of step B can be selected a kind of in r-(methacryloxy) propyl trimethoxy silicane, 7-octyl group Trimethoxy silane, vinyltrimethoxy silane, the vinyltriethoxysilane for use; Organic solvent can be a kind of in heptane, octane, benzene, toluene, the methylene dichloride;
The described thermal initiator of step C can be a kind of in Diisopropyl azodicarboxylate, dibenzoyl peroxide, dilauroyl peroxide, isopropyl benzene hydroperoxide, the peroxide tert pivalate ester.
4. according to the preparation method of claim 2, the mesoporous reactor of 3 described immobilized enzyme, it is characterized in that:
The preferred SBA-15 of the described mesoporous material of steps A;
The preferred r-of the described silane coupling agent of step B (methacryloxy) propyl trimethoxy silicane, 7-octyl group Trimethoxy silane;
The preferred Diisopropyl azodicarboxylate of the described thermal initiator of step C, dibenzoyl peroxide.
5. mesoporous reactor of immobilized enzyme, major technique feature are that this reactor is to adopt the described preparation method of claim 1 to prepare.
6. the mesoporous reactor of immobilized enzyme according to claim 5, its principal character be this mesoporous reactor microtexture as shown in Figure 1, the enzyme molecule is fixed in the mesoporous material, the aperture of mesoporous material is reduced by the chain web frame that the silane coupling agent polymerization forms, and the orifice diameter of mesoporous material is much smaller than the enzyme bulk of molecule.
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| CN100383242C (en) * | 2005-10-08 | 2008-04-23 | 北京化工大学 | Miniature enzyme reactor with controllable size and property and its prepn |
| CN101974509A (en) * | 2010-09-17 | 2011-02-16 | 北京化工大学 | Preparation method of multi-level structure immobilized enzyme |
| CN102241406A (en) * | 2010-05-11 | 2011-11-16 | 哈尔滨工业大学 | Carboxylated MCM-41 mesoporous molecular sieve for adsorbing heavy metal ions, and preparation method thereof |
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| US10881102B2 (en) | 2015-05-18 | 2021-01-05 | Zymtronix, Llc | Magnetically immobilized microbiocidal enzymes |
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| CN100383242C (en) * | 2005-10-08 | 2008-04-23 | 北京化工大学 | Miniature enzyme reactor with controllable size and property and its prepn |
| CN102241406A (en) * | 2010-05-11 | 2011-11-16 | 哈尔滨工业大学 | Carboxylated MCM-41 mesoporous molecular sieve for adsorbing heavy metal ions, and preparation method thereof |
| CN101974509A (en) * | 2010-09-17 | 2011-02-16 | 北京化工大学 | Preparation method of multi-level structure immobilized enzyme |
| CN101974509B (en) * | 2010-09-17 | 2012-05-30 | 北京化工大学 | Preparation method of multi-level structure immobilized enzyme |
| US9765324B2 (en) * | 2012-10-05 | 2017-09-19 | Cornell University | Hierarchical magnetic nanoparticle enzyme mesoporous assemblies embedded in macroporous scaffolds |
| US20150252352A1 (en) * | 2012-10-05 | 2015-09-10 | Cornell University | Magnetic hierarchical catalysts of nanoparticles and enzymes forming mesoporous assemblies embedded in macroporous scaffolds, and their use with magnetically-driven reactors and in chemical reactions |
| US10351841B2 (en) | 2012-10-05 | 2019-07-16 | Cornell University | Method for inhibiting growth of microorganisms with macroporous scaffolds |
| US10767172B2 (en) | 2012-10-05 | 2020-09-08 | Cornell University | Method for epoxidation to produce alkene oxide |
| US11236322B2 (en) | 2012-10-05 | 2022-02-01 | Cornell University | Enzyme forming mesoporous assemblies embedded in macroporous scaffolds |
| CN103893745A (en) * | 2012-12-26 | 2014-07-02 | 长春理工大学 | Methylated MCM-41 molecular sieve slow-release insulin and preparation method thereof |
| US10881102B2 (en) | 2015-05-18 | 2021-01-05 | Zymtronix, Llc | Magnetically immobilized microbiocidal enzymes |
| US11517014B2 (en) | 2015-05-18 | 2022-12-06 | Zymtronix, Inc. | Magnetically immobilized microbiocidal enzymes |
| US10792649B2 (en) | 2015-07-15 | 2020-10-06 | Zymtronix, Llc | Automated bionanocatalyst production |
| US10993436B2 (en) | 2016-08-13 | 2021-05-04 | Zymtronix Catalytic Systems, Inc. | Magnetically immobilized biocidal enzymes and biocidal chemicals |
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