CN114515603B - Preparation method of ionic conjugated polymer and molybdenum disulfide composite nanoenzyme - Google Patents
Preparation method of ionic conjugated polymer and molybdenum disulfide composite nanoenzyme Download PDFInfo
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- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 66
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 52
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 12
- 239000011733 molybdenum Substances 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 30
- 229920000642 polymer Polymers 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 15
- -1 molybdenum disulfide compound Chemical class 0.000 claims description 14
- 102000004190 Enzymes Human genes 0.000 claims description 12
- 108090000790 Enzymes Proteins 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
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- 238000001816 cooling Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 claims description 2
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 claims description 2
- 229920002098 polyfluorene Polymers 0.000 claims description 2
- 229920000128 polypyrrole Polymers 0.000 claims description 2
- 229920000123 polythiophene Polymers 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 229920000553 poly(phenylenevinylene) Polymers 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 102000003992 Peroxidases Human genes 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 108040007629 peroxidase activity proteins Proteins 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 239000002114 nanocomposite Substances 0.000 abstract 1
- 238000005580 one pot reaction Methods 0.000 abstract 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- 239000012071 phase Substances 0.000 description 10
- 210000004027 cell Anatomy 0.000 description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000004141 dimensional analysis Methods 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000003833 cell viability Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 150000002500 ions Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
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- 238000010899 nucleation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- CDOWNLMZVKJRSC-UHFFFAOYSA-N 2-hydroxyterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(O)=C1 CDOWNLMZVKJRSC-UHFFFAOYSA-N 0.000 description 1
- 206010006187 Breast cancer Diseases 0.000 description 1
- 208000026310 Breast neoplasm Diseases 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000004693 imidazolium salts Chemical class 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 210000004881 tumor cell Anatomy 0.000 description 1
Images
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- B01J35/40—
-
- B01J35/51—
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the field of high-molecular composite materials, and discloses a preparation method of an ionic conjugated polymer and molybdenum disulfide composite nanoenzyme. The preparation method is characterized in that a water-soluble side chain of an ionic conjugated polymer is combined with a molybdenum source molecule through coordination, and the ionic conjugated polymer and molybdenum disulfide nano-composite is prepared by one-step reduction by taking a rigid main chain structure of the conjugated polymer as a template. The preparation method provided by the invention is simple and easy to implement, can be used for preparing the molybdenum disulfide with a high specific surface area and a high proportion of metal 1T-phase structure by utilizing a one-pot method to carry out hydrothermal reaction, presents excellent peroxidase catalytic activity, and has good practical value in the field of biomedicine.
Description
Technical Field
The invention belongs to the field of high-molecular composite materials, and relates to a preparation method of an ionic conjugated polymer and molybdenum disulfide composite nanoenzyme.
Background
Natural biological enzymes are a class of proteins with catalytic activity. It is of great interest because of its specific and efficient catalytic properties. However, in the practical application process, the problems of complex purification process, difficult storage, insufficient stability and the like of the natural biological enzyme greatly limit the wide application of the natural biological enzyme. The artificial enzyme can effectively overcome the defects of natural enzyme, and has the advantages of large-scale production, convenient storage, high cost performance and the like. Therefore, the development of novel artificial enzymes has wide application prospect.
In recent years, molybdenum disulfide, as a transition metal sulfide, has a layered structure, is connected by covalent bonds in layers, and is connected between layers by van der waals force, shows enzyme-like properties, and has practical application value in the field of biomedicine. According to the electron filling condition on the Mo valence electron d orbit, the molybdenum disulfide is divided into a 2H phase (triangular prism coordination, the crystal unit cell comprises two layers), a 1T phase (regular octahedral coordination, the crystal unit cell only comprises one layer) and a 3R phase (triangular prism coordination, the unit cell comprises three layers). Wherein the 1T phase structure has metal-like conductivity, and can provide more catalytic active sites. However, the instability of the 1T phase limits the catalytic activity. In addition, the molybdenum disulfide material prepared by the traditional method has larger size, and particles are easy to agglomerate, so that active sites are buried, and the catalytic efficiency and the performance stability in use are reduced.
The introduction of the high molecular material can conveniently control the size, shape and structure of the product in a liquid phase system, thereby preparing the composite artificial enzyme, improving the stability of the product and optimizing the catalytic performance. The conjugated polymer material has a rigid conjugated framework, can be covalently connected with a side chain of a belt charge, introduces a coordination mechanism with metal ions, and further regulates and controls the size and the phase structure of the molybdenum disulfide. The method can be used for preparing the artificial complex enzyme which has high catalytic efficiency and stable performance and can be produced and stored in a large scale. The method has practical value for the application of the polymer composite material in the aspects of mimic enzyme and catalytic medicine.
Disclosure of Invention
The invention aims to overcome the defects of non-uniform hydrothermal reaction product of molybdenum disulfide, uncontrollable structural composition, unstable catalytic performance and the like, and provides a preparation method of an ionic conjugated polymer and molybdenum disulfide composite nanoenzyme, which has the activity of pseudoperoxidase.
The technical scheme of the invention is that the ionic conjugated polymer is mixed with a precursor solution to generate coordination to fix metal ions. And then carrying out hydrothermal reaction, and preparing the molybdenum disulfide and conjugated polymer composite nanoenzyme which has good dispersibility, small size, long-term storage and high proportion of metal 1T phase structure through one-step reduction, and has the capability of catalyzing hydrogen peroxide to generate active oxygen.
The method comprises the following specific steps:
(1) Weighing a proper amount of ionic conjugated polymer, dissolving the ionic conjugated polymer in a good solvent, fully and uniformly stirring, and then performing ultrasonic dispersion to obtain a polymer solution;
(2) Dissolving molybdenum source molecules and a reducing agent in a certain proportion in deionized water, fully and uniformly stirring, and performing ultrasonic dispersion to obtain a precursor solution;
(3) And (3) adding the polymer solution obtained in the step (1) into the precursor solution obtained in the step (2), uniformly mixing under an ultrasonic condition, transferring to a reaction kettle, introducing inert gas for a certain time, performing one-step hydrothermal reaction, cooling, centrifugally washing, and drying to obtain a conjugated polymer and molybdenum disulfide compound, namely the ionic conjugated polymer and molybdenum disulfide compound nanoenzyme.
Preferably, in step (1), the ionic conjugated polymer may be one of polyfluorene, polythiophene, polyparaphenylene vinylene, polypyrrole and polyaniline, which contain a conjugated main chain.
Further preferably, the ionic conjugated polymer in the step (1) is one of ionic side chain structures with the formulas (1) - (6).
The formula (1) is referred to as sulfonate conjugated polymer for short, the formula (2) is referred to as phosphate conjugated polymer for short, the formula (3) is referred to as carboxylate conjugated polymer for short, the formula (4) is referred to as quaternary ammonium salt conjugated polymer for short, the formula (5) is referred to as imidazolium salt conjugated polymer for short, and the formula (6) is referred to as pyridinium salt conjugated polymer for short.
Further preferably, the good solvent of the ionic conjugated polymer in the step (1) is one or more of ethanol, water, N-dimethylformamide and dimethyl sulfoxide.
Further preferably, the molybdenum source molecule in step (2) is one of ammonium molybdate, sodium molybdate, ammonium thiomolybdate, phosphomolybdic acid and molybdenum pentachloride. The reducing agent is one or more of thiourea, sodium sulfide, hydrazine hydrate or oxalic acid. The molar ratio of the molybdenum source molecules to the reducing agent is 1:2 to 1:8.
further preferably, the volume ratio of the polymer solution to the precursor solution in the step (3) is 1; the mass ratio of the polymer to the molybdenum element contained in the molybdenum source is 1:1 to 1:10.
further preferably, in the step (3), the inert gas introduced into the mixed solution is one of nitrogen and argon inert gas, and the introducing time is 5-15min.
Further preferably, the hydrothermal reaction temperature in the step (3) is 180-220 ℃, and the reaction time is 4-24h.
The ionic conjugated polymer and molybdenum disulfide composite nanoenzyme obtained by the method has small size, good dispersibility and pseudoperoxidase activity, and can catalyze hydrogen peroxide to generate hydroxyl radicals.
The key points of the technology of the invention are as follows:
1. the volume ratio of the polymer solution to the precursor solution is controlled, the mass ratio of the polymer to molybdenum element contained in the molybdenum source is controlled, nucleation is regulated and controlled by utilizing the coordination effect of the polymer ion group and the metal ion, the size of the molybdenum disulfide nano-particles is reduced, and a 1T phase with high proportion is obtained.
2. By controlling the hydrothermal reaction temperature and the reaction time, the ionic conjugated polymer and molybdenum disulfide composite nanoenzyme which can present excellent peroxidase-like activity is obtained, and by comparing different examples, the hydrothermal reaction temperature is kept at 200 ℃ for 24 hours when the volume ratio of the polymer solution to the precursor solution is controlled to be 1; the obtained composite nano enzyme has the best quality.
Compared with the prior art, the invention has the advantages and beneficial effects that: nucleation is regulated and controlled through coordination of polymer ion groups and metal ions, the size of the molybdenum disulfide nano particles is reduced, and meanwhile, a high proportion of 1T phase is obtained, so that the operation is simple and convenient; the ionic conjugated polymer and the molybdenum disulfide are compounded, so that the dispersity and stability of the nanoparticles are improved, active sites can be exposed, and the catalytic efficiency and the performance stability are improved. The obtained composite nano enzyme can present excellent peroxidase-like activity and has good application value in the field of catalytic medical treatment.
Drawings
FIG. 1 is a Scanning Electron Micrograph (SEM) of the ionic conjugated polymer and molybdenum disulfide composite nanoenzyme prepared in example 1.
FIG. 2 is a two-dimensional analysis diagram of molybdenum element in the ionic conjugated polymer and molybdenum disulfide composite nanoenzyme prepared in example 1.
FIG. 3 is a two-dimensional analysis chart of sulfur element in the ionic conjugated polymer and molybdenum disulfide composite nanoenzyme prepared in example 1.
FIG. 4 is the X-ray photoelectron spectrum of the molybdenum element in the ionic conjugated polymer and molybdenum disulfide composite nanoenzyme prepared in example 1.
FIG. 5 shows fluorescence spectra of ionic conjugated polymer prepared in example 1, molybdenum disulfide complex nanoenzyme and hydrogen peroxide at different times after terephthalic acid system is added.
FIG. 6 shows the cell viability of cells co-cultured with different concentrations of the ionic conjugated polymer and the molybdenum disulfide compound nanoenzyme.
Detailed Description
Example 1
(1) 5mg of quaternary ammonium salt conjugated polymer PFNBr is dissolved in 0.5mLN and N-dimethylformamide, and ultrasonic dispersion is carried out after full and uniform stirring to obtain a polymer solution.
(2) 36.3mg of sodium molybdate dihydrate and 34.2mg of thiourea are dissolved in 14.5mL of deionized water, and are subjected to ultrasonic dispersion after being fully and uniformly stirred to obtain a precursor solution.
(3) And (3) adding the polymer solution obtained in the step (1) into the precursor solution obtained in the step (2), uniformly mixing under an ultrasonic condition, transferring to a reaction kettle, introducing 10min of nitrogen, keeping at 200 ℃ for 24h, carrying out hydrothermal reaction, cooling, carrying out centrifugal washing for 3-4 times at 10000rpm, and drying for 24h to obtain a conjugated polymer and molybdenum disulfide compound, namely the ionic conjugated polymer and molybdenum disulfide compound nanoenzyme.
And (3) performance testing:
FIG. 1 is a Scanning Electron Micrograph (SEM) of the ionic conjugated polymer and molybdenum disulfide composite nanoenzyme prepared in example 1. As can be seen from FIG. 1, the complex nanoenzyme is spherical and has a diameter of about 200-300nm and a small size.
FIGS. 2 and 3 are two-dimensional analysis graphs of the ionic conjugated polymer and molybdenum disulfide composite nanoenzyme prepared in example 1 corresponding to molybdenum and sulfur elements. As can be seen from FIGS. 2 and 3, the ionic conjugated polymer and the molybdenum disulfide composite nanoenzyme have molybdenum and sulfur elements which are uniformly distributed, indicating the successful preparation of the molybdenum disulfide.
FIG. 4 is the X-ray photoelectron spectrum of molybdenum element in the ionic conjugated polymer and molybdenum disulfide composite nanoenzyme prepared in example 1. According to the peak separation result of fig. 4, the proportion of the prepared molybdenum disulfide 1T phase is about 67%.
FIG. 5 shows fluorescence spectra of ionic conjugated polymer prepared in example 1, molybdenum disulfide complex nanoenzyme and hydrogen peroxide at different times after terephthalic acid system is added. The test method comprises the following steps: the prepared ionic conjugated polymer was combined with molybdenum disulfide complex nanoenzyme (2. Mu.g/mL) and hydrogen peroxide (0.1 mM) to measure the fluorescence spectrum after addition of 1mL of terephthalic acid (2.5 mM) solution. As can be seen from FIG. 5, after incubation for 8h, fluorescence emission of hydroxyl terephthalic acid is observed, which indicates that the composite nanoenzyme has excellent peroxidase property and has the ability of catalyzing hydrogen peroxide to generate hydroxyl radicals.
FIG. 6 shows the cell viability of cells co-cultured with different concentrations of the ionic conjugated polymer and the molybdenum disulfide compound nanoenzyme. The test method comprises the following steps: MDA-MB-231 breast cancer cells were seeded into 96-well plates at a density of 6000 cells per well. Cells were exposed to 0, 30, 50, 70, 90. Mu.g/mL of complex nanoenzyme for 12h, then 100. Mu.L of thiazole blue (1 mg/mL) was added per well for 4h, and finally 100. Mu.L of dimethyl sulfoxide was added and the absorbance at 570nm was measured. As can be seen from FIG. 6, the ionic conjugated polymer and molybdenum disulfide composite nanoenzyme shows a certain killing property on tumor cells and changes depending on the concentration.
Example 2
(1) 50mg of quaternary ammonium salt conjugated polymer PFNBr is dissolved in 1mLN of N-dimethylformamide, and ultrasonic dispersion is carried out after full and uniform stirring to obtain polymer solution.
(2) 363mg of sodium molybdate dihydrate and 342mg of thiourea are dissolved in 14mL of deionized water, and are subjected to ultrasonic dispersion after being fully and uniformly stirred to obtain a precursor solution.
(3) And (3) adding the polymer solution obtained in the step (1) into the precursor solution obtained in the step (2), uniformly mixing under an ultrasonic condition, transferring to a reaction kettle, introducing 10min of nitrogen, keeping at 200 ℃ for 4h, carrying out hydrothermal reaction, cooling, carrying out centrifugal washing for 3-4 times at 10000rpm, and drying for 24h to obtain a conjugated polymer and molybdenum disulfide compound, namely the ionic conjugated polymer and molybdenum disulfide compound nanoenzyme.
Example 3
(1) Dissolving 15mg of quaternary ammonium salt conjugated polymer PFNBr in 0.5mLN and N-dimethylformamide, fully and uniformly stirring, and then carrying out ultrasonic dispersion to obtain a polymer solution.
(2) 108.9mg of sodium molybdate dihydrate, 102.6mg of thiourea and 18.1mg of oxalic acid are dissolved in 14.5mL of deionized water, and the mixture is fully stirred uniformly and then subjected to ultrasonic dispersion to obtain a precursor solution.
(3) And (3) adding the polymer solution obtained in the step (1) into the precursor solution obtained in the step (2), uniformly mixing under an ultrasonic condition, transferring to a reaction kettle, introducing 10min of nitrogen, keeping at 200 ℃ for 24h, carrying out hydrothermal reaction, cooling, carrying out centrifugal washing for 3-4 times at 10000rpm, and drying for 24h to obtain a conjugated polymer and molybdenum disulfide compound, namely the ionic conjugated polymer and molybdenum disulfide compound nanoenzyme.
Claims (9)
1. A preparation method of ionic conjugated polymer and molybdenum disulfide composite nano enzyme is characterized by comprising the following steps: the method comprises the following steps:
(1) Weighing a proper amount of ionic conjugated polymer, dissolving the ionic conjugated polymer in a good solvent, fully and uniformly stirring, and then performing ultrasonic dispersion to obtain a polymer solution;
(2) Dissolving molybdenum source molecules and a reducing agent in a certain proportion in deionized water, fully and uniformly stirring, and performing ultrasonic dispersion to obtain a precursor solution;
(3) Adding the polymer solution obtained in the step (1) into the precursor solution obtained in the step (2) to be uniformly mixed under an ultrasonic condition, transferring the mixture to a reaction kettle, introducing inert gas for a certain time, performing one-step hydrothermal reaction, cooling, centrifugally washing, and drying to obtain a conjugated polymer and molybdenum disulfide compound, namely an ionic conjugated polymer and molybdenum disulfide compound nanoenzyme; the composite nanoenzyme has a pseudoperoxidase activity;
the ionic conjugated polymer in the step (1) is one of the conjugated polymers with ionic side chain structures of formulas (1) - (6);
2. the method for preparing the ionic conjugated polymer and molybdenum disulfide composite nanoenzyme according to claim 1, wherein the ionic conjugated polymer in the step (1) is one of polyfluorene, polythiophene, poly-p-phenylene vinylene, polypyrrole and polyaniline which contain a conjugated main chain.
3. The method for preparing the ionic conjugated polymer and molybdenum disulfide composite nanoenzyme according to claim 1, wherein the good solvent of the ionic conjugated polymer in the step (1) is one or more of ethanol, water, N-dimethylformamide and dimethyl sulfoxide.
4. The method of claim 1, wherein the molybdenum source molecule in step (2) is one of ammonium molybdate, sodium molybdate, ammonium thiomolybdate, phosphomolybdic acid, and molybdenum pentachloride.
5. The method for preparing the ionic conjugated polymer and molybdenum disulfide composite nanoenzyme according to claim 1, wherein the reducing agent in the step (2) is one or more of thiourea, sodium sulfide, hydrazine hydrate or oxalic acid.
6. The method for preparing the ionic conjugated polymer and molybdenum disulfide composite nanoenzyme according to claim 1, wherein the molar ratio of the molybdenum source molecule to the reducing agent in step (2) is 1:2 to 1:8.
7. the method for preparing the ionic conjugated polymer and molybdenum disulfide composite nanoenzyme according to claim 1, wherein the volume ratio of the polymer solution to the precursor solution in the step (3) is 1; the mass ratio of the polymer to the molybdenum element contained in the molybdenum source is 1:1 to 1:10.
8. the method for preparing the ionic conjugated polymer and molybdenum disulfide composite nanoenzyme according to claim 1, wherein the inert gas introduced into the mixed solution in the step (3) is one of nitrogen and argon, and the introduction time is 5-15min.
9. The method for preparing the ionic conjugated polymer and molybdenum disulfide composite nanoenzyme according to claim 1, wherein the hydrothermal reaction temperature in the step (3) is 180-230 ℃, and the reaction time is 4-24h.
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