CN107267494A - The@Fe of enzyme@ZIF 83O4Magnetic Nano enzyme reactor and preparation method thereof - Google Patents
The@Fe of enzyme@ZIF 83O4Magnetic Nano enzyme reactor and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of@Fe of enzyme@ZIF 83O4Magnetic Nano enzyme reactor and preparation method thereof, using denovo methods in Fe3O4ZIF 8 is coated after magnetic nano-particle surface modification citric acid, the@Fe of ZIF 8 are formed3O4Core shell structure, at the same it is during ZIF 8 is coated that chloroperoxidase, horseradish peroxidase or cromoci is immobilized on ZIF 8, obtain the@Fe of enzyme@ZIF 8 with Magnetic Isolation effect3O4The Fe of magnetic Nano enzyme reactor, wherein citric acid modification3O4The particle diameter of magnetic nano-particle is 250~300nm, and the thickness of the shells of ZIF 8 of its surface coated enzyme immobilization is 50~80nm.Preparation method of the present invention is easy, the@Fe of gained enzyme@ZIF 83O4The heat endurance and ph stability of magnetic Nano enzyme reactor are significantly increased compared with resolvase, and with splendid reusability.
Description
Technical field
The invention belongs to fixation techniques for enzyme field, and in particular to a kind of magnetic Nano enzyme reactor being easily isolated
Enzyme@ZIF-8@Fe3O4And preparation method thereof.
Background technology
Enzymic catalytic reaction due to mild condition, efficiently and directionally, it is environment-friendly the features such as, be nowadays widely used in
The fields such as organic synthesis, medicine preparation, are considered as the important means of chemicals green syt, to realizing that the strategy of sustainable development has
It is significant.The protein that enzyme is made up of amino acid, with level Four space structure, its higher structure is very quick to environment
Sense, many extraneous factors such as physical factor (temperature, pressure), chemical factor (redox, organic solvent, pH, ionic strength,
Metal ion) and biological factor (modification of enzyme, enzyme degraded) can all have to the activity of enzyme and compare large effect.Enzyme is even in most suitable
Under the conditions of reacted, reaction speed can also be declined with extending with for reaction time, and resolvase participate in reaction after,
It is difficult to which recycling, adds reaction cost.These inferior positions of enzyme can be improved by enzyme immobilizatio, so as to increase it
Operational stability.
Metal-organic framework materials (Metal-Organic Frameworks, abbreviation MOFs), also known as inorganic-organic
Hybrid material, refers to that what is be self-assembly of between metal center and multiple tooth organic ligand has one-dimensional, two-dimentional or Magnetic Properties of Three-Dimensional Supramolecular Complex
The crystalline state porous material of microporous network structure.MOFs materials have that good pore structure, pore distribution are uniform, specific surface area is big,
High stability and the features such as 26S Proteasome Structure and Function has adjustability, therefore in gas absorption and separation, chemical catalysis, drug delivery
And there is utilization widely in the field such as release, protein immobilization.MOFs materials are used as enzyme immobilizatio carrier, in enzyme
During use can compared with limits the leakage for avoiding enzyme, improve its operational stability and reusability.Because
The group of the suitable hole size of MOFs materials, perfect pattern and some surface modifications is conducive to enzyme immobilizatio.With MOFs materials
Expect that microfluidic platform design synthesis immobilized enzyme reactor is a newer research field, constructed by changing in MOFs materials process
Organic ligand type, can construct out the MOFs materials of different pore size size and surface with different modifying group is used for enzyme
Immobilization.
The content of the invention
It is an object of the invention to provide a kind of enzyme@ZIF-8@Fe being easily isolated3O4Magnetic Nano enzyme reactor, and
The preparation method of the reactor.
Solving the technical scheme that is used of above-mentioned technical problem is：The magnetic Nano enzyme reactor is with citric acid modification
Fe3O4Magnetic nano-particle is core, in one layer of ZIF-8 shell of its Surface coating, forms ZIF-8@Fe3O4Core shell structure, then will
Enzyme is fixed on carrier, wherein described enzyme is any one in chloroperoxidase, horseradish peroxidase, cromoci
Kind, the Fe of citric acid modification3O4The particle diameter of magnetic nano-particle is outside 250~300nm, the ZIF-8 of its surface coated enzyme immobilization
The thickness of shell is 50~80nm.
Enzyme@ZIF-8@Fe of the present invention3O4The preparation method of magnetic Nano enzyme reactor is made up of following step：
1st, citric acid modification Fe3O4Magnetic nano-particle
By magnetic Fe3O4Powder is dispersed in ultra-pure water, 1~3mol/L aqueous citric acid solution is then added, in N2
Lower 80~100 DEG C of protection is stirred 60~120 minutes, is cooled to room temperature, and with pure water is used after magnet separation product, vacuum is done
It is dry, obtain the Fe of citric acid modification3O4Magnetic nano-particle.
2nd, enzyme@ZIF-8@Fe are prepared3O4Magnetic Nano enzyme reactor
By the Fe of citric acid modification3O4Magnetic nano-particle is dispersed in ethanol water, adds Zn (NO3)2, matter
It is 37% HCl/water solution, 2-methylimidazole, polyvinylpyrrolidone, enzyme to measure fraction, and stirring at normal temperature 10~20 minutes uses magnetic
After iron separation product, successively with ethanol and milli-Q water, vacuum drying obtains enzyme@ZIF-8@Fe3O4Magnetic Nano enzyme reaction
Device.
In upper step 1, preferred magnetic Fe3O4The mol ratio of powder and citric acid is 1:(2~3), further preferably in N2Protect
Lower 90 DEG C are protected to stir 90 minutes.
In above-mentioned steps 2, Zn (NO3)2, 2-methylimidazole, HCl mol ratio be 1:(8~12):(0.05~0.2), lemon
The Fe of lemon acid modification3O4Magnetic nano-particle and enzyme, Zn (NO3)2, polyvinylpyrrolidone mass ratio be 100:(0.1~1):
(80~150):(150~250), preferably Zn (NO3)2, HCl, 2-methylimidazole mol ratio be 1:0.1:10, citric acid modification
Fe3O4Magnetic nano-particle and enzyme, Zn (NO3)2, polyvinylpyrrolidone mass ratio be 100:0.4:110:180.
In above-mentioned steps 2, the volumetric concentration of ethanol is preferably 40%~60% in the ethanol water.
The weight average molecular weight of above-mentioned polyvinylpyrrolidone is 8000~12000.
The present invention is using denovo methods in Fe3O4ZIF-8 is coated after magnetic nano-particle surface modification citric acid, is formed
ZIF-8@Fe3O4Core shell structure, while by chloroperoxidase (CPO), horseradish peroxidase during ZIF-8 is coated
(HRP) the enzyme@ZIF-8@with Magnetic Isolation effect and three kinds of enzymes of cromoci (Cyt C) are immobilized on ZIF-8, are obtained
Fe3O4Magnetic Nano enzyme reactor.Preparation method of the present invention is easy, gained enzyme@ZIF-8@Fe3O4Magnetic Nano enzyme reactor
Heat endurance and ph stability are significantly increased compared with resolvase, and with splendid reusability.
Brief description of the drawings
Fig. 1 is HRP@ZIF-8@Fe prepared by embodiment 13O4The scanning electron microscope (SEM) photograph of magnetic Nano enzyme reactor.
Fig. 2 is HRP@ZIF-8@Fe prepared by embodiment 13O4The transmission electron microscope picture of magnetic Nano enzyme reactor.
Fig. 3 is ZIF-8, Fe3O4、CA-Fe3O4The HRP@ZIF-8@Fe prepared with embodiment 13O4Magnetic Nano enzyme reactor
And CPO@ZIF-8@Fe prepared by embodiment 23O4The X-ray powder diffraction figure of magnetic Nano enzyme reactor.
Fig. 4 is ZIF-8, CA-Fe3O4The HRP@ZIF-8@Fe prepared with embodiment 13O4Magnetic Nano enzyme reactor and reality
Apply the CPO@ZIF-8@Fe of the preparation of example 23O4The infrared spectrogram of magnetic Nano enzyme reactor.
Fig. 5 is HRP@ZIF-8@Fe prepared by embodiment 13O4The EDS energy spectrum diagrams of magnetic Nano enzyme reactor.
Fig. 6 is ZIF-8@Fe3O4The HRP@ZIF-8@Fe prepared with embodiment 13O4The thermogravimetric of magnetic Nano enzyme reactor point
Analysis figure.
Fig. 7 is ZIF-8@Fe3O4The CPO@ZIF-8@Fe prepared with embodiment 23O4The thermogravimetric of magnetic Nano enzyme reactor point
Analysis figure.
Fig. 8 is ZIF-8@Fe3O4The Cyt C@ZIF-8@Fe prepared with embodiment 33O4The thermogravimetric of magnetic Nano enzyme reactor
Analysis chart.
Fig. 9 is the HRP@ZIF-8@Fe that temperature is prepared to HRP resolvases and embodiment 13O4Magnetic Nano enzyme reactor is catalyzed
The influence of activity.
Figure 10 is the CPO@ZIF-8@Fe that temperature is prepared to CPO resolvases and embodiment 23O4Magnetic Nano enzyme reactor is urged
Change the influence of activity.
Figure 11 is the Cyt C@ZIF-8@Fe that temperature is prepared to CytC resolvases and embodiment 33O4Magnetic Nano enzyme reactor
The influence of catalytic activity.
Figure 12 is HRP@ZIF-8@Fe prepared by HRP resolvases and embodiment 13O4Magnetic Nano enzyme reactor is at 60 DEG C
React influence of the different time to catalytic activity.
Figure 13 is CPO@ZIF-8@Fe prepared by CPO resolvases and embodiment 23O4Magnetic Nano enzyme reactor is at 50 DEG C
React influence of the different time to catalytic activity.
Figure 14 is Cyt C@ZIF-8@Fe prepared by CytC resolvases and embodiment 33O4Magnetic Nano enzyme reactor is at 70 DEG C
Influence of the lower reaction different time to catalytic activity.
Figure 15 is HRP@ZIF-8@Fe prepared by HRP resolvases and embodiment 13O4The pH of magnetic Nano enzyme reactor is stable
Property.
Figure 16 is CPO@ZIF-8@Fe prepared by CPO resolvases and embodiment 23O4The pH of magnetic Nano enzyme reactor is stable
Property.
Figure 17 is CytC@ZIF-8@Fe prepared by CytC resolvases and embodiment 33O4The pH of magnetic Nano enzyme reactor is steady
It is qualitative.
Figure 18 is HRP@ZIF-8@Fe prepared by embodiment 13O4The reusability design sketch of magnetic Nano enzyme reactor.
Figure 19 is CPO@ZIF-8@Fe prepared by embodiment 23O4The reusability design sketch of magnetic Nano enzyme reactor.
Figure 20 is Cyt C@ZIF-8@Fe prepared by embodiment 33O4The reusability effect of magnetic Nano enzyme reactor
Figure.
Embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited only to
These embodiments.
Embodiment 1
1st, citric acid modification Fe3O4Magnetic nano-particle
By 1.0g (4mmol) magnetic Fe3O4Powder, 50mL ultra-pure waters are added in 250mL three-necked flasks, ultrasonic under agitation
20 minutes, make magnetic Fe3O4Powder is dispersed in ultra-pure water, then adds 4.5mL 2.0mol/L aqueous citric acid solution,
In N2Protect lower 90 DEG C to stir 90 minutes, be cooled to room temperature, isolate product with magnet, product with pure water it is clean after be placed in
60 DEG C are dried in vacuo 5 hours in vacuum drying chamber, obtain the Fe of citric acid modification3O4Magnetic nano-particle (CA-Fe3O4)。
2nd, HRP@ZIF-8@Fe are prepared3O4Magnetic Nano enzyme reactor
By the Fe of 50.0mg citric acid modifications3O4It is placed in after magnetic nano-particle grinding in 100mL beakers, adds 10mL bodies
Fraction is 50% ethanol water, adds 55.0mg (0.29mmol) Zn (NO3)2And 3mg mass fractions are 37%
The HCl/water solution of (0.029mmol), mixed liquor is ultrasonic 20 minutes at room temperature, solid powder is dispersed in ethanol water
In solution, the polyvinylpyrrolidine that 235.0mg (2.86mmol) 2-methylimidazole, 90mg weight average molecular weight are 10000 is added
Ketone and 200 μ L 1mg/mL horseradish peroxidases, stir mixed liquor 10 minutes after shaking up, and collect product with magnet, use respectively
Ethanol and milli-Q water three times, obtained product are placed in vacuum drying chamber 30 DEG C and are dried in vacuo 8 hours, obtain HRP@ZIF-
8@Fe3O4Magnetic Nano enzyme reactor.
Embodiment 2
In the present embodiment, with etc. quality chloroperoxidase (CPO) alternative embodiment 1 in horseradish peroxidase,
Other steps are same as Example 1, obtain CPO@ZIF-8@Fe3O4Magnetic Nano enzyme reactor.
Embodiment 3
In the present embodiment, with etc. quality cromoci (Cyt C) alternative embodiment 1 in horseradish peroxidase, its
His step is same as Example 1, obtains Cyt C@ZIF-8@Fe3O4Magnetic Nano enzyme reactor.
Inventor uses environmental scanning electron microscope-EDS power spectrums, transmission electron microscope, X-ray diffractometer, Fu Li
Leaf transformation infrared spectrometer, thermal analysis system are characterized to the gained magnetic Nano enzyme reactor of embodiment 1~3 respectively, as a result
See Fig. 1~8.From Fig. 1,2, the magnetic Fe of citric acid modification3O4Size is significantly increased after ZIF-8 has been coated, and citric acid is repaiied
The magnetic Fe of decorations3O4Particle diameter be about 250~300nm, ZIF-8 shells are about 50~80nm, the HRP@ZIF-8@Fe of formation3O4
Magnetic Nano enzyme reactor is homogeneous spherical of pattern.As seen from Figure 3, HRP@ZIF-8@Fe3O4With CPO@ZIF-8@Fe3O4Magnetic
Property nanometer enzyme reactor diffraction maximum in existing ZIF-8 characteristic peak, also there is Fe3O4Characteristic diffraction peak, the addition of enzyme is simultaneously
ZIF-8@Fe are not interfered with3O4Structure.From fig. 4, it can be seen that HRP@ZIF-8@Fe3O4With CPO@ZIF-8@Fe3O4Magnetic Nano enzyme
Reactor has Fe simultaneously3O4The functional group having with ZIF-8, as seen from Figure 5, HRP@ZIF-8@Fe3O4With CPO@ZIF-8@
Fe3O4There are several elements of C, N, O, Fe, Zn in magnetic Nano enzyme reactor.The characterization result explanation of Fig. 3~5 is successfully synthesized
Enzyme@ZIF-8@Fe3O4Core shell structure.
From Fig. 6,7,8, HRP@ZIF-8@Fe3O4、CPO@ZIF-8@Fe3O4With CytC@ZIF-8@Fe3O4Magnetic Nano
The weightless ratio of enzyme reactor is all higher than ZIF-8@Fe3O4Weightless ratio, the decomposition of protein in sample can be attributed to, said
Bright three kinds of enzymes can introduce ZIF-8@Fe3O4Structure, the process for fixation has universality to these three enzymes.
In order to prove beneficial effects of the present invention, the magnetic Nano enzyme reactor that inventor is prepared using embodiment 1~3 is urged
Change ABTS peroxidizations and generate glaucous ABTS+, ABTS conversion ratio and phase is catalyzed with three kinds of magnetic Nano enzyme reactors
The stability of these three magnetic Nano enzyme reactors is investigated to conversion ratio, specific experiment and result are as follows：
1st, heat endurance
Magnetic Nano enzyme reactor prepared by three kinds of resolvases (HRP, CPO and Cyt C) and embodiment 1~3 exists respectively
It is used to be catalyzed ABTS peroxidizations after warm bath 3h under different temperatures, compares the thermally-stabilised of resolvase and magnetic Nano enzyme reactor
Property size.In reaction system：H2O2Concentration is 0.1molL-1, pH=5, HRP concentration be 200 μm of olL-1, CPO concentration be
400μmol·L-1, Cyt C concentration be 500 μm of olL-1.Result of the test is shown in Fig. 9~11.The result of Fig. 9~11 shows, dissociates
HRP, CPO and Cyt C optimal reaction temperature are respectively 25 DEG C, 35 DEG C and 40 DEG C, and HRP@ZIF-8@Fe3O4、CPO@ZIF-8@
Fe3O4With CytC@ZIF-8@Fe3O4Optimal reaction temperature be respectively 30 DEG C, 40 DEG C and 50 DEG C, optimal reactive temperature is
Improve.After optimal reactive temperature, under the catalytic activity of resolvase and magnetic Nano enzyme reactor is all with the rise of temperature
Drop, compared with resolvase, three kinds of magnetic Nano enzyme reactors all show good heat endurance under the conditions of higher temperatures.
Magnetic Nano enzyme reactor prepared by three kinds of resolvases (HRP, CPO and Cyt C) and embodiment 1~3 exists respectively
(HRP under certain temperature：60℃；CPO：50℃；Cyt C：70 DEG C) warm bath 3h, compares resolvase and magnetic Nano enzyme reactor
Heat endurance size.From Figure 12~14, with the extension of warm bath time, the catalysis of resolvase and magnetic Nano enzyme reactor
Activity is gradually reduced, the catalytic activity for HRP only residues 30.1% of dissociating after 60 DEG C of warm bath 3h, and magnetic prepared by embodiment 1
Nanometer enzyme reactor still has 71.4% catalytic activity；CPO catalytic activity of dissociating after 50 DEG C of warm bath 3h is less than 10%, and embodiment
The 2 magnetic Nano enzyme reactors prepared still have 81.3% catalytic activity；After 70 DEG C of warm bath 3h, the Cyt C that dissociate only are remained
31.7% catalytic activity, and magnetic Nano enzyme reactor prepared by embodiment 3 still has 84.1% catalytic activity, further
Illustrate that three kinds of magnetic Nano enzyme reactors show higher heat endurance than corresponding resolvase.
2nd, ph stability
Magnetic Nano enzyme reactor prepared by three kinds of resolvases (HRP, CPO and Cyt C) and embodiment 1~3 is in difference
It is used to be catalyzed ABTS peroxidizations in pH (3.0~7.0) 0.1mol/L phosphate buffer solutions, investigates them different pH's
Ph stability size (concentration of substrate in phosphate buffer solution：400mol/L；H2O2Concentration：0.1mol/L；Temperature：30℃).
Result of the test is shown in Figure 15~17.Swum more accordingly from the optimal pH of Figure 15~17, three kinds of magnetic Nano enzyme reactor reaction
Shifted from enzyme, under different pH, the catalytic efficiency of magnetic Nano enzyme reactor is always above resolvase.
3rd, reusability
Magnetic Nano enzyme reactor prepared by embodiment 1~3 is respectively used to after ABTS peroxidizations, reaction 30min
Centrifugation determines absorbance of the upper strata reaction solution at 415nm, and the magnetic Nano enzyme reactor of lower floor is used to be catalyzed next time
ABTS peroxidizations, using first time ABTS conversion ratio as 100%, the conversion ratio and the ratio of first time each time by after
Compared with the reusability of residual activity sign magnetic Nano enzyme reactor.As a result Figure 18~20 are seen.From Figure 18~20,
Magnetic Nano enzyme reactor prepared by embodiment 1~3 is respectively provided with splendid reusability, HRP@ZIF-8@Fe3O4、CPO@
ZIF-8@Fe3O4With Cyt C@ZIF-8@Fe3O4Magnetic Nano enzyme reactor keeps 90.0% respectively after reusing 5 times,
89.1%th, 88.4% catalytic activity, reuse 12 times after keep more than 50% catalytic activity.
Claims (10)
1. a kind of enzyme@ZIF-8@Fe3O4Magnetic Nano enzyme reactor, it is characterised in that：The reactor is with citric acid modification
Fe3O4Magnetic nano-particle is core, in one layer of ZIF-8 shell of its Surface coating, forms ZIF-8@Fe3O4Core shell structure, then will
Enzyme is fixed on carrier.
2. enzyme@ZIF-8@Fe according to claim 13O4Magnetic Nano enzyme reactor, it is characterised in that：Described enzyme is
Any one in chloroperoxidase, horseradish peroxidase, cromoci.
3. enzyme@ZIF-8@Fe according to claim 1 or 23O4Magnetic Nano enzyme reactor, it is characterised in that：Described lemon
The Fe of lemon acid modification3O4The particle diameter of magnetic nano-particle is 250~300nm, the ZIF-8 shells of its surface coated enzyme immobilization
Thickness is 50~80nm.
4. the enzyme@ZIF-8@Fe described in a kind of claim 13O4The preparation method of magnetic Nano enzyme reactor, it is characterised in that it
It is made up of following step：
(1) citric acid modification Fe3O4Magnetic nano-particle
By magnetic Fe3O4Powder is dispersed in ultra-pure water, 1~3mol/L aqueous citric acid solution is then added, in N2Protection
Lower 80~100 DEG C are stirred 60~120 minutes, are cooled to room temperature, and with pure water is used after magnet separation product, vacuum drying is obtained
To the Fe of citric acid modification3O4Magnetic nano-particle；
(2) enzyme@ZIF-8@Fe are prepared3O4Magnetic Nano enzyme reactor
By the Fe of citric acid modification3O4Magnetic nano-particle is dispersed in ethanol water, adds Zn (NO3)2, mass fraction
For 37% HCl/water solution, 2-methylimidazole, polyvinylpyrrolidone, enzyme, stirring at normal temperature 10~20 minutes is separated with magnet
After product, successively with ethanol and milli-Q water, vacuum drying obtains enzyme@ZIF-8@Fe3O4Magnetic Nano enzyme reactor；
Above-mentioned Zn (NO3)2, 2-methylimidazole, HCl mol ratio be 1:(8~12):(0.05~0.2), citric acid modification
Fe3O4Magnetic nano-particle and enzyme, Zn (NO3)2, polyvinylpyrrolidone mass ratio be 100:(0.1~1):(80~150):
(150~250).
5. enzyme@ZIF-8@Fe according to claim 43O4The preparation method of magnetic Nano enzyme reactor, it is characterised in that：
In step (1), the magnetic Fe3O4The mol ratio of powder and citric acid is 1:(2~3).
6. the enzyme@ZIF-8@Fe according to claim 4 or 53O4The preparation method of magnetic Nano enzyme reactor, its feature exists
In：In step (1), in N2Lower 90 DEG C are protected to stir 90 minutes.
7. enzyme@ZIF-8@Fe according to claim 43O4The preparation method of magnetic Nano enzyme reactor, it is characterised in that：
In step (2), described enzyme is any one in chloroperoxidase, horseradish peroxidase, cromoci.
8. enzyme@ZIF-8@Fe according to claim 43O4The preparation method of magnetic Nano enzyme reactor, it is characterised in that：
In step (2), described Zn (NO3)2, HCl, 2-methylimidazole mol ratio be 1:0.1:10, the Fe of citric acid modification3O4
Magnetic nano-particle and enzyme, Zn (NO3)2, polyvinylpyrrolidone mass ratio be 100:0.4:110:180.
9. enzyme@ZIF-8@Fe according to claim 43O4The preparation method of magnetic Nano enzyme reactor, it is characterised in that：
In step (2), the volumetric concentration of ethanol is 40%~60% in described ethanol water.
10. enzyme@ZIF-8@Fe according to claim 43O4The preparation method of magnetic Nano enzyme reactor, it is characterised in that：
The weight average molecular weight of described polyvinylpyrrolidone is 8000~12000.
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| CN108396023A (en) * | 2018-02-09 | 2018-08-14 | 兰州大学 | Magnetism MOF materials are prepared with polishing and for the fixation of enzyme |
| CN108893459A (en) * | 2018-06-07 | 2018-11-27 | 宁夏大学 | A kind of MOFs enzyme immobilization, preparation method and application |
| CN109234261A (en) * | 2018-08-21 | 2019-01-18 | 江苏大学 | Horseradish peroxidase magnetic Nano flower and its preparation method and application |
| CN109266636A (en) * | 2018-09-25 | 2019-01-25 | 江苏大学 | A kind of nano enzyme and its preparation method and application |
| CN109364899A (en) * | 2018-12-21 | 2019-02-22 | 上海纳米技术及应用国家工程研究中心有限公司 | The preparation method and products thereof of magnetic ZIF-8 Nano composite granules |
| CN109913440A (en) * | 2019-03-27 | 2019-06-21 | 南京工业大学 | A method of passing through pressure synthesising biological enzyme/MOFs composite functional material |
| CN110540984A (en) * | 2019-08-29 | 2019-12-06 | 浙江工业大学 | HRP/Co3O4@ ZIF-8 composite catalyst and preparation method thereof |
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| CN109913440A (en) * | 2019-03-27 | 2019-06-21 | 南京工业大学 | A method of passing through pressure synthesising biological enzyme/MOFs composite functional material |
| CN110540984A (en) * | 2019-08-29 | 2019-12-06 | 浙江工业大学 | HRP/Co3O4@ ZIF-8 composite catalyst and preparation method thereof |
| CN111233252A (en) * | 2020-01-15 | 2020-06-05 | 北京建筑大学 | Zeolite imidazolate-like framework-horseradish peroxidase biomineralization embedding precoat, preparation thereof and application thereof in ultrafiltration membrane water purification |
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| CN111876406A (en) * | 2020-06-18 | 2020-11-03 | 南京师范大学 | Magnetic nanoparticle-lipase-metal organic framework composite catalytic material and preparation method and application thereof |
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