CN114504071A - Metal organic framework sterilization material based on ultrasonic assistance and preparation method and application thereof - Google Patents

Metal organic framework sterilization material based on ultrasonic assistance and preparation method and application thereof Download PDF

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CN114504071A
CN114504071A CN202210081556.2A CN202210081556A CN114504071A CN 114504071 A CN114504071 A CN 114504071A CN 202210081556 A CN202210081556 A CN 202210081556A CN 114504071 A CN114504071 A CN 114504071A
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organic framework
metal organic
ultrasonic
material based
sterilization material
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孙大文
吕鸣春
周希艺
蒲洪彬
韦庆益
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South China University of Technology SCUT
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    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
    • A23L3/358—Inorganic compounds
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
    • A23L2/42—Preservation of non-alcoholic beverages
    • A23L2/44—Preservation of non-alcoholic beverages by adding preservatives
    • 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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel

Abstract

The invention belongs to the technical field of food sterilization, and discloses a metal organic framework sterilization material based on ultrasonic assistance, and a preparation method and application thereof. The method comprises the following steps: firstly, nickel acetate, cobalt acetate, ferrous acetate and 2-amino terephthalic acid react in a solvent to obtain a mixed solution; then carrying out ultrasonic treatment on the mixed solution to obtain a metal organic framework sterilization material; the reaction time is 20-40 min; the ultrasonic treatment time is 0.5-1.5 h. The sterilization material of the invention is in a grid-shaped two-dimensional structure and can catalyze H2O2Decomposing into OH with strong bactericidal capacity, simultaneously improving the specific surface area and the mesoporous structure of MOFs by ultrasonic assistance, enhancing the charge transfer among catalytic active sites, and greatly enhancing the metal by combining the synergistic catalytic effect of three metal ionsThe catalytic activity and the antibacterial activity of the organic framework achieve the purpose of high-efficiency sterilization. The sterilization material of the invention is used for inhibiting food-borne pathogenic bacteria.

Description

Metal organic framework sterilization material based on ultrasonic assistance and preparation method and application thereof
Technical Field
The invention belongs to the field of food sterilization, and particularly relates to a metal organic framework sterilization material based on ultrasonic assistance, and a preparation method and application thereof.
Background
Food and water are vital resources and are extremely easily polluted by pathogenic bacteria such as escherichia coli and staphylococcus aureus. Food-borne pathogenic bacteria are often present in foods with rich nutrition such as bread, leftovers, milk and the like, and after people eat the foods by mistake or are infected with the foods, the food poisoning, the skin ulceration, the reduction of the immune system function and other hazards are usually caused, and even meningeal inflammation and shock are caused in severe cases. Human health problems caused by food-borne pathogens have become a leading public health problem worldwide.
The Fenton reaction refers to hydrogen peroxide (H)2O2) Under acidic condition by Fe2+Catalyzing the generation of hydroxyl radicals (. OH) which are very oxidizing. The generated OH is more specific to bacteria than hydrogen peroxide (H)2O2) Has stronger toxicity, can effectively kill bacteria without selection, has broad-spectrum antibacterial property and solves the problem of bacterial drug resistance. The traditional Fenton system has low oxidation utilization rate and narrow pH range, and aims to ensure that H is generated2O2Rapid and efficient decomposition, stronger fenton catalysts need to be developed.
The Metal Organic Frameworks (MOFs) are crystalline porous materials formed by metal sites and organic ligands, have high specific surface area, high porosity and well-dispersed active centers, and the topological structure of the materials is adjustable. MOFs have been extensively studied as heterogeneous fenton-like catalysts whose active centers (metal sites) are stabilized by chemical bonds that are strong enough to stabilize their structure, making the material robust, while weak enough not to impede its activity. MOFs as Fenton catalyst can catalyze H2O2OH is generated by decomposition, so that the antibacterial activity is strong, the problem of bacterial drug resistance does not exist, but the defects of poor catalytic effect, large dosage and the like cannot be overcome by the conventional MOFs, and the effective sterilization effect cannot be achieved.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a preparation method of a metal organic framework sterilization material based on ultrasonic assistance, which is simple to operate, low in cost and expected to be used for industrial production.
Another object of the present invention is to provide a method for preparing the sameA metal organic framework sterilization material based on ultrasonic assistance can efficiently catalyze H2O2Decomposing to generate OH.
Still another object of the present invention is to provide the application of the metal organic framework sterilization material based on ultrasonic assistance. The metal organic framework sterilization material based on ultrasonic assistance is used for inhibiting food-borne pathogenic bacteria. The metal organic framework bactericidal material can be used as a Fenton catalyst to catalyze H in bacterial suspension2O2The metal organic framework is decomposed into OH with strong sterilization capability, meanwhile, the specific surface area and the mesoporous structure of MOFs are improved through ultrasonic assistance, charge transfer among catalytic active sites is enhanced, the synergistic catalytic effect of three metal ions is combined, the catalytic activity and the antibacterial activity of the metal organic framework are greatly enhanced, and the purpose of efficient sterilization is achieved.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a metal organic framework sterilization material based on ultrasonic assistance comprises the following steps:
s1: reacting nickel acetate, cobalt acetate, ferrous acetate and 2-amino terephthalic acid in a solvent to obtain a mixed solution;
s2: carrying out ultrasonic treatment on the mixed solution to obtain a metal organic framework sterilization material based on ultrasonic assistance;
the ultrasonic treatment conditions are as follows: the ultrasonic power is 400-600W, and the ultrasonic time is 0.5-1.5 h, preferably 1 h; the temperature was room temperature.
The solvent is at least one of N, N-dimethylformamide and methanol.
In step S1, the ratio of the amounts of the nickel acetate, the cobalt acetate and the ferrous acetate is 1:3:6 to 6:3:1, preferably 1 (0.5 to 1.5) to (0.5 to 1.5), and more preferably 1:1: 1.
The ratio of the amount of the 2-aminoterephthalic acid substance to the total amount of the nickel acetate, cobalt acetate and ferrous acetate in step S1 is 1:2 to 2:1, preferably 1: 1.
The reaction time in the step S1 is 20-40 min. The reaction temperature was room temperature.
The reaction in step S1 is carried out under the condition of stirring, and the stirring speed is 200-400 rpm.
The specific step of step S1: dissolving nickel acetate, cobalt acetate and ferrous acetate in a solvent to obtain a solution A; dissolving 2-amino terephthalic acid in a solvent to obtain a solution B; then, the solution A and the solution B are mixed and reacted at room temperature under the condition of stirring to obtain a mixed solution.
The volume ratio of the solvent in the solution A to the solvent in the solution B is 1: 1-3: 1, and the preferable volume ratio is 2: 1.
The volume ratio of the total amount of nickel acetate, cobalt acetate and ferrous acetate in the solution A to the solvent is 1mmol (5-15) mL;
the volume ratio of the 2-amino terephthalic acid substance in the liquid B to the solvent is 1mmol: (4-10) mL.
After the ultrasonic treatment in step S2, the system is subjected to a subsequent treatment. The subsequent treatment refers to centrifugation, washing and drying. The washing is to wash by adopting N, N-dimethylformamide and ethanol respectively; the drying is vacuum drying.
The method comprises the steps of respectively washing by adopting N, N-dimethylformamide and ethanol for 2-3 times.
The temperature of vacuum drying is 55-65 ℃.
And the vacuum drying time is 10-15 h.
The metal organic framework sterilization material in the S2 is a latticed metal organic framework sterilization material.
The metal organic framework sterilization material based on ultrasonic assistance is prepared by the preparation method. The metal organic framework sterilization material based on ultrasonic assistance is used for preparing antibacterial products, in particular products for inhibiting food-borne pathogenic bacteria.
An antibacterial product comprises the metal organic framework sterilization material based on ultrasonic assistance and H2O2。
The metal organic framework sterilization material based on ultrasonic assistance and H2O2The mass molar ratio of (95-110) μ g: (5-20) mu mmol.
The application of the metal organic framework sterilization material based on ultrasonic assistance in inhibiting food-borne pathogenic bacteria comprises the following steps: the metal organic framework sterilization material based on ultrasonic assistance and H2O2Placing the sample in a sample containing bacteria, and performing sterilization treatment.
The bacteria include Escherichia coli, Staphylococcus aureus, and Salmonella.
The density of bacteria in the sample containing bacteria is 105～108CFU/mL, preferably 106CFU/mL。
The time of the sterilization treatment is 2-4 h. The temperature of the sterilization treatment is more than or equal to room temperature.
The final concentration of the metal organic framework is 95-105 mug/mL, and preferably 100 mug/mL.
Said H2O2The final concentration of (b) is 5 to 15mM, preferably 10 mM.
The application of the metal organic framework sterilization material based on ultrasonic assistance in inhibiting food-borne pathogenic bacteria refers to the utilization of the metal organic framework sterilization material based on ultrasonic assistance and H2O2The method of (1) for sterilization.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the preparation method of the metal organic framework sterilization material based on ultrasonic assistance is simple, does not need complex instruments and equipment, has low cost, and is expected to be used for industrial production.
(2) The invention adopts the metal organic framework as a sterilization material, which can be used as a Fenton catalyst to catalyze H2O2Decomposing into OH with strong bactericidal ability, thereby inactivating bacteria by using OH, and having broad-spectrum antibacterial property, low toxicity to normal cells, and no generation of antibacterial drug resistance. In addition, the metal organic framework sterilization material based on ultrasonic assistance effectively reduces the sterilization material and H2O2The dosage is reduced, the toxic and side effects are reduced, and the bactericidal material and H are improved2O2The utilization ratio of (2).
(3) Compared with the prior sterilization technology, the method has the advantages that,the metal organic framework sterilization material is a latticed two-dimensional nanosheet material prepared by ultrasonic assistance and capable of catalyzing H2O2The compound is decomposed into OH with strong toxicity, and simultaneously, the ultrasonic assistance not only improves the specific surface area and the mesoporous structure of MOFs, but also enhances the charge transfer among catalytic active sites, and combines the synergistic catalytic effect of three metal ions, thereby greatly enhancing the catalytic activity and the antibacterial activity of a metal organic framework and achieving the purpose of high-efficiency sterilization.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) representation (magnification is 20000 times) of the metal organic framework sterilization material based on ultrasonic assistance obtained in example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) representation (magnification of 5000 times) of the metal organic framework sterilization material based on ultrasonic assistance obtained in example 1;
FIG. 3 shows the metal organic framework sterilization material Ni based on ultrasonic assistance obtained in example 46Co3Fe1-Scanning Electron Microscope (SEM) characterization of MOFs (magnification 20000);
FIG. 4 shows the metal organic framework sterilization material Ni based on ultrasonic assistance obtained in example 46Co3Fe1-Scanning Electron Microscope (SEM) characterization of MOFs (5000 x magnification);
FIG. 5 shows the Ni concentrations in example 41Co1Fe1-MOF (A) and Ni6Co3Fe1-graph of MIC test results of mof (b) material against staphylococcus aureus with antimicrobial concentrations from left to right: 6.25, 12.5, 25, 50, 100, 200, 300, 400, 500. mu.g/mL.
Detailed Description
Embodiments of the present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto. The various starting materials, reagents, instruments, equipment, etc. described in the examples are commercially available or can be prepared by existing methods.
The antibacterial performance test steps of the bactericidal material in the embodiments 1-3 are as follows:
(1) culturing strains: a small amount of bacterial strains are streaked on an LB solid culture medium, and then the solid culture medium is placed in an incubator at 37 ℃ for culture. Picking single colony from LB solid culture medium and dispersing into 100mLLB liquid culture medium, moving the liquid culture medium into a 37 ℃ incubator, shaking at the speed of 150rpm on a shaking table, taking bacterial suspension cultured to logarithmic phase, and centrifuging to obtain bacterial cell. Then, using sterile physiological saline (pH7.0 quality concentration of 0.9% NaCl solution) to wash cells for 3 times to remove the growth medium residues, dispersing the cell sediment in a certain volume of sterile physiological saline again, diluting the bacterial suspension, and storing for later use;
(2) and (3) bacteriostatic test: using blank control solution and H respectively for equal volume of bacterial suspension2O2Metal organic framework + H without ultrasonic treatment2O2Metal organic frame sterilizing material + H2O2And (3) treating, placing the treated bacteria liquid in a 37 ℃ incubator on a shaking table to shake at the speed of 150rpm, taking 100 mu L of the treated bacteria liquid, inoculating the bacteria liquid to an LB solid culture medium according to a plate coating method, placing the bacteria liquid in the 37 ℃ incubator to be cultured, then counting viable bacteria colonies, and researching the antibacterial performance of the bacteria liquid. The bactericidal rate is (number of colonies in control group-number of colonies in experimental group)/number of colonies in control group × 100%.
The strains in the step (1) comprise escherichia coli, staphylococcus aureus and salmonella.
The cultivation time of the LB solid culture medium in the step (1) is 24-48 h, and preferably 36 h.
The culture time of the LB liquid culture medium in the step (1) is 3.5-4 h.
The bacterial density of the bacterial suspension in the step (1) is 105～108CFU/mL, preferably 106CFU/mL。
The volume of the bacterial suspension in the step (2) is 5 mL. The blank control solution in the step (2) is sterile normal saline.
The final concentration of the metal-organic framework which is not subjected to ultrasonic treatment in the step (2) is 95-105 mug/mL, and preferably 100 mug/mL.
The final concentration of the metal organic framework in the step (2) is 95-105 mug/mL, and preferably 100 mug/mL.
H in the step (2)2O2The final concentration of (b) is 5 to 15mM, preferably 10 mM.
And (3) oscillating for 2-4 h, preferably for 2 h.
The cultivation time of the LB solid culture medium in the step (2) is 24-48 h, and preferably 36 h.
Example 1
A preparation method of a metal organic framework sterilization material based on ultrasonic assistance comprises the following steps:
(1) dissolving nickel acetate, cobalt acetate and ferrous acetate in a substance amount ratio of 1:1:1 (total substance amount is 1mmol) into 10mLN, N-dimethylformamide to obtain solution A, dissolving 1mmol of 2-amino terephthalic acid into 5mLN, N-dimethylformamide to obtain solution B, then pouring the solution A into the solution B under magnetic stirring (rotating speed of 300rpm), and mixing and reacting at room temperature for 30 min;
(2) and (2) carrying out ultrasonic treatment on the mixed solution obtained in the step (1) at room temperature for 1h (the ultrasonic power is 500W), centrifuging after the treatment is finished to obtain a product, washing the product for 2 times by using N, N-dimethylformamide and ethanol respectively, then carrying out vacuum drying at 60 ℃ for 12h to obtain a sterilization material (the sterilization material based on ultrasonic assistance), and storing the sterilization material in a normal-temperature sealed container.
Non-sonicated metal organic framework: preparing a metal organic framework which is not subjected to ultrasonic treatment according to the same method in the step (1), wherein the mixing reaction time at room temperature is 1.5 h; then washing, drying and storing the prepared material in a normal-temperature sealed container.
Fig. 1 is a Scanning Electron Microscope (SEM) characterization diagram (magnification is 20000 times) of the metal organic framework bactericidal material based on ultrasonic assistance obtained in example 1, which shows the morphology of the metal organic framework.
Fig. 2 is a Scanning Electron Microscope (SEM) characterization image (with a magnification of 5000 times) of the metal organic framework bactericidal material based on ultrasonic assistance obtained in example 1, and shows the morphology of the metal organic framework.
The metal organic framework sterilization material based on ultrasonic assistance is applied to inhibition of food-borne pathogenic bacteria.
And (3) testing antibacterial performance:
(S1) taking a small amount of staphylococcus aureus (ATCC6538, the strain is purchased from the development center of Guangdong food and microorganism safety engineering technology) to streak on an LB solid culture medium, and then putting the solid culture medium into an incubator at 37 ℃ for culturing for 36 h. Picking single colony from LB solid culture medium and dispersing into 100mLLB liquid culture medium, transferring the liquid culture medium into a 37 ℃ incubator, shaking at the speed of 150rpm on a shaking table, taking bacterial suspension after 4.5h of culture, and centrifuging to obtain bacterial cell. Then, the cells were washed 3 times with sterile physiological saline (0.9% NaCl solution by mass concentration at pH 7.0) to remove the growth medium residue, the cell pellet was redispersed in a volume of sterile physiological saline, and the bacterial density of the bacterial suspension was diluted to 106CFU/mL, and storing for later use;
(S2) 5mL of the Staphylococcus aureus suspension obtained in the step (S1) was treated with sterile physiological saline (0.9% NaCl solution by mass, 50. mu.L) (control group, group 1), H2O2(10mM) (group 2), non-sonicated metal organic framework (100. mu.g/mL) + H2O2(10mM) (group 3), Metal organic framework Sterilization Material (100. mu.g/mL) + H2O2(10mM) (group 4), placing the mixture in an incubator at 37 ℃ and shaking the mixture on a shaking table at the speed of 150rpm, taking 100 mu L of the treated bacterium solution after 2h, inoculating the bacterium solution to an LB solid culture medium according to a plate coating method, placing the LB solid culture medium in the incubator at 37 ℃ for culturing for 36h, then counting viable bacteria colonies, and calculating the sterilization rate according to the following formula:
the bactericidal rate is (number of colonies in control group-number of colonies in experimental group)/number of colonies in control group × 100%
The calculated bactericidal rates for group 2, group 3 and group 4 were 1.97%, 85.12% and 99.54%, respectively, indicating 10mM H alone2O2Almost has no bactericidal effect on staphylococcus aureus; 100. mu.g/mL of non-sonicated metal organic framework and 10mM of H2O2Can kill most of Staphylococcus aureus; while 100. mu.g/mL of the metal-organic framework bactericidal material and 10mM of H2O2The synergistic effect of (A) can almost completely kill staphylococcus aureus.
Example 2
A preparation method of a metal organic framework sterilization material based on ultrasonic assistance comprises the following steps:
(1) dissolving nickel acetate, cobalt acetate and ferrous acetate in a substance amount ratio of 1:1:1 (total substance amount is 1mmol) into 10mLN, N-dimethylformamide to obtain solution A, dissolving 1mmol of 2-amino terephthalic acid into 5mLN, N-dimethylformamide to obtain solution B, then pouring the solution A into the solution B under magnetic stirring (rotating speed of 300rpm), and mixing and reacting at room temperature for 30 min;
(2) and (2) carrying out ultrasonic treatment on the mixed solution obtained in the step (1) at room temperature for 1h, centrifuging after the treatment to obtain a product, washing the product for 2 times by using N, N-dimethylformamide and ethanol respectively, then carrying out vacuum drying at 60 ℃ for 12h to obtain a sterilizing material, and storing the sterilizing material in a normal-temperature sealed container.
Non-sonicated metal organic framework: preparing a metal organic framework which is not subjected to ultrasonic treatment according to the same method in the step (1), wherein the mixing reaction time at room temperature is 1.5 h; then washing, drying and storing the prepared material in a normal-temperature sealed container.
The metal organic framework sterilization material based on ultrasonic assistance is applied to inhibition of food-borne pathogenic bacteria.
And (3) testing antibacterial performance:
(S1) streaking a small amount of Salmonella (ATCC14028, strain purchased from Guangdong center for research and development of food and microorganism safety engineering) on LB solid medium, and then culturing the solid medium in an incubator at 37 ℃ for 36 h. Picking single colony from LB solid culture medium and dispersing into 100mLLB liquid culture medium, transferring the liquid culture medium into a 37 ℃ incubator, shaking at the speed of 150rpm on a shaking table, taking bacterial suspension after 3.5h of culture, and centrifuging to obtain bacterial cell. Then, the cells were washed 3 times with sterile physiological saline (0.9% NaCl solution by mass concentration at pH 7.0) to remove the growth medium residue, the cell pellet was redispersed in a volume of sterile physiological saline, and the bacteria of the bacterial suspension were suspendedDiluting to density of 106CFU/mL, and storing for later use;
(S2) 5mL of the Salmonella suspension obtained in the step (S1) was treated with sterile physiological saline (0.9% NaCl solution by mass, 50. mu.L) (control group, group 1), and H, respectively2O2(10mM) (group 2), non-sonicated metal organic framework (100. mu.g/mL) + H2O2(10mM) (group 3), Metal organic framework Sterilization Material (100. mu.g/mL) + H2O2(10mM) (group 4), placing the mixture in an incubator at 37 ℃ and shaking the mixture on a shaking table at the speed of 150rpm, taking 100 mu L of the treated bacterium solution after 2h, inoculating the bacterium solution to an LB solid culture medium according to a plate coating method, placing the LB solid culture medium in the incubator at 37 ℃ for culturing for 36h, then counting viable bacteria colonies, and calculating the sterilization rate according to the following formula:
the bactericidal rate is (number of colonies in control group-number of colonies in experimental group)/number of colonies in control group × 100%
The calculated bactericidal rates for group 2, group 3 and group 4 were 1.77%, 74.28% and 98.23%, respectively, indicating 10mM H2O2The sterilization effect on salmonella is almost no; 100. mu.g/mL of non-sonicated metal organic framework and 10mM of H2O2Can kill most of salmonella; and 100 mu g/mL of metal organic framework bactericidal material and 10mM of H2O2The synergistic effect of (A) can almost completely kill the salmonella.
Example 3
A preparation method of a metal organic framework sterilization material based on ultrasonic assistance comprises the following steps: the same as in example 1.
Non-sonicated metal organic framework: the same as in example 1.
The metal organic framework sterilization material based on ultrasonic assistance is applied to inhibition of food-borne pathogenic bacteria.
And (3) testing antibacterial performance:
(S1) streaking a small amount of Escherichia coli (ATCC700728, strain purchased from Guangdong research center for food and microorganism safety engineering) on LB solid medium, and culturing in 37 deg.C incubator for 36 h. Picking single colony from LB solid culture medium and dispersing to 100mLLB liquidIn the culture medium, the liquid culture medium is transferred to a 37 ℃ incubator and is shaken on a shaking table at the speed of 150rpm, and bacterial suspension after 3.5h of culture is taken and centrifuged to obtain bacterial cells. Then, the cells were washed 3 times with sterile physiological saline (0.9% NaCl solution by mass concentration at pH 7.0) to remove the growth medium residue, the cell pellet was redispersed in a volume of sterile physiological saline, and the bacterial density of the bacterial suspension was diluted to 106CFU/mL, and storing for later use;
(S2) 5mL of the E.coli suspension obtained in the step (S1) were treated with sterile physiological saline (0.9% NaCl solution by mass, 50. mu.L) (control group, group 1), H2O2(10mM) (group 2), non-sonicated metal organic framework (100. mu.g/mL) + H2O2(10mM) (group 3), Metal organic framework Sterilization Material (100. mu.g/mL) + H2O2(10mM) (group 4), placing the mixture in a 37 ℃ incubator, shaking the mixture on a shaking table at the speed of 150rpm, taking 100 mu L of the treated bacterium solution after 2 hours, inoculating the bacterium solution to an LB solid culture medium according to a plate coating method, placing the LB solid culture medium in the incubator at 37 ℃ for 36 hours, counting viable bacteria colonies, and calculating the sterilization rate according to the following formula:
the bactericidal rate is (number of colonies in control group-number of colonies in experimental group)/number of colonies in control group × 100%
The calculated bactericidal rates for group 2, group 3 and group 4 were 1.88%, 50.94% and 93.33%, respectively, indicating 10mM H2O2Almost has no bactericidal effect on escherichia coli; 100. mu.g/mL of non-sonicated metal organic framework and 10mM of H2O2Can kill part of Escherichia coli; while 100. mu.g/mL of the metal-organic framework bactericidal material and 10mM of H2O2The synergistic effect of (A) can kill most of Escherichia coli.
Example 4
A preparation method of a metal organic framework sterilization material based on ultrasonic assistance comprises the following steps:
(1) dissolving nickel acetate, cobalt acetate and ferrous acetate with the mass ratio of 6:3:1 (the total mass is 1mmol) into 10mLN, N-dimethylformamide to obtain solution A, dissolving 1mmol of 2-amino terephthalic acid into 5mLN, N-dimethylformamide to obtain solution B, then pouring the solution A into the solution B under magnetic stirring (rotating speed of 300rpm), and mixing and reacting at room temperature for 30 min;
(2) dissolving nickel acetate, cobalt acetate and ferrous acetate in a substance amount ratio of 1:1:1 (total substance amount is 1mmol) into 10mLN, N-dimethylformamide to obtain solution A, dissolving 1mmol of 2-amino terephthalic acid into 5mLN, N-dimethylformamide to obtain solution B, then pouring the solution A into the solution B under magnetic stirring (rotating speed of 300rpm), and mixing and reacting at room temperature for 30 min;
(3) respectively carrying out ultrasonic treatment on the mixed solution obtained in the step (1) and the step (2) at room temperature for 1h (the ultrasonic power is 500W), centrifuging after the treatment is finished to obtain a product, washing the product for 2 times by using N, N-dimethylformamide and ethanol respectively, and then carrying out vacuum drying at 60 ℃ for 12h to respectively obtain a sterilization material Ni6Co3Fe1-MOF and Ni1Co1Fe1-MOF, storing in a hermetically sealed container at ambient temperature.
FIG. 3 shows the metal organic framework sterilization material Ni based on ultrasonic assistance obtained in example 46Co3Fe1Scanning Electron Microscope (SEM) characterization of MOFs (magnification 20000) showing the morphology of the metal-organic framework.
FIG. 4 shows the metal organic framework sterilization material Ni based on ultrasonic assistance obtained in example 46Co3Fe1Scanning Electron Microscopy (SEM) characterization of MOFs (magnification 5000), showing the morphology of the metal-organic framework.
The metal organic framework sterilization material based on ultrasonic assistance is applied to inhibition of food-borne pathogenic bacteria.
And (3) testing antibacterial performance:
(S1) taking a small amount of staphylococcus aureus (ATCC6538, the strain is purchased from the development center of Guangdong food and microorganism safety engineering technology) to streak on an LB solid culture medium, and then putting the solid culture medium into an incubator at 37 ℃ for culturing for 36 h. Picking single colony from LB solid culture medium, dispersing into 100mLLB liquid culture medium, transferring the liquid culture medium into 37 deg.C incubator, shaking at 150rpm on shakerAnd (4) taking the bacterial suspension after 4.5h of culture, and centrifuging to obtain bacterial cells. Then, the cells were washed 3 times with sterile physiological saline (0.9% NaCl solution by mass concentration at pH 7.0) to remove the growth medium residue, the cell pellet was redispersed in a volume of sterile physiological saline, and the bacterial density of the bacterial suspension was diluted to 108CFU/mL, and storing for later use;
(S2) separately collecting Ni as a sterilizing material6Co3Fe1-MOF and Ni1Co1Fe1The MOF is prepared into a sterile aqueous solution of 1mg/mL, and after uniform dispersion under ultrasound, the suspension is respectively diluted into a series of test solutions with concentration gradients of 800, 600, 400, 200, 100, 50, 25, 12.5 and 6.25 mu g/mL.
(S3) 2.5mL of each of the test solutions having different concentrations obtained in the step (S2) and 2.5mL of double LB liquid medium were mixed in a test tube. Then 100. mu.L of the bacterial suspension (10) prepared in the step (S1) was taken8CFU/mL), inoculated in tubes containing different concentrations of MOFs material and double LB liquid medium, as experimental groups. Another 100. mu.L of the bacterial suspension prepared in step (S1) was inoculated into 5mL of LB liquid medium containing no MOFs material as a positive control. Test tubes containing only 5mL of LB liquid medium served as a negative control group. The test tube was placed in a constant temperature shaker (speed 150rmp/min), incubated overnight at 37 ℃ and the experimental results were observed to determine the Ni produced6Co3Fe1-MOF and Ni1Co1Fe1-Minimum Inhibitory Concentration (MIC) of MOF.
MIC refers to the lowest concentration of drug required to inhibit bacterial growth, and the lowest concentration of drug that does not allow bacterial growth to be seen to the naked eye during testing can be considered MIC.
FIG. 5 shows the Ni concentrations in example 41Co1Fe1-MOF (A) and Ni6Co3Fe1-graph of MIC test results of mof (b) material against staphylococcus aureus with antimicrobial concentrations from left to right: 6.25, 12.5, 25, 50, 100, 200, 300, 400, 500. mu.g/mL.
As can be seen from FIG. 5, golden yellow dextran in test tube without antibacterial effectStaphylococci multiply and eventually lead to turbid culture fluid. When the nutrient solution in the test tube is kept clear and transparent, the growth of staphylococcus aureus is considered to be inhibited, and the concentration of the antibacterial agent corresponding to the test tube which is clear and transparent is the MIC, so that Ni1Co1Fe1MIC of MOF 200. mu.g/mL, Ni6Co3Fe1The MIC of MOF was 300. mu.g/mL. Indicating Ni1Co1Fe1-MOF ratio Ni6Co3Fe1MOFs have better antibacterial properties.
Without being limited to the above embodiments, other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the invention should be construed as equivalents thereof and are intended to be included in the scope of the invention.

Claims (10)

1. A preparation method of a metal organic framework sterilization material based on ultrasonic assistance is characterized by comprising the following steps: the method comprises the following steps:
s1: reacting nickel acetate, cobalt acetate, ferrous acetate and 2-amino terephthalic acid in a solvent to obtain a mixed solution; in the step S1, the mass ratio of the nickel acetate, the cobalt acetate and the ferrous acetate is 1:3: 6-6: 3: 1; the ratio of the amount of the 2-amino terephthalic acid substance to the total amount of the nickel acetate, cobalt acetate and ferrous acetate in the step S1 is 1:2 to 2: 1;
s2: carrying out ultrasonic treatment on the mixed solution to obtain a metal organic framework sterilization material based on ultrasonic assistance;
the ultrasonic treatment conditions are as follows: the ultrasonic power is 400-600W, and the ultrasonic time is 0.5-1.5 h.
2. The preparation method of the metal organic framework sterilization material based on ultrasonic assistance according to claim 1, is characterized in that: conditions of the ultrasonic processing in step S2: the ultrasonic power is 500W, and the ultrasonic time is 1 h; the temperature is room temperature;
in the step S1, the solvent is at least one of N, N-dimethylformamide and methanol;
the reaction time in the step S1 is 20-40 min.
3. The preparation method of the metal organic framework sterilization material based on ultrasonic assistance according to claim 1, is characterized in that: the temperature of the reaction in step S1 is room temperature;
the reaction in the step S1 is carried out under the condition of stirring, and the stirring rotating speed is 200-400 rpm;
after the ultrasonic treatment in the step S2, carrying out subsequent treatment on the system; the subsequent treatment refers to centrifugation, washing and drying.
4. The preparation method of the metal organic framework sterilization material based on ultrasonic assistance according to claim 1, is characterized in that: the specific step of step S1: dissolving nickel acetate, cobalt acetate and ferrous acetate in a solvent to obtain a solution A; dissolving 2-amino terephthalic acid in a solvent to obtain a solution B; then, the solution A and the solution B are mixed and reacted at room temperature under the condition of stirring to obtain a mixed solution.
5. The preparation method of the metal organic framework sterilization material based on ultrasonic assistance according to claim 4, is characterized in that: the volume ratio of the solvent in the solution A to the solvent in the solution B is 1: 1-3: 1;
the volume ratio of the total amount of nickel acetate, cobalt acetate and ferrous acetate in the solution A to the solvent is 1mmol (5-15) mL;
the volume ratio of the 2-amino terephthalic acid substance in the liquid B to the solvent is 1mmol: (4-10) mL.
6. The metal organic framework sterilization material based on ultrasonic assistance obtained by the preparation method of any one of claims 1 to 5.
7. The application of the metal organic framework sterilization material based on ultrasonic assistance according to claim 6 is characterized in that: the metal organic framework sterilization material based on ultrasonic assistance is used for preparing an antibacterial product.
8. An antimicrobial article characterized by: comprising the metal-organic framework sterilizing material based on ultrasonic assistance of claim 6 and H2O2；
The metal organic framework sterilization material based on ultrasonic assistance and H2O2The mass molar ratio of (95-110) μ g: (5-20) mu mmol.
9. The application of the metal-organic framework sterilizing material based on ultrasonic assistance in inhibiting food-borne pathogenic bacteria according to claim 6 is characterized in that: the method comprises the following steps: the metal-organic framework sterilization material based on ultrasonic assistance of claim 6 and H2O2Placing the sample in a sample containing bacteria, and performing sterilization treatment.
10. Use according to claim 9, characterized in that: the strains comprise escherichia coli, staphylococcus aureus and salmonella; the dosage ratio of the metal organic framework sterilization material to bacteria is (95-105) mu g: (105～108) A CFU; the metal organic framework sterilization material and H2O2The dosage ratio of (95-105) mu g: (5-15) mu mmol;
the density of bacteria in the sample containing bacteria is 105～108CFU/mL；
The time of the sterilization treatment is 2-4 h; the temperature of the sterilization treatment is more than or equal to room temperature.
CN202210081556.2A 2022-01-24 2022-01-24 Metal organic framework sterilization material based on ultrasonic assistance and preparation method and application thereof Pending CN114504071A (en)

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