CN103397015A - Method for preparing magnetically regenerable immobilized bio-enzyme - Google Patents
Method for preparing magnetically regenerable immobilized bio-enzyme Download PDFInfo
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- CN103397015A CN103397015A CN2013103569433A CN201310356943A CN103397015A CN 103397015 A CN103397015 A CN 103397015A CN 2013103569433 A CN2013103569433 A CN 2013103569433A CN 201310356943 A CN201310356943 A CN 201310356943A CN 103397015 A CN103397015 A CN 103397015A
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Abstract
The invention relates to a method for preparing a magnetically regenerable immobilized bio-enzyme. The method comprises the following steps of firstly preparing ferromagnetism nano particles, mixing absolute ethyl alcohol, deionized water and a silane coupling agent, after hydrolysis, adding the ferromagnetism nano particles, stirring and reacting for 1-2 hours under the protection of nitrogen, adsorbing and settling with a magnet, washing and drying the settled solid to obtain the surface-modified ferromagnetism nano particles, then dropping a cross-linking agent for crosslinking and activating, metering a bio-enzyme preparation and oscillating at constant temperature so as to obtain the magnetically regenerable immobilized bio-enzyme. The magnetic material and the high efficient catalytic characteristics of alpha-amylase and cellulose in the bio-enzyme are combined and play a synergistic effect so as to prepare the magnetically regenerable immobilized bio-enzyme, so that the used bio-enzyme is benefit to being recycled efficiently and regenerated, and the preliminary trial on the two enzymes finds that the preparation method can be expanded to be applied to the immobilization of the whole bio-enzyme field.
Description
Technical field
But the present invention relates to a kind of preparation method of immobilized biological enzyme of magnetic force regeneration, adopt hydrothermal method to prepare nano ferriferrous oxide or micro-emulsion method for preparing nano Zero-valent Iron, modify with silane coupling agent, activate with linking agent again, introduce biological enzyme and make novel immobilized biological enzyme, belong to the biological enzyme technical field.
Background technology
Biological enzyme is as a kind of natural biological catalyst, more and more pay close attention to because its selectivity very excellent under the condition of gentleness and incomparable high-level efficiency are subject to the scientific worker, and in biological medicine, chemical industry, food and textile industry, be widely used.Yet, to do in the process of catalyzer at the applying biological enzyme, a challenge that at first runs into is exactly biological enzyme " inactivation " problem., because its reactive conditions is too harsh, must work under specific temperature, specific microenvironment (solvent system), specific potential of hydrogen.At it in use, anyly cause the small variation of biological enzyme agent environment of living in all may cause the decline of catalytic performance, even lose activity; An another one difficult problem is exactly recovery, the recycle problem of biological enzyme agent.The free enzyme of regeneration is almost impossible in reaction solvent, usually will pass through a series of purification step, and the consequent is high regeneration cost.So the load of biological enzyme, immobilization just become a kind of approach that reclaims a difficult problem that solves.But the recycling of supported biological enzyme agent still faces the problem of how to separate from reaction system, is usually to be accompanied by to filter or the unit operation such as centrifugal, and the loss that causes biological enzyme is inactivation even, and regeneration effect causes anxiety.Therefore, find a kind of can high-level efficiency, large capacity, the biological enzyme carrier that easily reclaims become the focus of this area research.
Nano magnetic material is due to the special magnetic effect of its generation, thereby has a not available performance of conventional material, make its potential application in all fields very extensive, research work for nano magnetic material and application prospect thereof no longer has been confined to single subject and single research method, but the comprehensive utilization of multidisciplinary and multiple research method is extensive at area researches such as biology, catalysis, coating, storage, medical science at present.Although magnetic nano-particle has reached nano-scale, but its size distribution is wider usually, and surface exposure, chemical property is active, very easily oxidation in air,, due to the effect of magnetic attraction and Van der Waals force, very easily occur to reunite and the coagulation phenomenon again, make magneticsubstance lose single domain magnetic pole, dispersibility or lose the distinctive character of nano material.So, it is carried out surface coating modification, to improve dispersion of particles and stability, and make it to be more widely used and seem particularly important.
Summary of the invention
But the preparation method who the purpose of this invention is to provide the immobilized biological enzyme of a kind of magnetic force regeneration, be able to high efficiente callback and regeneration after biological enzyme is used.
The technical scheme that the present invention takes is:
But a kind of preparation method of immobilized biological enzyme of magnetic force regeneration comprises that step is as follows:
(1) prepare ferromagnetism nanometer particle: prepare nano level Fe
3O
4Magnetic particle or nano zero-valence ferromagnetic particles;
(2) dehydrated alcohol, deionized water, silane coupling agent are mixed, add ferromagnetism nanometer particle after hydrolysis, stirring reaction 1-2 hour under nitrogen protection, use the magnet adsorption sedimentation, with the dry ferromagnetism nanometer particle that obtains finishing of solids wash after sedimentation;
(3) with the ferromagnetism nanometer particle of the finishing for preparing in above-mentioned steps, add buffered soln, drip linking agent, crosslinked activation 10-20min, measure biological enzyme formulation, add in the mixture after activation, reaction 1-3 hour in 30-40 ℃ of constant temperature oscillator, use deionized water wash, prepare the nano magnetic material of immobilized biological enzyme.
The described nano level Fe of step in above-mentioned preparation method (1)
3O
4The preferred following method preparation of magnetic particle: with the NaOH aqueous solution and Na
2S
2O
3Aqueous solution is in reaction flask, and then with FeSO
4The aqueous solution is added dropwise in reaction flask, after dropwising, open electric mixer and stir 1-2h, afterwards the reactant in there-necked flask is all changed in water heating kettle, reaction 12-16 hour under 160-170 ℃ of condition, after reaction finishes, product is all changed in watch-glass,, with sucking-off supernatant liquor after the magnet sedimentation, use deionized water wash 3～4 times, dry under normal temperature and pressure, obtain nano level Fe
3O
4Magnetic particle.Mol ratio NaOH:Na
2S
2O
3: FeSO
4=4:2:3.
The preferred following method preparation of described nano zero-valence ferromagnetic particles: hexadecyl Tetrabutyl amonium bromide, propyl carbinol and isooctyl alcohol are added in reaction flask and stir into uniform mixture, liquor ferri trichloridi is added in mixture, strong stirring is extremely orange transparent, and passes into N
2Protection, more slowly add SODIUM BOROHYDRIDE POWDER, continue to stir and logical N
2Protection, after the blackening of system color and no longer emitting gas, then continue to stir 0.5-1 hour; standing treat in system that black powder all is sink to bottle at the bottom of, the sucking-off supernatant liquid, add the mixing washing lotion washing of methyl alcohol and trichloromethane; use again absolute ethanol washing, obtain the nano zero-valence ferromagnetic particles.Hexadecyl Tetrabutyl amonium bromide and propyl carbinol as the consumption (but hexadecyl Tetrabutyl amonium bromide and propyl carbinol arbitrary proportion) of tensio-active agent be the isooctyl alcohol quality 20%, liquor ferri trichloridi concentration is that 0.1-0.2mol/L, SODIUM BOROHYDRIDE POWDER are 3:1 with the ratio of the amount of substance of iron trichloride, the volume ratio of liquor ferri trichloridi and isooctyl alcohol is 1:5-7.
The mass ratio of the described dehydrated alcohol of step (2), deionized water, silane coupling agent, ferromagnetism nanometer particle is 18:1:0.6-0.8:0.1-0.2, and described hydrolysis time is 1-10min.The preferred KH550 of described silane coupling agent.
The described buffered soln of step (3) is acetic acid-sodium acetate solution, pH=4-6; The mass ratio of the ferromagnetism nanometer particle of finishing, buffered soln, linking agent, biological enzyme formulation is 1:400:10:10.The preferred α-amylase of described biological enzyme formulation or cellulase.
The present invention adopts hydrothermal method to prepare magnetic nanoparticle, with silane coupling agent (KH550), modifies, and to improve dispersion of particles and stability, then, with the linking agent activation, introduces biological enzyme and makes novel immobilized biological enzyme.For example with Fe
3O
4Magnetic and biological enzyme in α-amylase, the efficient catalytic characteristic of cellulase combine, both are acted synergistically, but thereby the immobilized biological enzyme of preparation magnetic force regeneration, be convenient to high efficiente callback and regeneration after biological enzyme uses, the tentative experiment that two kinds of enzymes carry out is found this method to be expanded to be applied to the immobilized of whole biological enzyme field.
The product that the present invention makes has solved biological enzyme can not repeatedly reuse aspect practical application bottleneck.The activity that the immobilized biological enzyme of preparation is reused enzyme after 5 times still can keep 50-65%.And the present invention can adopt biological enzyme magnetic force to reclaim easily, repeatedly utilize, and so just greatly reduces the usage quantity of free enzyme, has reduced use cost.Suppose that same active free enzyme is identical with the enzyme immobilization price, every 1 batch is used bioenzyme activity to keep 10% valency to be worth 1000 yuan, and free enzyme needs again to add 10000 yuan after using 1 time, and the enzyme after immobilized uses 1 batch only need to add 3500-5000 unit.To use 5 times as benchmark, the transformation efficiency hypothesis is low to moderate 55% most, and so free enzyme and enzyme immobilization use the production cost contrast of 5 batches of generations in Table 1.
The immobilized biological enzyme of table 1 and free enzyme use cost contrast (cellulase)
By as seen from Table 1, the production cost of 5 batches, enzyme immobilization reduces half left and right than free enzyme.And it is more to reuse number of times, and production cost reduces more.
Description of drawings
But the immobilized biological enzyme infrared spectrogram of the magnetic force that Fig. 1 the present invention makes regeneration;
But the TEM photo of the immobilized biological enzyme of the magnetic force that Fig. 2 the present invention makes regeneration;
But the immobilized biological enzyme access times design sketch of Fig. 3 the present invention magnetic force regeneration;
Embodiment
The present invention will be described in detail below in conjunction with drawings and Examples.
Accurately take 13.104gFeSO with electronic balance
47H
2O in small beaker, dissolves after adding the 50ml deionized water and stirring; 13.886gNa
2S
2O
35H
2O in small beaker, dissolves after adding the 25ml deionized water and stirring; 4.480g dissolve after granular NaOH in small beaker, adds the 25ml deionized water and stirring; To be dissolved complete after, with the NaOH aqueous solution and Na
2S
2O
3The aqueous solution changes in the 250ml there-necked flask.And then with FeSO
4The aqueous solution changes in constant pressure funnel, and coutroi velocity is added dropwise in there-necked flask by the aqueous solution.After dropwising, open electric mixer and stir 1h, afterwards the reactant in there-necked flask is all changed in water heating kettle, reaction is 16 hours under 160 ℃ of conditions.Reaction all changes product in watch-glass after finishing, and, with sucking-off supernatant liquor after the magnet sedimentation, uses deionized water wash 3～4 times, and is dry under normal temperature and pressure, obtains nano level Fe
3O
4Magnetic particle.
Take the 54g dehydrated alcohol with the 100ml small beaker, add 3g deionized water (mass ratio: dehydrated alcohol water=18:1), adding 2.38g KH550(to account for system total mass mark with small beaker again is 4%), hydrolysis 10min left and right in small beaker, the nanometer Fe that adds 0.5g to prepare
3O
4In, strong stirring and logical nitrogen N
2Protection, reaction 2h.Stop stirring, magnet is placed in the flask below, the nanometer Fe after to be finished
3O
4At the bottom of all being sunken to bottle, with syringe sucking-off upper strata clear liquid, be transferred to for 3 times in watch-glass with deionized water wash dry, the Fe after the acquisition finishing
3O
4Particle, pack into and preserve with sealing in the triangular flask of grinding port plug.
With the nanoparticle for preparing in above-mentioned steps approximately 0.1g be put in the there-necked flask of 250ml, add 100ml buffered soln, drip the linking agent glutaraldehyde of (accounting for cumulative volume) 1%, crosslinked activation 20min, measure the cellulase preparation of 0.5ml, add in the solution after activation, reaction is 2 hours in constant temperature oscillator,, with deionized water wash 3-4 time, prepare the nano magnetic material of immobilized cellulase.After testing, the cellulase activity after immobilized reaches 85% of resolvase, and in the activity of using enzyme after 5 times still more than 50%.
Fe after finishing
3O
4The preparation of particle with embodiment 1.
The α-amylase that takes 1.0g is dissolved in the 100ml beaker of buffered soln, with glass stick, stirs for some time until the solid starch enzyme dissolves, and with filter paper filtering, removes insoluble impurity, and the clarified liq that obtains is transferred in the 100ml volumetric flask, and constant volume is stand-by.
Take the Fe after the 0.1g finishing
3O
4Particle be placed in the Erlenmeyer flask of 250ml, the buffered soln that adds 100ml, the linking agent glutaraldehyde that adds (accounting for cumulative volume) 1%, crosslinked activation 20min, measure the α-amylase solution 10ml that has configured, add in the solution after activation, reaction is 2 hours in constant temperature oscillator, with deionized water wash repeatedly, prepare the nano magnetic material of immobilized α-amylase.After testing, the amylase activity after immobilized reaches 87% of resolvase, and in the activity of using enzyme after 5 times still more than 60%.
5.50g hexadecyl Tetrabutyl amonium bromide (CTAB), 16.50g propyl carbinol and 68.00g isooctyl alcohol are added in the 250ml there-necked flask and stir into uniform mixture, the liquor ferri trichloridi 10ml of 0.1M is added in mixture, strong stirring is extremely orange transparent, and passes into N
2Protection, more slowly add the 0.12g SODIUM BOROHYDRIDE POWDER, continue to stir and logical N
2Protection, after the blackening of system color and no longer emitting gas, then continue to stir half an hour.Standing treat in system that black powder all is sink to bottle at the bottom of, the sucking-off supernatant liquid, add the mixing washing lotion washing of 50ml methyl alcohol and trichloromethane, and with same method sucking-off washings, use again the 50ml dehydrated alcohol, also, with same quadrat method washing, obtain the nano zero-valence ferromagnetic particles.
Take the 54g dehydrated alcohol, add the 3g deionized water, then add 2.38g KH570, hydrolysis 10min left and right, add in the nanometer nulvalent iron particle of the above-mentioned preparation of 0.3g, strong stirring and logical N
2Protection, reaction 3h.Sucking-off upper strata clear liquid, can separate with the suction filtration method with the nano zero valence iron of KH570 parcel, obtains the nanometer nulvalent iron particle that KH570 modifies.
With the nanometer nulvalent iron particle for preparing in above-mentioned steps approximately 0.1g be put in the there-necked flask of 250ml, add 100ml buffered soln, drip the linking agent oxalic dialdehyde of (accounting for cumulative volume) 1%, crosslinked activation 20min, measure the cellulase preparation of 0.5ml, add in the solution after activation, reaction is 2 hours in constant temperature oscillator,, with deionized water wash 3-4 time, prepare the nano magnetic material of immobilized cellulase.After testing, the cellulase activity after immobilized reaches 80% of resolvase, and in the activity of using enzyme after 5 times still more than 55%.
The preparation of the nanometer nulvalent iron particle that KH570 modifies is with embodiment 3.
The nanometer nulvalent iron particle that takes the 0.1gKH570 modification is placed in the Erlenmeyer flask of 250ml, the buffered soln that adds 100ml, the linking agent oxalic dialdehyde that adds (accounting for cumulative volume) 1%, crosslinked activation 20min, measure α-amylase solution (with the embodiment 2) 10ml that configures, add in the solution after activation, reaction is 2 hours in constant temperature oscillator, with deionized water wash repeatedly, prepare the nano magnetic material of immobilized α-amylase.After testing, the amylase activity after immobilized reaches 85% of resolvase, and in the activity of using enzyme after 5 times still more than 65%.
Claims (10)
1. but the preparation method of the immobilized biological enzyme of a magnetic force regeneration, is characterized in that, comprises that step is as follows:
(1) prepare ferromagnetism nanometer particle: prepare nano level Fe
3O
4Magnetic particle or nano zero-valence ferromagnetic particles;
(2) dehydrated alcohol, deionized water, silane coupling agent are mixed, add ferromagnetism nanometer particle after hydrolysis, stirring reaction 1-2 hour under nitrogen protection, use the magnet adsorption sedimentation, with the dry ferromagnetism nanometer particle that obtains finishing of solids wash after sedimentation;
(3) with the ferromagnetism nanometer particle of the finishing for preparing in above-mentioned steps, add buffered soln, drip linking agent, crosslinked activation 10-20min, measure biological enzyme formulation, add in the mixture after activation, reaction 1-3 hour in 30-40 ℃ of constant temperature oscillator, use deionized water wash, prepare the nano magnetic material of immobilized biological enzyme.
2. but the preparation method of the immobilized biological enzyme of a kind of magnetic force regeneration according to claim 1, is characterized in that the described nano level Fe of step (1)
3O
4Magnetic particle selects following method preparation: with the NaOH aqueous solution and Na
2S
2O
3Aqueous solution is in reaction flask, and then with FeSO
4The aqueous solution is added dropwise in reaction flask, after dropwising, open electric mixer and stir 1-2h, afterwards the reactant in there-necked flask is all changed in water heating kettle, reaction 12-16 hour under 160-170 ℃ of condition, after reaction finishes, product is all changed in watch-glass,, with sucking-off supernatant liquor after the magnet sedimentation, use deionized water wash 3～4 times, dry under normal temperature and pressure, obtain nano level Fe
3O
4Magnetic particle.
3. but the preparation method of the immobilized biological enzyme of a kind of magnetic force regeneration according to claim 1, it is characterized in that, described nano zero-valence ferromagnetic particles is selected following method preparation: hexadecyl Tetrabutyl amonium bromide, propyl carbinol and isooctyl alcohol are added in reaction flask and stir into uniform mixture, liquor ferri trichloridi is added in mixture, strong stirring is extremely orange transparent, and passes into N
2Protection, more slowly add SODIUM BOROHYDRIDE POWDER, continue to stir and logical N
2Protection, after the blackening of system color and no longer emitting gas, then continue to stir 0.5-1 hour; standing treat in system that black powder all is sink to bottle at the bottom of, the sucking-off supernatant liquid, add the mixing washing lotion washing of methyl alcohol and trichloromethane; use again absolute ethanol washing, obtain the nano zero-valence ferromagnetic particles.
4. but the preparation method of the immobilized biological enzyme of a kind of magnetic force regeneration according to claim 1, it is characterized in that, the mass ratio of the described dehydrated alcohol of step (2), deionized water, silane coupling agent, ferromagnetism nanometer particle is 18:1:0.6-0.8:0.1-0.2.
5. but the preparation method of the immobilized biological enzyme of a kind of magnetic force regeneration according to claim 1, is characterized in that, the described silane coupling agent of step (2) selects KH550.
6. but the preparation method of the immobilized biological enzyme of a kind of magnetic force regeneration according to claim 1, is characterized in that, the described buffered soln of step (3) is acetic acid-sodium acetate solution, pH=4-6.
7. but the preparation method of the immobilized biological enzyme of a kind of magnetic force regeneration according to claim 1, is characterized in that the mass ratio 1:400:10:10 of the ferromagnetism nanometer particle of finishing, buffered soln, linking agent, biological enzyme formulation.
8. but the preparation method of the immobilized biological enzyme of a kind of magnetic force regeneration according to claim 1, is characterized in that the preferred α-amylase of described biological enzyme formulation or cellulase.
9. but the preparation method of the immobilized biological enzyme of a kind of magnetic force regeneration according to claim 1, is characterized in that, described linking agent is glutaraldehyde or oxalic dialdehyde.
10. the immobilized biological enzyme of method preparation claimed in claim 1, is characterized in that, the activity of reusing enzyme after 5 times still keeps 50-65%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107418948A (en) * | 2017-07-20 | 2017-12-01 | 苏州凯邦生物技术有限公司 | A kind of high efficiency process for fixation of alkaline pectase |
| CN109315795A (en) * | 2018-11-27 | 2019-02-12 | 湖北文理学院 | A kind of method of enzyme process joint infra-red drying removal walnut kernel pellicle |
| CN110302807A (en) * | 2019-07-01 | 2019-10-08 | 山东大学 | A kind of preparation method and application of modified Zero-valent Iron liquid catalyst |
| CN111908754A (en) * | 2020-06-17 | 2020-11-10 | 华南理工大学 | Iron-silicon biological enzyme magnetic composite material for sludge dewatering and synthetic method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107418948A (en) * | 2017-07-20 | 2017-12-01 | 苏州凯邦生物技术有限公司 | A kind of high efficiency process for fixation of alkaline pectase |
| CN107418948B (en) * | 2017-07-20 | 2020-05-12 | 苏州凯邦生物技术有限公司 | High-efficiency immobilization method of alkaline pectinase |
| CN109315795A (en) * | 2018-11-27 | 2019-02-12 | 湖北文理学院 | A kind of method of enzyme process joint infra-red drying removal walnut kernel pellicle |
| CN110302807A (en) * | 2019-07-01 | 2019-10-08 | 山东大学 | A kind of preparation method and application of modified Zero-valent Iron liquid catalyst |
| CN110302807B (en) * | 2019-07-01 | 2021-12-28 | 山东大学 | Preparation method and application of modified zero-valent iron liquid catalyst |
| CN111908754A (en) * | 2020-06-17 | 2020-11-10 | 华南理工大学 | Iron-silicon biological enzyme magnetic composite material for sludge dewatering and synthetic method |
| CN111908754B (en) * | 2020-06-17 | 2022-02-15 | 华南理工大学 | Iron-silicon biological enzyme magnetic composite material for sludge dewatering and synthetic method |
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