CN112275267A - Magnetic molecularly imprinted polymer material and application thereof in electrochemical detection of catechin - Google Patents
Magnetic molecularly imprinted polymer material and application thereof in electrochemical detection of catechin Download PDFInfo
- Publication number
- CN112275267A CN112275267A CN202011133698.6A CN202011133698A CN112275267A CN 112275267 A CN112275267 A CN 112275267A CN 202011133698 A CN202011133698 A CN 202011133698A CN 112275267 A CN112275267 A CN 112275267A
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- Prior art keywords
- catechin
- zif
- rgo
- polymer material
- molecularly imprinted
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Links
- ADRVNXBAWSRFAJ-UHFFFAOYSA-N catechin Natural products OC1Cc2cc(O)cc(O)c2OC1c3ccc(O)c(O)c3 ADRVNXBAWSRFAJ-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 235000005487 catechin Nutrition 0.000 title claims abstract description 87
- 229950001002 cianidanol Drugs 0.000 title claims abstract description 75
- PFTAWBLQPZVEMU-DZGCQCFKSA-N (+)-catechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-DZGCQCFKSA-N 0.000 title claims abstract description 74
- 239000002861 polymer material Substances 0.000 title claims abstract description 27
- 238000000835 electrochemical detection Methods 0.000 title claims abstract description 25
- 229920000344 molecularly imprinted polymer Polymers 0.000 title claims abstract description 25
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 95
- 239000000463 material Substances 0.000 claims abstract description 68
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims abstract description 40
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002105 nanoparticle Substances 0.000 claims abstract description 15
- 238000001903 differential pulse voltammetry Methods 0.000 claims abstract description 13
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- 238000004458 analytical method Methods 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 238000001514 detection method Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
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- 238000012986 modification Methods 0.000 claims description 13
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
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- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 3
- 238000000944 Soxhlet extraction Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012488 sample solution Substances 0.000 claims description 3
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 150000001765 catechin Chemical class 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 11
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 11
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
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- IQPNAANSBPBGFQ-UHFFFAOYSA-N luteolin Chemical compound C=1C(O)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(O)C(O)=C1 IQPNAANSBPBGFQ-UHFFFAOYSA-N 0.000 description 7
- LRDGATPGVJTWLJ-UHFFFAOYSA-N luteolin Natural products OC1=CC(O)=CC(C=2OC3=CC(O)=CC(O)=C3C(=O)C=2)=C1 LRDGATPGVJTWLJ-UHFFFAOYSA-N 0.000 description 7
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- 238000003786 synthesis reaction Methods 0.000 description 4
- -1 zeolite imidazole ester Chemical class 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
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- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000007885 magnetic separation Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical group CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- BOXYODYSHAHWPN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1.OC(=O)C1=CC=C(O)C=C1 BOXYODYSHAHWPN-UHFFFAOYSA-N 0.000 description 1
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- PFTAWBLQPZVEMU-UHFFFAOYSA-N catechin Chemical compound OC1CC2=C(O)C=C(O)C=C2OC1C1=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
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Abstract
The invention provides a magnetic molecularly imprinted polymer material and application thereof in electrochemical detection of catechin, wherein the magnetic molecularly imprinted polymer material is prepared by polymerizing catechin, functionalized ferroferric oxide nanoparticles and acrylic monomers and then removing the catechin; the functionalized ferroferric oxide nano particles are silane coupling agent modified ferroferric oxide nano particles. The electrochemical response performance of the rGO-ZIF-8 nano composite material and the mMIP modified glassy carbon electrode to the catechin solution can be evaluated by electrochemical detection modes such as cyclic voltammetry, differential pulse voltammetry and the like, and feasibility analysis is provided for electrochemical detection in actual samples. The modified electrode disclosed by the invention combines advanced electrochemical performances of GO and ZIF-8 and specific enrichment capacity of mMIP, has the advantages of higher sensitivity, wider linear range and the like for detecting catechin, and has a better application prospect.
Description
Technical Field
The invention relates to the technical field of electrochemical detection, in particular to a magnetic molecularly imprinted polymer material and application thereof in electrochemical detection of catechin, such as preparation of a modified electrode and electrochemical detection of a catechin solution.
Background
Catechin is mainly present in tea and other plants, has multiple biological functions of resisting bacteria, tumors, atherosclerosis and the like, and is researched as a potential anticancer drug by scientists. The prior method for measuring catechin is mainly chromatography, but has the defects of complex operation, low sensitivity and the like. The research focus in this field has been mainly focused on the synthesis and preparation of nanostructured nickel compound modified electrodes for the analytical detection of catechins using electrochemical methods. However, the intensity and detection selectivity of the quantitative analysis of catechins by electrochemical methods are currently in need of improvement.
In recent years, researchers have combined Metal Organic Framework (MOF) materials with some fluorescent materials (e.g., carbon dots, quantum dots, and fluorescent molecules) to improve their sensitivity, selectivity, and fluorescence intensity to analytes in detection. For example, researchers have encapsulated copper nanoclusters (CuNCs) in zeolite imidazole ester Framework-8 (Zeolite Imidazolate Framework-8, ZIF-8) to construct fluorescent nanocomposite CuNCs @ ZIF-8, which enhances the fluorescence intensity of CuNCs, improves the stability of CuNCs, and can sensitively detect hydrogen peroxide (ZIF-8)H2O2). Wherein ZIF-8 is formed by imidazole ligand (2-methylimidazole) and Zn2+Coordinated MOF materials with a zeolitic crystal topology. Due to Zn2+The zinc-doped zinc oxide has strong affinity with nitrogen atoms on imidazole ligands, ZIF-8 is a few MOF materials with excellent stability in water environment, and has good application prospect in the field of water treatment.
Graphene (GN) is composed of closely arranged sp2Hybridized carbon atoms form a single-layer honeycomb-shaped two-dimensional lattice structure which has excellent mechanical strength and electric and heat conduction properties; GN is used as a filler to modify the material, so that the conductivity of the material can be well improved, and the application range of the material is further widened. However, few studies have been reported to complex GN with ZIF-8 and simultaneously improve GN strength and detection selectivity.
Disclosure of Invention
In view of the above, the application provides a magnetic molecularly imprinted polymer material and an application thereof in electrochemical detection of catechin, and the magnetic molecularly imprinted polymer material provided by the invention has good selectivity on catechin and can improve the sensitivity of electrochemical detection of catechin.
The invention provides a magnetic molecularly imprinted polymer material, which is prepared by polymerizing catechin, functionalized ferroferric oxide nanoparticles and acrylic monomers and then removing catechin; the functionalized ferroferric oxide nano particles are silane coupling agent modified ferroferric oxide nano particles.
The magnetic molecularly imprinted polymer material provided by the invention is named mMIP, has magnetic and selective adsorption capacity, has obvious adsorption effect on catechins, and can be applied to electrochemical detection and analysis of catechins.
In a micro-morphology structure, the magnetic molecularly imprinted polymer material takes ferroferric oxide nano particles as a core, and the surface of the core has an uneven structure which is mainly polymerized organic components, cavities and the like; the components are mainly iron element and elements such as carbon, oxygen and the like brought by modification. Compared with other core materials such as silicon dioxide and the like, the molecular imprinting material taking ferroferric oxide as the core has the characteristics of better conductivity and the like, and is favorable for electrochemical detection of catechin.
In an embodiment of the present invention, the preparation method of the magnetic molecularly imprinted polymer material includes the following steps:
providing ferroferric oxide nano particles modified by silane coupling agent, wherein the silane coupling agent is preferably 3- (methacryloyloxy) propyl trimethoxy silane and is marked as Fe3O4-MPS or Fe3O4@MPS；
And (3) polymerizing the catechin serving as a template molecule with the modified and functionalized ferroferric oxide nano particles and the acrylic acid monomer, and then removing the template molecule to obtain the mMIP.
The functionalized ferroferric oxide nano particle can be prepared in the following way: firstly preparing to obtain Fe3O4Magnetic nanoparticles, followed by further modification with MPS. In general, iron salts such as ferric chloride, sodium acetate and polyethylene glycol are dissolved in ethylene glycol, and after ultrasonic stirring at room temperature, the solution can be transferred to a stainless steel autoclave lined with polytetrafluoroethylene, and the reaction is heated, for example, at 180 ℃ for 6 hours, and the obtained black product is separated by a magnet and washed with ethanol for a plurality of times for subsequent modification.
Preparation of Fe3O4In @ MPS, Fe may be substituted3O4Dispersing magnetic nanoparticles in ethanol solution, adding a certain amount of MPS methanol solution into Fe under mechanical stirring after ultrasonic action3O4Magnetic nano particle suspension; after the addition, stirring may be carried out at room temperature for 24 hours, and finally, Fe may be collected with a magnet3O4@ MPS product, washed three times with ethanol and stored at 4 ℃.
In some embodiments of the present invention, an acrylic polymer component is employed in the magnetic molecularly imprinted polymer material; acrylic monomers include methacrylic acid (MAA) and ethylene glycol dimethacrylate (EDGMA). In preparing the mip of the preferred embodiment of the present invention, the catechin and MAA are first dissolved in an organic solvent, preferably acetonitrile, and preferably in an ice-water bathAnd (3) carrying out reaction under the condition of stirring to obtain a template solution. Thereby adding Fe3O4-MPS, EDGMA and the initiator AIBN are dispersed in acetonitrile, sonicated, after which the dispersion is mixed with the above-mentioned template solution and subjected to polymerization, after a certain time the product is isolated with a magnet and washed three times with acetonitrile. Among them, it is preferable to seal the reactor after removing dissolved oxygen and carry out polymerization in an oil bath at 50 to 60 ℃ for a reaction time of generally 24 hours.
In order to remove the template molecules, the present embodiment preferably employs soxhlet extraction of the mip with a methanol solution until no catechins are observed by spectrophotometry, and the mip is synthesized. Finally, embodiments of the invention can store the mip in methanol at 4 ℃.
The invention provides a modified electrode, which is prepared by surface modification of a glassy carbon electrode by a functional material; the functional material comprises graphene substances, ZIF-8 and the magnetic molecularly imprinted polymer material.
According to the invention, graphene substances are compounded with ZIF-8, and the magnetic molecularly imprinted polymer material is added, and the materials modify a glassy carbon electrode together, so that electric signals such as response current of the electrode to catechin can be obviously improved, and the method has advantages in aspects such as sensitivity and linear detection range of electrochemical detection of catechin.
The method for carrying out surface modification on the electrode in the embodiment of the invention specifically comprises the following steps: coating the surface of a glassy carbon electrode with a compound of a graphene substance and ZIF-8, coating the surface of the glassy carbon electrode with the magnetic molecularly imprinted polymer material, and drying to obtain the magnetic molecularly imprinted polymer material.
The embodiment of the invention can clean the surface of the electrode firstly: the bare electrode (bare GCE) was first polished with alumina (0.05 μm) polishing powder, then sonicated in water for 3 minutes to remove the polishing powder remaining on the electrode surface, and the electrode surface was blow-dried with nitrogen gas for subsequent surface modification.
In some embodiments of the present invention, the graphene-based material and ZIF-8 composite is prepared by ultrasonically mixing and/or hydrothermally mixing the graphene-based material and ZIF-8. Wherein the graphene-based material may be a Graphene Nanoplate (GN) or a graphene nanoplateReducing graphene oxide rGO; essentially rGO and GN properties were identical except that different synthesis processes resulted in different expression. The graphene GN generally adopts a physical synthesis path, and in addition, graphene oxide GO can be synthesized first and then reduced into rGO. As mentioned above, ZIF-8 is a complex of imidazole ligand (2-methylimidazole) and Zn2+Coordinated MOF materials with a zeolitic crystal topology.
According to some embodiments of the invention, the graphene substance and the ZIF-8 have the advantages of good conductivity, large specific surface area, excellent holding performance and the like, and the rGO-ZIF-8 nano composite material is prepared mainly by a method of heating reaction kettle-assisted self-assembly. Specifically, the rGO and the ZIF-8 are subjected to ultrasonic treatment and mixing in ultrapure water, then hydrothermal reaction is carried out in a reaction kettle, the temperature is 150 ℃, and 4 hours are carried out, so as to prepare uniform dispersion liquid; after the reaction is finished, ultrasonic treatment is continued for 10 minutes to obtain the self-assembled rGO-ZIF-8 nano composite material. The rGO-ZIF-8 nano composite material is prepared by mixing and reacting two materials in a hydrothermal environment for a period of time, and excessive structural change is not generated in the process.
In other embodiments, the rGO-ZIF-8 nano composite material can be obtained by carrying out ultrasonic reaction on the rGO and the ZIF-8 nano composite material for 30min or carrying out hydrothermal reaction for several hours, and the rGO-ZIF-8 nano composite material can be called as a composite of the rGO and the ZIF-8 nano composite material, and is mainly in a state of mixing the rGO and the ZIF-8 nano composite material together. In some embodiments of the invention, the mass ratio of the graphene-like substance to the ZIF-8 is (1-4): (1-3) is, for example, 1:1, 1:2, 1:3, 2:1, 3:1, 4:1, preferably 4: 1.
According to the embodiment of the invention, a certain amount of rGO-ZIF-8 suspension can be dripped on the surface of a cleaned electrode and dried; and then, uniformly dripping the mMIP solution on the surface of the electrode, drying to superpose single coatings, and marking the finally prepared electrode as mMIP/rGO-ZIF-8/GCE. In some embodiments of the present invention, the amount of the graphene-based material and ZIF-8 complex applied is 5 to 10. mu.L, preferably 7 to 8. mu.L, and more preferably 8. mu.L. And the coating amount of the magnetic molecularly imprinted polymer material is preferably 7-8 muL. And the drying can be natural airing, so that the modified electrode is prepared.
The electrochemical response performance of the rGO-ZIF-8 nano composite material and the mMIP modified glassy carbon electrode to a catechin (0.1mol/L PBS) solution can be evaluated through electrochemical detection modes such as Cyclic Voltammetry (CV) and Differential Pulse Voltammetry (DPV), and feasibility analysis is provided for electrochemical detection in actual samples. The modified electrode combines the advanced electrochemical performances of graphene materials (GN and rGO) and ZIF-8 and the specific enrichment capacity of mMIP, can be used as a sensor for detecting catechin, and has a good application prospect.
The embodiment of the invention provides an electrochemical detection method of catechin solution, which comprises the following steps:
and (3) detecting the sample solution to be detected by using the modified electrode as a working electrode and adopting a cyclic voltammetry method or a differential pulse voltammetry method, and analyzing according to an electric signal to obtain the content of catechin.
The detection method mainly aims at catechin, and has the advantages of low detection limit, high sensitivity and wide quantitative range, and can reach the detection concentration of 0.01 nM.
Cyclic voltammetry is a commonly used electrochemical study in which a linear sweep voltage is applied to the electrodes, one or more repeated sweeps are swept at a constant rate of change over a range of potentials that allow different reduction and oxidation reactions to occur alternately at the electrodes, and a current-potential curve is recorded.
Differential pulse voltammetry is an electrochemical measurement method derived from linear sweep voltammetry and step sweep voltammetry, i.e. based on which a certain voltage pulse is added and the current is measured before the potential changes, in such a way that the influence of the charging current is reduced.
The electrochemical detection device of the embodiment of the invention comprises: electrochemical workstation, electrolytic cell, three electrodes (working electrode, auxiliary electrode and reference electrode) and electrolyte solution. The main technical means of the detection method is not particularly limited; the experimental parameters of the CV method were set as follows: the potential sweep ranged from-0.2V to 1.0V, with a sweep rate of 10 mV/s. In some embodiments of the invention, the pH of the electrolyte at the time of detection is 6 to 9, preferably 7 to 8, more preferably 7; the scanning rate of the cyclic voltammetry is 0.01-0.3V/s.
In the embodiment of the present invention, the DPV method can perform quantitative analysis, and the experimental parameters are set as follows: the potential was swept from-0.2V to 0.6V at a sweep rate of 10mV/s, a pulse amplitude of 50mV, and a pulse width of 50 ms. In addition, all experiments were performed at room temperature (25. + -. 2 ℃).
In some embodiments of the invention, the modified electrode has a detection range of 0.01nM to 10. mu.M, with a minimum detection limit of 0.003 nmol/L. The modified electrode developed by the invention has the advantages of higher sensitivity, wider linear range and the like for the detection application of catechin, and has great practical value in the field of detecting natural components such as catechin and the like.
Drawings
FIG. 1 is a transmission electron micrograph of the starting material and the synthesized mMIP material of an example of the present invention;
FIG. 2 is a scanning electron micrograph of the starting material and the synthesized mMIP material of an example of the present invention;
FIG. 3 is a mapping diagram of the elements of the rGO-ZIF-8 nanocomposite material under a scanning electron microscope in the embodiment of the invention;
FIG. 4 is a mapping diagram of elements of the mMIP material under a scanning electron microscope in the embodiment of the present invention;
FIG. 5 is an XRD pattern of starting material and synthesized mMIP material in an example of the present invention;
FIG. 6 is an IR spectrum of the starting material and the synthesized mMIP material of an example of the present invention;
FIG. 7 is a graph of the magnetic saturation curves of starting and synthesized mMIP materials in an example of the present invention;
FIG. 8 is a diagram showing the physical and magnetic separation effects of the synthesized mMIP material;
FIG. 9 is a graph comparing the adsorption capacity of mMIP materials for catechin, luteolin, p-hydroxybenzoic acid and puerarin in examples of the present invention;
FIG. 10 is a DPV graph of 0.01mmol/L catechin for different modified electrodes;
FIG. 11 is a graph of the effect of different rGO to ZIF-8 material ratios on the electrochemical response of catechin solutions;
FIG. 12 is a graph of the effect of the amount of rGO-ZIF-8 drops applied to a modified electrode on the electrochemical response of a catechin solution;
FIG. 13 is a graph of the effect of the amount of mMIP applied to a modified electrode on the electrochemical response of a catechin solution;
FIG. 14 is a graph of the effect of different pH values on the current response of 0.01mmol/L catechin (0.1mol/L PBS);
FIG. 15 is a graph plotting peak current versus catechin concentration for mMIP/rGO-ZIF-8/GCE assays in logarithmic form;
FIG. 16 is the anti-interference experimental results of mMIP/rGO-ZIF-8/GCE;
FIG. 17 is a repeat experiment of mMIP/rGO-ZIF-8/GCE;
FIG. 18 shows the results of stability experiments with mMIP/rGO-ZIF-8/GCE.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to further understand the present application, the magnetic molecularly imprinted polymer material provided by the present application and the application thereof in electrochemical detection of catechin are specifically described below with reference to examples.
Example 1: preparation of magnetic molecularly imprinted polymer material
(1) Preparation of Fe3O4Magnetic nanoparticles: 1.35g of ferric chloride, 3.60g of sodium acetate and 1.0g of PEG6000 were weighed and dissolved in 50mL of ethylene glycol, stirred ultrasonically at room temperature for 30min, and then transferred to a stainless steel autoclave lined with polytetrafluoroethylene and kept at 180 ℃ for 6 h. The resulting black product was further modified by magnet separation, three washes with ethanol.
(2) Preparation of Fe3O4@ MPS, 0.6g of Fe3O4Dispersing magnetic nanoparticles in ethanol solution, and performing ultrasonic treatment for 30min25mL of MPS solution (20% methanol, v/v) was added dropwise to Fe with mechanical stirring3O4Magnetic nano particle suspension; after the addition, the mixture was stirred at room temperature for 24 hours, and finally Fe was collected with a magnet3O4@ MPS product, washed three times with ethanol and stored at 4 ℃.
(3) First, 0.1g of catechin and 2.5mmol/LMAA (methacrylic acid) were dissolved in 30 ml of acetonitrile, and reacted for 12 hours under magnetic stirring in an ice-water bath to obtain a template solution. 500 mg of Fe3O4MPS, 20 mmol of EDGMA (ethylene glycol dimethacrylate) and 50 mg of AIBN (azobisisobutyronitrile), dispersed in a 250 ml round bottom flask with 70 ml of acetonitrile. After ultrasonic treatment is carried out for 30min, the obtained dispersion is mixed with template solution, nitrogen is bubbled for 5min, and dissolved oxygen in the solution is removed; the flask was sealed and the polymerization was carried out in a 55 ℃ oil bath, after 24h the product was isolated with a magnet and washed three times with acetonitrile.
To remove the template molecules, the mip was extracted by soxhlet extraction with methanol solution until no catechins were observed by spectrophotometry. Finally, the synthesized mMIPs were stored in methanol at 4 ℃.
For comparison, mNIP is made according to the same procedure except for the template; mNIP is a magnetic polymer material without template molecules.
Example 2: modified electrode preparation
(1) Preparation of rGO-ZIF-8
The rGO and the ZIF-8 are subjected to ultrasonic treatment and mixing in ultrapure water, and then hydrothermal reaction is carried out in a reaction kettle at 150 ℃ for 4 hours to prepare uniform dispersion liquid. After the reaction is finished, ultrasonic treatment is continued for 10 minutes to obtain the self-assembled rGO-ZIF-8 nano composite material.
Wherein, the rGO is obtained according to the following synthesis steps:
1.50g of flake graphite was mixed with 9.00g of potassium permanganate, and 180mL of concentrated sulfuric acid and 20mL of nitric acid were added. The resulting mixture was reacted for 12h at 50 ℃ with magnetic stirring. After the reaction is finished, pouring the product into 200mL of ice water containing a certain amount of hydrogen peroxide to obtain a yellow product. The mixture was centrifuged to remove the supernatant, washed three times with 0.1M hydrochloric acid solution and water in sequence, and the product was retained by centrifugation each time to obtain Graphene Oxide (GO). Adding 200mg of GO into 50mL of water, transferring the GO into a polytetrafluoroethylene reaction kettle, reacting for 6 hours at 180 ℃ to obtain rGO, and storing the obtained black product for later use.
(2) Before electrode modification, a Glassy Carbon Electrode (GCE) is carefully polished by using alumina sand paper polishing powder, is subjected to ultrasonic treatment for 5min and is washed by water. After GCE cleaning, 8 mu L of uniformly dispersed rGO-ZIF-8 nano composite solution (2mg/mL) is uniformly dripped on the surface of an electrode and naturally dried. And then, uniformly dripping 8 mu L of mMIP aqueous solution (4mg/mL) on the same surface of the electrode, naturally airing, and finally marking the finally manufactured electrode as mMIP/rGO-ZIF-8/GCE.
Furthermore, 8. mu.L of rGO and ZIF-8 were modified in the same procedure as controls to compare the performance of rGO/GCE, ZIF-8/GCE and mMIP/rGO-ZIF-8/GCE.
Example 3: material characterization and Performance Studies
(1)rGO，ZIF-8，rGO-ZIF-8，Fe3O4Characterization of magnetic nanoparticles and synthetic mMIP materials
The morphology and the structure are characterized by an electron microscope (SEM) and a Transmission Electron Microscope (TEM); FIG. 1 is a transmission electron micrograph of several materials, (a) is a TEM image of rGO, (b) is a TEM image of an rGO-ZIF-8 nanocomposite, and (c) is Fe3O4TEM photographs of magnetic nanoparticles, and (d) TEM photographs of mMIP. FIG. 2 is a scanning electron micrograph, (a) is an SEM of rGO, (b) is an SEM of ZIF-8, (c) is an SEM of rGO-ZIF-8 nanocomposite, and (d) is an SEM of mMIP. FIG. 3 is an element mapping image of an rGO-ZIF-8 nano composite material under a scanning electron microscope, and FIG. 4 is an element mapping image of an mMIP material under the scanning electron microscope.
The transmission electron microscope and the scanning electron microscope display the shapes of the micro structures of the rGO and the ZIF-8, and the compound is in a state of mixing the two; the mapping plot shows the presence of zinc and carbon elements, and also indicates that the composite is a mixture of the two. The magnetic molecularly imprinted material (mMIP) mainly shows that ferroferric oxide nanoparticles are used as cores, polymerization reaction is carried out on the surfaces of the ferroferric oxide nanoparticles to form a material with a molecular recognition function, and an electron microscope shows that the ferroferric oxide modified surfaces have changes and have uneven structures, and are probably organic matters, cavities and the like caused by polymerization. The Mapping graph can see that the iron element exists and the carbon, nitrogen and oxygen elements are brought by modification.
Fig. 5 is an X-ray diffraction (XRD) pattern of several materials, fig. 6 is an infrared analysis spectrum, fig. 7 is a magnetic saturation graph, and fig. 8 is a photograph of a real object with mip material.
XRD and infrared spectrum show that the composition process does not change the essential structural characteristics of rGO, ZIF-8 and ferroferric oxide. The magnetic saturation curve shows that the mMIP material can be separated under a magnetic field, and the mMIP material can be rapidly separated under the attraction of a magnet according to a real object and a magnetic separation diagram of the mMIP material.
(2) The mMIP material has selective adsorption capacity and obvious adsorption effect on Catechin (Catechin), and the comparison of the mNIP which is a magnetic polymer material without template molecules can show that the mMIP material has the effect brought by the imprinting process. The specific experiment is as follows:
selective experiments of mMIP and mNIP were carried out by selecting structural analogs Luteolin (Luteolin), p-hydroxybenzoic acid (p-hydroxybenzoic acid) and Puerarin (Puerarin), and the chemical structures of the analogs and catechin are shown below.
To 5mL of catechin (40. mu. mol/L), luteolin (40. mu. mol/L), p-hydroxybenzoic acid (40. mu. mol/L) and puerarin (40. mu. mol/L), 20mg of mMIP or mNIP was added, respectively. After mechanical shaking at 25 ℃ for 30min, the material was collected, the concentration of the remaining sample solution was measured, and the corresponding amount of adsorption was calculated using a standard curve, as shown in FIG. 9.
The adsorption amounts of luteolin, p-hydroxybenzoic acid and puerarin were 1.63, 1.09 and 0.48. mu. mol/g, respectively, as compared with the adsorption amount of catechin (4.7. mu. mol/g). The results show that the adsorption capacity of mMIP to catechin is 2.88, 4.31 and 9.79 times of that of luteolin, p-hydroxybenzoic acid and puerarin respectively. This indicates that the material mip has a high selectivity for catechins, which may be due to the formation of a number of specific cavities on the surface of the mip, which have a high affinity for the template molecule. Luteolin, the most similar molecule to catechin, showed the highest adsorption (1.63 μmol/g) among the three analogues; puerarin shows the lowest capacity, because the space of the molecule is larger than that of the template due to the glucoside group, and the probability of entering a cavity is reduced. However, the adsorption of mNIP to catechin and the like (0.37 to 0.50. mu. mol/g) was non-specific, based on the adsorption amount of mNIP. Thus, these comparisons indicate that mip has good recognition and adsorption capacity for catechins.
Example 4: electrochemical detection
(1) Comparison of different modified electrodes
To determine the preparation process, the electrochemical response of catechins was compared with different modified electrodes (naked GCE, ZIF-8/GCE, rGO/GCE, mMIP/GCE, rGO-ZIF-8/GCE and mMIP/rGO-ZIF-8/GCE).
According to FIG. 10, the signal current of rGO/GCE (1.77 μ A), ZIF-8/GCE (1.35 μ A) were all higher than the signal current of bare GCE (0.59 μ A), indicating that these materials contribute to improved conductivity. Meanwhile, the rGO-ZIF-8/GCE and the mMIP/rGO-ZIF-8/GCE obviously enhance signals with higher peak current. In the electrochemical response of these modified electrodes, the combination of rGO and ZIF-8 showed better enhancement (4.02 μ A) than either component alone, probably due to the three-dimensional structure of ZIF-8 and the good adsorption and conductivity properties of rGO. After the addition of the mMIP with imprinted cavities on the surface, the mMIP/rGO-ZIF-8/GCE has better adsorption capacity on catechin and corresponds to an electric signal (7.59 mu A), especially in the catechin with lower concentration. Therefore, the mMIP/rGO-ZIF-8 complex modified electrode produced the best electrical signal response to catechin.
(2) Optimization of rGO-ZIF-8 material proportion
Under 0.01mmol/L catechin (0.1mol/L PBS), the material mass ratio (1:1, 1:2, 1:3, 2:1, 3:1, 4:1) of the nano material rGO and ZIF-8 is researched by a DPV method, the electrochemical response of a catechin solution is detected, and the experiment is repeated for 3 times in parallel, and the hydrothermal reaction: 150 ℃ and 4 h.
As shown in FIG. 11, FIG. 11 is a DPV plot of different rGO to ZIF-8 material ratios in a 0.010mmol/L catechin solution, (a) bare GCE, (b)1:1, (c)1:2, (d)1:3, (e)2:1, (f)3:1, (g)4: 1. When the material ratio was 4:1, the peak current of catechin was the maximum. Therefore, the optimal material ratio of the rGO-ZIF-8 suspension for the modified electrode is 4: 1.
(3) Optimization of rGO-ZIF-8 drop coating amount
The influence of the dripping amount (5 muL, 6 muL, 7 muL, 8 muL and 9 muL) of the electrode modification material rGO-ZIF-8 on the electrochemical response of the catechin solution is researched by DPV. As shown in FIG. 12, when the droplet application amount of rGO-ZIF-8 was gradually increased from 5.0. mu.L to 10.0. mu.L, the peak current of catechin was gradually increased to the maximum value and then decreased. When the volume of coated rGO-ZIF-8 is too small, the electrode will not be fully covered and the current response is relatively low; when too much rGO-ZIF-8 is dispensed, the thickness of the film is increased, so that electron transfer between electrodes is hindered, and the current response is reduced. When the dripping amount of the rGO-ZIF-8 composite material on the surface of the electrode is 8.0 mu L, the electrochemical response of the modified electrode reaches the maximum value, so that the optimal dripping amount of the rGO-ZIF-8 suspension of the modified electrode is 8.0 mu L.
(4) Optimization of mMIP drop application volume
On the basis of the dropping amount of the rGO-ZIF-8 material, the influence of different dropping amounts of the mMIP on the detection signal is also examined, and as shown in FIG. 13, the current value of the catechin increases along with the increase of the dropping amount of the mMIP and reaches the maximum value at 8.0 muL, so that the optimal dropping amount of the mMIP of the modified electrode mMIP/rGO-ZIF-8/GCE is 8.0 muL.
(5) Optimization of pH
Electrochemical detection of catechins on the electrode mMIP/rGO-ZIF-8/GCE was performed by DPV studies of pH values (4.0, 5.0, 6.0, 7.0, 8.0 and 9.0) of electrolytes in different buffer solutions (0.1mol/L PBS). The experimental results are shown in fig. 14; the oxidation peak current of catechin gradually increased as the pH value was from 4.0 to 7.0, reached a maximum at pH7.0, and then began to decrease. At pH7.0, the catechin can obtain the maximum oxidation peak current on rGO-ZIF-8, which indicates that the catechin is subjected to effective electrochemical oxidation and has the strongest response signal. Therefore, PBS having a pH of 7.0 was used as a supporting electrolyte in the following experiment.
(6) The detection range of the modified electrode of the present application can be from 0.01nM to 10. mu.M, with essentially two quantitative curves, which are then compared to many reported materials. The specific experiment is as follows:
DPV detection was performed with mMIP/rGO-ZIF-8/GCE for different concentrations of catechin PBS solution (0.1mol/L, pH7.0) under optimal experimental conditions. In the range of 0.01nmol/L to 10. mu. mol/L, peak current of catechin increased linearly with logarithmic increase of concentration, see FIG. 15. It can be seen that the fitted linear equation can be divided into two segments, i.e., Ip is 0.52logC +3.513 (R)20.998, 0.01nmol/L to 0.5 μmol/L) and Ip 1.96log C +8.357(R ═ g20.998, 0.5 to 10 μmol/L). The minimum detection Limit (LOD) can be up to 0.003nmol/L (S/N is 3).
Relative to some previously reported electrodes, mMIP/rGO-ZIF-8/GCE has a lower LOD and a wider linear range.
(7) Interference rejection and stability
The detection of the anti-interference capability is mainly used for evaluating the anti-interference capability of mMIP/rGO-ZIF-8/GCE in electrochemical detection of catechin. Firstly, in the experiment, sodium chloride (5.0mmol/L), potassium chloride (5.0mmol/L), calcium chloride (5.0mmol/L), aluminum nitrate (5.0mmol/L), ferrous sulfate (5.0mmol/L) and isoquercitrin (1.0mmol/L) are selected as interference substances, then the interference substances are respectively added into 0.01mmol/L catechin, and the electrochemical detection is carried out by adopting a DPV method.
The anti-interference capability of mMIP/rGO-ZIF-8/GCE is evaluated by calculating the current ratio (%) and is defined as the peak current ratio measured before and after the addition of an interfering substance. As shown in fig. 16, the electrochemical response of catechin was not significantly affected when the current ratio was between 0.05% and 1.16% in the presence of these relatively high concentrations of interferon; and the same amount of catechin is added into the electrolyte, and the current ratio reaches 103.5 percent, which shows that the anti-interference test and the related calculation are reliable. The result shows that the mMIP/rGO-ZIF-8/GCE has good anti-interference capability when detecting catechin.
Meanwhile, the reproducibility of the signal is evaluated by continuously recording the results of electric signals detected six times by mMIP/rGO-ZIF-8/GCE in catechin solution. A single piece of mMIP/rGO-ZIF-8/GCE was left for six days and assayed once a day to assess its stability. As shown in FIG. 17, FIG. 18, the relative standard deviations of the reproducibility and stability experiments for mMIP/rGO-ZIF-8/GCE were 5.19% and 6.07%, respectively. This demonstrates the good reproducibility and stability of catechins as measured by mMIP/rGO-ZIF-8/GCE.
(8) Actual sample detection and recovery test
In order to evaluate the sensitivity and the practicability of detecting catechin by mMIP/rGO-ZIF-8/GCE, green tea is used as a real sample. 1.0g of green tea leaves were soaked in 50mL of hot water for 20min, cooled, filtered, and subjected to 100-fold dilution measurement using PBS buffer. And a standard addition method is adopted for carrying out a recovery rate experiment so as to ensure the accuracy of the result. The results are as follows:
TABLE 1 detection of catechins in Green tea samples (n ═ 3)
As shown in Table 1, the content of catechin in the green tea sample is 0.688mol/L, the recovery rate of catechin detected by mMIP/rGO-ZIF-8/GCE is between 99.11% and 101.26%, and the relative standard deviation value is between 0.16% and 1.04%. Therefore, the prepared mMIP/rGO-ZIF-8/GCE can be successfully used for measuring catechin samples, and has higher accuracy and precision.
The above description is only a preferred embodiment of the present invention, and it should be noted that various modifications to these embodiments can be implemented by those skilled in the art without departing from the technical principle of the present invention, and these modifications should be construed as the scope of the present invention.
Claims (10)
1. A magnetic molecularly imprinted polymer material is characterized in that catechin, functionalized ferroferric oxide nano particles and acrylic monomers are polymerized, and then catechin is removed to prepare the magnetic molecularly imprinted polymer material; the functionalized ferroferric oxide nano particles are silane coupling agent modified ferroferric oxide nano particles.
2. The magnetic molecularly imprinted polymer material of claim 1, wherein the acrylic monomers comprise methacrylic acid and ethylene glycol dimethacrylate; the polymerization is carried out in acetonitrile in the presence of an azobisisobutyronitrile initiator; the removal of catechin adopts a methanol solution Soxhlet extraction method.
3. A modified electrode is characterized in that the modified electrode is prepared by surface modification of a glassy carbon electrode by a functional material; the functional material comprises graphene-like substances, ZIF-8 and the magnetic molecularly imprinted polymer material as claimed in any one of claims 1 to 2.
4. The modified electrode according to claim 3, wherein the mass ratio of the graphene-like substance to the ZIF-8 is (1-4): (1-3), preferably 4: 1.
5. The modified electrode according to claim 3, wherein the surface modification is in particular: coating the surface of a glassy carbon electrode with a compound of a graphene substance and ZIF-8, coating the surface of the glassy carbon electrode with the magnetic molecularly imprinted polymer material, and drying to obtain the magnetic molecularly imprinted polymer material.
6. The modified electrode of claim 5, wherein the graphene-based material and ZIF-8 composite is prepared by ultrasonic and/or hydrothermal mixing of graphene and ZIF-8.
7. The modified electrode according to claim 6, wherein the amount of the graphene-based material and ZIF-8 complex applied is 5 to 10 μ L, preferably 7 to 8 μ L.
8. An electrochemical detection method of catechin solution comprises the following steps:
the modified electrode of any one of claims 3 to 6 is used as a working electrode, a sample solution to be detected is detected by adopting cyclic voltammetry or differential pulse voltammetry, and the content of catechin is obtained according to electric signal analysis.
9. The electrochemical detection method according to claim 8, wherein the pH of the electrolyte at the time of detection is 6 to 9, preferably 7 to 8.
10. The electrochemical detection method of claim 8, wherein the modified electrode has a detection range of 0.01nM to 10 μ M and a minimum detection limit of 0.003 nmol/L.
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| CN114984926A (en) * | 2022-05-11 | 2022-09-02 | 东北电力大学 | Preparation method of high-agglomeration-resistance RGO-based magnetic lithium ion imprinted polymer |
| CN115678540A (en) * | 2022-09-20 | 2023-02-03 | 湖北大学 | Preparation method and application of ZIF-8 coating-based composite material |
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| CN114984926A (en) * | 2022-05-11 | 2022-09-02 | 东北电力大学 | Preparation method of high-agglomeration-resistance RGO-based magnetic lithium ion imprinted polymer |
| CN115678540A (en) * | 2022-09-20 | 2023-02-03 | 湖北大学 | Preparation method and application of ZIF-8 coating-based composite material |
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