CN114747579A - APG @ ZIF-8 composite material with pH response slow-release bacteriostatic function and preparation method and application thereof - Google Patents
APG @ ZIF-8 composite material with pH response slow-release bacteriostatic function and preparation method and application thereof Download PDFInfo
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/18—Vapour or smoke emitting compositions with delayed or sustained release
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- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Agronomy & Crop Science (AREA)
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- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
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Abstract
An APG @ ZIF-8 composite material with a pH response slow-release bacteriostatic function and a preparation method and application thereof. The invention belongs to the field of metal organic framework composite materials. The invention aims to solve the technical problems that apigenin cannot be stably stored at room temperature, the bioactivity is not high and the application of ZIF-8 is limited to a certain extent by the powdery form at present. The APG @ ZIF-8 composite material with the pH response slow-release bacteriostatic function consists of apigenin and ZIF-8, wherein the apigenin is encapsulated in the ZIF-8, and the APG @ ZIF-8 composite material is in a rhombic dodecahedron shape. The APG @ ZIF-8 with the pH response slow-release bacteriostatic function is used for preparing an APG @ ZIF-8 composite bacteriostatic film. The APG @ ZIF-8 composite material prepared by the invention has a good drug pH response slow release function. The prepared antibacterial film is used for food packaging. The composite material and the propolis show good synergistic antibacterial action, and the inhibition rate of both gram-positive bacteria and gram-negative bacteria can reach 100%.
Description
Technical Field
The invention belongs to the field of metal organic framework composite materials, and particularly relates to an APG @ ZIF-8 composite material with a pH response slow-release bacteriostatic function, and a preparation method and application thereof.
Background
Food-borne pathogens can cause a number of diseases and seriously harm human health. According to the world health organization data, about 7.7% of people worldwide suffer from food-borne diseases. In the food industry, resistance of food-borne pathogens to traditional disinfectants is increasing, leading to the risk of food contamination. Therefore, it is necessary to develop and utilize a novel natural antibacterial agent having a good antibacterial effect. The control of food-borne pathogens requires not only a production process but also a reasonable selection of packaging materials to reduce the pollution after treatment. The development of packaging films having antibacterial functions is becoming a trend in food packaging.
Apigenin (APG) is a natural flavonoid compound, and has antiinflammatory, antioxidant, anticancer and antibacterial effects. However, apigenin is not stable for storage at room temperature and has low bioavailability. In addition, the inhibition effect of apigenin on gram-positive bacteria is weak, and the broad-spectrum inhibition requirement on various pathogenic bacteria in actual production cannot be met. Therefore, there is a need for encapsulation or modification of APG to modulate its biological activity and enhance its antibacterial effect.
ZIF-8 is a porous metal-organic framework (MOFs) composed of metallic zinc and an organic ligand, 2-methylimidazole. ZIF-8 has been widely studied for its high and stable porosity and large specific surface area. In addition, it has excellent biocompatibility, remains stable in physiological environments, disintegrates under acidic conditions, and is suitable for encapsulation and delivery of drugs. The antibacterial function of ZIF-8 has also been demonstrated over the past few years. Meanwhile, the low cytotoxicity of ZIF-8 has been confirmed by in vitro cell experiments and in vivo animal experiments, so that ZIF-8 has advantages in the fields of medicine and food. However, the powdered form of ZIF-8 has somewhat limited its use.
Disclosure of Invention
The invention aims to solve the technical problems that apigenin cannot be stably stored at room temperature and has low bioactivity at present and the application of ZIF-8 is limited to a certain extent by the powdery form of the ZIF-8, and provides an APG @ ZIF-8 composite material with a pH response slow-release antibacterial function and a preparation method and application thereof.
The APG @ ZIF-8 composite material with the pH response slow-release bacteriostatic function consists of apigenin and ZIF-8, wherein the apigenin is encapsulated in the ZIF-8, the APG @ ZIF-8 composite material is in the form of an orthorhombic dodecahedron, and the mass fraction of APG in the APG @ ZIF-8 composite material is 5-12%.
Further limited, the particle size of the APG @ ZIF-8 composite material is 200 nm-300 nm, and the pore volume is 0.6cm3/g~1.0cm3G, the aperture is 10 nm-20 nm, the specific surface area is 1000m2/g~1400m2/g。
The preparation method of the APG @ ZIF-8 composite material with the pH response slow-release bacteriostatic function comprises the following steps:
step 1: dissolving 2-methylimidazole in methanol, adding APG, and performing ultrasonic treatment until complete dispersion;
step 2: adding a zinc acetate solution at room temperature, magnetically stirring for reaction, centrifuging, washing with methanol, and drying to obtain the APG @ ZIF-8 composite material.
Further defined, the ratio of the mass of 2-methylimidazole to the volume of methanol in step 1 is 330 mg: (10-20) mL, wherein the mass ratio of the 2-methylimidazole to the APG in the step 1 is 330: (4-6).
Further limiting, in the step 2, the mass concentration of the zinc acetate solution is 11 mg/mL-22 mg/mL, and the mass ratio of the zinc acetate to the 2-methylimidazole in the zinc acetate solution is 110: (300-360), wherein the rotating speed of the centrifugation in the step 2 is 7000 rpm-9000 rpm, the time is 10 min-20 min, the drying temperature in the step 2 is 40-60 ℃, and the time is 20 h-24 h.
The APG @ ZIF-8 with the pH response slow-release bacteriostatic function is used for preparing an APG @ ZIF-8 composite bacteriostatic film.
Further limited, the APG @ ZIF-8 composite bacteriostatic film has the thickness of 97.56-157.89 microns, the water content of 20.57-10.59%, the water solubility of 67.29-42.69%, the tensile strength of 5.06-2.85 MPa and the elongation at break of 36.84-14.26%.
Further limited, the preparation process of the APG @ ZIF-8 composite bacteriostatic film is as follows: adding gelatin, propolis and APG @ ZIF-8 into distilled water, performing ultrasonic treatment to completely disperse the mixture, then adding glycerol to obtain a film-forming solution, performing ultrasonic treatment on the film-forming solution, then pouring the film-forming solution into a polymethyl methacrylate mold, and drying to obtain the APG @ ZIF-8 composite antibacterial film, wherein the mass fraction of the APG @ ZIF-8 in the film-forming solution is 0.75-1.00%.
Further limited, the APG @ ZIF-8 composite bacteriostatic film is used for killing food-borne pathogenic bacteria.
Further defined, the food-borne pathogenic bacteria include, but are not limited to, staphylococcus aureus, escherichia coli.
Compared with the prior art, the invention has the advantages that:
1) the APG @ ZIF-8 composite material prepared by the invention has a good drug pH response slow release function.
2) The addition of APG @ ZIF-8 enables the propolis-gelatin composite membrane to show stronger water stability and flexibility, and is more suitable for food packaging. The composite material and propolis show good synergistic antibacterial action, and the inhibition rate of the composite material on gram-positive bacteria (staphylococcus aureus) and gram-negative bacteria (escherichia coli) can reach 100% under the condition of appropriate addition amount.
3) The invention encapsulates antibacterial natural substances in ZIF-8, and provides a new strategy for preparing food packaging films.
Drawings
FIG. 1a is a scanning electron micrograph of ZIF-8;
FIG. 1b is an APG @ ZIF-8 scanning electron micrograph;
FIG. 2 is a Fourier transform infrared spectrum of apigenin, ZIF-8 and APG @ ZIF-8;
FIG. 3 is an x-ray diffraction pattern of apigenin, ZIF-8, and APG @ ZIF-8;
FIG. 4 is a thermogravimetric plot of apigenin, ZIF-8, and APG @ ZIF-8;
FIG. 5 is an adsorption curve and a desorption curve for ZIF-8 and APG @ ZIF-8;
FIG. 6 is a release curve of apigenin in APG @ ZIF-8 under different pH environments;
FIG. 7 is an x-ray diffraction pattern of a composite film of different compositions;
FIG. 8 is an electron microscope image of a composite film of different compositions; wherein a-comparative example 3, b-comparative example 4, c-comparative example 5, d-comparative example 6, e-comparative example 7, f-example 2, g-example 3;
FIG. 9 is a graph of water contact angles of composite films of different compositions; wherein a-comparative example 3, b-comparative example 4, c-comparative example 5, d-comparative example 6, e-comparative example 7, f-example 2, g-example 3;
FIG. 10a is a graph showing killing and inhibition rate of Staphylococcus aureus by composite film;
FIG. 10b is a graph showing the killing of Escherichia coli and the inhibition rate of the composite film;
FIG. 11a is a scanning electron micrograph of Staphylococcus aureus bacteria prior to treatment;
FIG. 11b is the SEM image of the Staphylococcus aureus bacteria after treatment;
FIG. 11c is a scanning electron micrograph of the bacterial morphology of E.coli prior to treatment;
FIG. 11d is the scanning electron micrograph of the morphology of the E.coli bacteria after treatment.
Detailed Description
Example 1: the preparation method of the APG @ ZIF-8 composite material with the pH response slow-release bacteriostatic function is carried out according to the following steps:
step 1: dissolving 330mg of 2-methylimidazole in 10mL of methanol, adding 5mg of APG, and carrying out ultrasonic treatment for 10min until complete dispersion;
and 2, step: adding a zinc acetate solution (110mg, 5mL) at room temperature, reacting for 5min by magnetic stirring, centrifuging at 8000rpm for 15min, washing with methanol for 3 times, and drying at 50 ℃ for 24h to obtain the APG @ ZIF-8 composite material.
The form of the obtained APG @ ZIF-8 composite material is an orthorhombic dodecahedron, and the mass fraction of APG in the APG @ ZIF-8 composite material is 11.94%.
Comparative example 1: this example differs from example 1 in that: the amount of APG added is 3mg, 10mg, 15mg, 20mg, 25mg or 30 mg. The other steps and parameters were the same as in example 1.
And (3) determining the encapsulation rate and the drug loading rate:
collecting supernatant in the synthesis process of the APG @ ZIF-8 composite material, and measuring an OD value at 337nm, wherein the encapsulation rate is (apigenin addition amount-apigenin mass in supernatant)/apigenin addition amount; the drug loading rate (apigenin addition amount-apigenin mass in supernatant)/APG @ ZIF-8 mass, and the results are shown in Table 1.
TABLE 1 APG @ ZIF-8 encapsulation efficiency and drug loading efficiency
And (3) morphological observation:
the APG @ ZIF-8 and ZIF-8 powder samples of example 1 were adhered to double-sided carbon conductive tape on a sample stage, excess sample that was not adhered was blown off with an ear-washing ball, and the sample stage was then placed in an ion sputtering apparatus for 2 x 30s of gold spraying. Among them, ZIF-8 was prepared by the same method as in example 1 except for the presence or absence of APG. The sample after metal spraying is placed in a scanning electron microscope along with a sample table for sample observation, and the result is shown in figure 1, and as can be seen from figure 1, the form of the ZIF-8 is an orthorhombic dodecahedron with the particle size of 230nm, and the form of the APG @ ZIF-8 composite material of the embodiment 1 is an orthorhombic dodecahedron with the particle size of 250 nm.
Characterization of an APG @ ZIF-8 composite material:
the Fourier transform infrared spectrum characterization result is shown in figure 2. Characterization of the composite crystal by x-ray diffraction the crystal characteristics are shown in figure 3. Thermogravimetric analysis verified the amount of apigenin encapsulated in APG @ ZIF-8, see figure 4. The pore characteristics of APG @ ZIF-8 and ZIF-8 were analyzed using a fully automatic specific surface area porosity analyzer, confirming that the synthesized material had a typical microporous structure with a small number of mesopores, see FIG. 5, and the specific surface area, pore volume and pore diameter were determined, the results are shown in Table 2.
TABLE 2 specific surface area, pore volume and pore diameter of ZIF-8 and APG @ ZIF-8
The results show that the composite material is successfully prepared and has a large specific surface area, the average pore volume of the composite material is reduced after the apigenin is added, and the average pore diameter is increased, because the apigenin fills small pores, the apigenin is proved to be encapsulated in ZIF-8.
The APG @ ZIF-8 has the release performance in different pH environments:
APG @ ZIF-8 of example 1 was dispersed in phosphate buffer solutions at pH 5.0 and 7.5, the release state of apigenin was examined, the solutions were shaken at 37 ℃ (200rpm), and the OD value at 337nm was measured at different time intervals, and the results are shown in fig. 6. As can be seen from FIG. 6, APG @ ZIF-8 of example 1 reached a maximum drug release of 73.70% at pH 5.0 for about 12 hours; the release amount reaches 18.83% in the environment of pH 7.4 for two hours, the release rate increases slowly, and the maximum release amount reaches 23.27% in about 8 hours. The APG @ ZIF-8 is proved to have a good pH response slow release function, and the pH value moves to acidity in the early food decay stage, so that the APG @ ZIF-8 can effectively inhibit bacteria for a long time.
Example 2: the APG @ ZIF-8 composite antibacterial film is prepared by adopting the APG @ ZIF-8 prepared in the embodiment 1, and the preparation method specifically comprises the following steps:
Adding 4g of gelatin, 2.5mg of propolis and 0.75g of APG @ ZIF-8 prepared in the embodiment 1 into 100mL of distilled water, performing ultrasonic treatment to completely disperse the gelatin, adding glycerol to obtain a film-forming solution, performing ultrasonic treatment on the film-forming solution for 10min, pouring the film-forming solution into a polymethyl methacrylate mold, and drying at 40 ℃ to obtain the APG @ ZIF-8 composite antibacterial film, wherein the mass fraction of APG @ ZIF-8 in the film-forming solution is 0.75%, and the adding amount of the glycerol in the film-forming solution is 1.5 vol%.
Example 3: the present embodiment differs from embodiment 2 in that: the mass fraction of APG @ ZIF-8 in the film-forming solution is 1.00%. The other steps and parameters were the same as in example 2.
Comparative example 3: the present embodiment differs from embodiment 2 in that: no APG @ ZIF-8 was added. The other steps and parameters were the same as in example 2.
Comparative example 4: this example differs from example 2 in that: APG @ ZIF-8 was replaced with apigenin, the content was changed from 0.75 wt% to 0.25 wt%. The other steps and parameters were the same as in example 2.
Comparative example 5: this example differs from example 2 in that: the content of the APG @ ZIF-8 is changed from 0.75 wt% to 0.25 wt% by replacing ZIF-8 with the APG @ ZIF-8. The other steps and parameters were the same as in example 2.
Comparative example 6: this example differs from example 2 in that: the mass fraction of APG @ ZIF-8 in the film-forming solution is 0.25%. The other steps and parameters were the same as in example 2.
Comparative example 7: this example differs from example 2 in that: the mass fraction of APG @ ZIF-8 in the film-forming solution is 0.50%. The other steps and parameters were the same as in example 2.
Characterization of the composite film:
the composite membrane was stored at room temperature at a relative humidity of 50%. The integrity of the material in the composite film was characterized using x-ray diffraction and the results are shown in figure 7. The apparent morphology of the composite film was observed by scanning electron microscopy and the results are shown in FIG. 8.
Testing the water stability of the composite film: evaluation of Water stability of composite films by Water content and Water solubility
(1) Cutting the composite film into 20 × 20mm squares with initial mass of M0The film was left at 80 ℃ for 24h to remove all water and reach a constant weight M1. Placing the dried film into 8mL of distilled water, shaking at room temperature for 12h, filtering to remove supernatant, drying the precipitate at 80 deg.C for 24h, and weighing M2。
The water content is (M)1-M0)/M0(ii) a Water soluble ═ M1-M2)/M1The results are shown in Table 3. It can be seen that with the addition of APG @ ZIF-8, the water content and water solubility of the composite film are both obviously reduced, which proves that the water stability is enhanced.
(2) The contact angle was measured by dropping 3. mu.L of water onto the film, and as a result, as shown in FIG. 9, the contact angle reached 126.52 ° when APG @ ZIF-8 was added at 1%.
Testing the mechanical property of the composite film:
The thickness of the composite film was measured with a hand-held digital micrometer, the mechanical properties of the composite film including tensile strength and elongation at break were measured with a texture analyzer, the film was cut into strips of 10mm x 50mm, the initial separation distance was 30mm, the crosshead speed was 50mm/min, and the results are shown in table 3. It can be seen that with the addition of APG @ ZIF-8, the tensile strength of the composite film decreases, demonstrating increased elasticity.
TABLE 3 Water stability and mechanical Properties of the composite films
Bacteriostatic activity of the composite film:
the deposition solutions of examples 2-3 and comparative examples 3-7 were irradiated with UV light for 12 hours to achieve aseptic conditions, and the concentrations of Staphylococcus aureus ATCC 13565 and Escherichia coli ATCC 25922 were adjusted to 106cfu/mL, 1mL of the bacterial solution was mixed with 2mL of the deposition solution, incubated at 37 ℃ for 8 hours, after gradient dilution, the mixed solution (100. mu.L) was uniformly spread on LB medium, incubated at 37 ℃ for 12 hours, and the viable count and the inhibition rate were calculated, and the results are shown in FIG. 10. The results show that the phenomenon that the gram-positive bacteria killing effect of the apigenin is weak is improved by encapsulating the apigenin by using the ZIF-8, and the inhibition rate of the composite film on staphylococcus aureus reaches 100% when the addition amount of the APG @ ZIF-8 is 0.75%. The composite film has stronger killing effect on gram-negative bacteria, and the inhibition rate of the composite film on escherichia coli reaches 100% when the addition amount of APG @ ZIF-8 is 0.25%. The shapes of the bacterial cells before and after the treatment are observed by a scanning electron microscope, the result is shown in figure 11, and the bacterial cells treated by the film-forming solution can be observed to obviously fold and damage and gather, thus proving that the film-forming solution of the composite film can damage the cell structure.
Claims (10)
1. The APG @ ZIF-8 composite material with the pH response slow-release bacteriostatic function is characterized by being composed of apigenin and ZIF-8, wherein the apigenin is encapsulated in the ZIF-8, the APG @ ZIF-8 composite material is in an orthorhombic dodecahedron shape, and the mass fraction of APG in the APG @ ZIF-8 composite material is 5% -12%.
2. The APG @ ZIF-8 composite material with the pH response slow-release bacteriostatic function as claimed in claim 1, wherein the particle size of the APG @ ZIF-8 composite material is 200-300 nm, and the pore volume is 0.6cm3/g~1.0cm3G, the aperture is 10 nm-20 nm, the specific surface area is 1000m2/g~1400m2/g。
3. The preparation method of the APG @ ZIF-8 composite material with the pH response slow-release bacteriostatic function as claimed in claim 1 or 2, characterized in that the preparation method comprises the following steps:
step 1: dissolving 2-methylimidazole in methanol, adding APG, and performing ultrasonic treatment until complete dispersion;
and 2, step: adding a zinc acetate solution at room temperature, magnetically stirring for reaction, centrifuging, washing with methanol, and drying to obtain the APG @ ZIF-8 composite material.
4. The preparation method of the APG @ ZIF-8 composite material with the pH response slow-release bacteriostatic function according to claim 3, wherein the ratio of the mass of the 2-methylimidazole to the volume of the methanol in the step 1 is 330 mg: (10-20) mL, wherein the mass ratio of the 2-methylimidazole to the APG in the step 1 is 330: (4-6).
5. The preparation method of the APG @ ZIF-8 composite material with the pH response slow-release bacteriostatic function according to claim 3, wherein the mass concentration of the zinc acetate solution in the step 2 is 11 mg/mL-22 mg/mL, and the mass ratio of zinc acetate to 2-methylimidazole in the zinc acetate solution is 110: (300-360), wherein the rotation speed of the centrifugation in the step 2 is 7000 rpm-9000 rpm, the time is 10 min-20 min, the drying temperature in the step 2 is 40-60 ℃, and the time is 20 h-24 h.
6. The application of the APG @ ZIF-8 composite material with the pH response slow-release bacteriostatic function in claim 1 or 2, wherein the APG @ ZIF-8 composite material is used for preparing an APG @ ZIF-8 composite bacteriostatic film.
7. The application of the APG @ ZIF-8 composite material with the pH response slow-release antibacterial function is characterized in that the thickness of the APG @ ZIF-8 composite antibacterial film is 97.56-157.89 microns, the water content is 20.57-10.59%, the water solubility is 67.29-42.69%, the tensile strength is 5.06-2.85 MPa, and the elongation at break is 36.84-14.26%.
8. The application of the APG @ ZIF-8 composite material with the pH response slow-release bacteriostatic function according to claim 6, wherein the APG @ ZIF-8 composite bacteriostatic film is prepared by the following steps: adding gelatin, propolis and APG @ ZIF-8 into distilled water, performing ultrasonic treatment to completely disperse the mixture, then adding glycerol to obtain a film-forming solution, performing ultrasonic treatment on the film-forming solution, then pouring the film-forming solution into a polymethyl methacrylate mold, and drying to obtain the APG @ ZIF-8 composite antibacterial film, wherein the mass fraction of the APG @ ZIF-8 in the film-forming solution is 0.75-1.00%.
9. The application of the APG @ ZIF-8 composite material with the pH response slow-release bacteriostatic function in claim 6, wherein the APG @ ZIF-8 composite bacteriostatic film is used for killing food-borne pathogenic bacteria.
10. The application of the APG @ ZIF-8 composite material with the pH response slow-release bacteriostatic function according to claim 9, characterized in that the food-borne pathogenic bacteria comprise staphylococcus aureus and escherichia coli.
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CN115843809A (en) * | 2022-12-29 | 2023-03-28 | 福建农林大学 | Climate response type nano herbicide and preparation method thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109758474A (en) * | 2019-03-06 | 2019-05-17 | 大连民族大学 | A kind of Ag/ZIF-8 antibacterial agent and preparation method thereof |
CN110506741A (en) * | 2019-09-20 | 2019-11-29 | 天津科技大学 | A kind of compound antibacterial material of novel nano and preparation method thereof and purposes |
CN110934138A (en) * | 2019-11-22 | 2020-03-31 | 华南理工大学 | Nano antibacterial material with blue light excitation and acid response release functions, preparation method and application |
CN112156171A (en) * | 2020-10-15 | 2021-01-01 | 安徽医科大学第一附属医院 | Preparation method and application of zinc organic framework composite material capable of releasing vancomycin in light response mode |
CN114028581A (en) * | 2021-10-15 | 2022-02-11 | 南方科技大学 | PH response composite material and preparation method and application thereof |
-
2022
- 2022-04-02 CN CN202210342483.8A patent/CN114747579B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109758474A (en) * | 2019-03-06 | 2019-05-17 | 大连民族大学 | A kind of Ag/ZIF-8 antibacterial agent and preparation method thereof |
CN110506741A (en) * | 2019-09-20 | 2019-11-29 | 天津科技大学 | A kind of compound antibacterial material of novel nano and preparation method thereof and purposes |
CN110934138A (en) * | 2019-11-22 | 2020-03-31 | 华南理工大学 | Nano antibacterial material with blue light excitation and acid response release functions, preparation method and application |
CN112156171A (en) * | 2020-10-15 | 2021-01-01 | 安徽医科大学第一附属医院 | Preparation method and application of zinc organic framework composite material capable of releasing vancomycin in light response mode |
CN114028581A (en) * | 2021-10-15 | 2022-02-11 | 南方科技大学 | PH response composite material and preparation method and application thereof |
Non-Patent Citations (4)
Title |
---|
唐明: "肿瘤微环境响应型MOF-199及ZIF-90复合材料的合成及应用研究", 《硕士电子期刊》, pages 2 * |
张新娟等: "芹菜素联合抗生素的抗耐甲氧西林金黄色葡萄球菌作用", 《中国医院药学杂志》, pages 755 - 758 * |
管靖玮: "ZIF-8包载姜黄素纳米材料的抗菌性能与机理研究", 《硕士电子期刊》 * |
高金龙;贾云婷;谷娜;赵扩林;王奎涛;张炳烛;: "ZIF-8的制备及其作为杀菌药物载体的研究", 分子科学学报, no. 04 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115843809A (en) * | 2022-12-29 | 2023-03-28 | 福建农林大学 | Climate response type nano herbicide and preparation method thereof |
CN115843809B (en) * | 2022-12-29 | 2023-09-08 | 福建农林大学 | Weather-responsive nano herbicide and preparation method thereof |
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