Modified prussian blue analogue as well as preparation method and application thereof

Abstract

The invention relates to the technical field of food sterilization materials, and discloses a modified prussian blue analogue as well as a preparation method and application thereof. The method comprises the following steps: (1) dissolving a nickel source, a manganese source and sodium citrate in water to obtain a mixture I; (2) carrying out contact reaction on a potassium ferricyanide solution and the mixture I, and then sequentially carrying out aging, water washing, alcohol washing and first drying to obtain a Prussian blue analogue; (3) dispersing the Prussian blue analogue in a mixed solution of sulfuric acid and ethylene glycol to obtain a mixture II; and (4) performing microwave treatment on the mixture II, and performing purification and secondary drying to obtain the modified prussian blue analogue. The modified Prussian blue analogue prepared by the method provided by the invention has photo-thermal performance and catalase-like activity, can achieve the purpose of efficient and synergistic sterilization on food-borne pathogenic bacteria, and effectively reduces the use of a sterilization material and H2O2 at the same time.

Description

Technical Field

[0001] The present invention relates to the technical field of food sterilization materials, and particularly relates to a modified Prussian blue analogue, a preparation method thereof and an application thereof. Background Art

[0002] Foodborne pathogenic bacteria pose a serious threat to food safety and human health, and the current situation is not optimistic. On the one hand, common foodborne pathogenic bacteria such as Salmonella, Vibrio parahaemolyticus, Staphylococcus aureus, Listeria monocytogenes, etc. are widely present in various foods. On the other hand, the diseases caused by foodborne pathogenic bacteria are seriously harmful. Patients will experience symptoms such as vomiting, diarrhea, abdominal pain, fever, etc., and may even lead to dehydration, shock and endanger life. With the increasing complexity of food production, processing, transportation and sales and other links, the transmission routes of foodborne pathogenic bacteria are more diversified, increasing the difficulty of prevention and control.

[0003] Therefore, food microorganism killing is very important in the risk assessment of foodborne pathogenic bacteria. Commonly used sterilization technologies include thermal sterilization, irradiation sterilization, high-voltage pulsed electric field sterilization, ultrasonic sterilization and cold plasma sterilization, etc. Research shows that foodborne pathogenic bacteria have developed certain tolerance and drug resistance to traditional processing and killing technologies, posing a severe challenge to food safety.

[0004] Photocatalytic sterilization technology, as a fast, effective and antibiotic-free antibacterial means, has received more and more attention from researchers. Photocatalytic sterilization mainly activates photosensitive materials through light response to generate hydroxyl radicals, which destroy the bacterial membrane and cell wall of bacteria when combined with bacteria, thereby destroying the bacterial defense system and inactivating the bacteria. The adjustable characteristics and surface functions of photosensitive nanomaterials provide more precise and flexible design space, and can maximize the antibacterial performance to ensure food safety.

[0005] As a functional nanomaterial simulating enzymes, Prussian blue nanoparticles are metal-organic frameworks composed of trivalent iron, ferrous and cyanide complexes. Their multiple activities and significant advantages have enabled them to be widely used in emerging interdisciplinary fields such as biomedicine, analytical chemistry, environment, food and agriculture. In recent years, Prussian blue analogues synthesized by replacing divalent and trivalent iron ions in Prussian blue with different transition metals, with octahedral configurations centered on different metal ions and cyanide ligands, have shown significant absorption and excellent photothermal conversion efficiency in the near-infrared region due to their open porous structures, demonstrating good photothermal properties. However, current Prussian blue analogues still face some challenges: on the one hand, crystal defects are easily generated during their synthesis process, affecting the overall performance of the materials; on the other hand, the existence of multiple crystal morphologies leads to insufficient stability. In addition, their peroxidase-like activity, antibacterial performance and photothermal performance all need to be further improved.

[0006] Therefore, the research on improving the performance of octahedral configuration Prussian blue compounds has important practical significance for ensuring food safety and human health. Summary of the Invention

[0007] The object of the present invention is to solve the problems of low bactericidal efficiency, poor stability, high cost, high toxicity, and emergence of drug resistance of antibacterial agents in the prior art.

[0008] In order to achieve the above object, the first aspect of the present invention provides a method for preparing a modified Prussian blue analogue, the method comprising the following steps:

[0009] (1) Dissolve a nickel source, a manganese source, and sodium citrate in water to obtain a mixture I;

[0010] (2) Contact-react a potassium ferrocyanide solution with the mixture I, and then successively carry out aging, water washing, alcohol washing, and first drying to obtain a Prussian blue analogue;

[0011] (3) Disperse the Prussian blue analogue in a mixed solution of sulfuric acid and ethylene glycol to obtain a mixture II;

[0012] (4) Subject the mixture II to microwave treatment, and obtain a modified Prussian blue analogue after purification and second drying.

[0013] The second aspect of the present invention provides a modified Prussian blue analogue prepared by the method described in the first aspect.

[0014] The third aspect of the present invention provides the application of the modified Prussian blue analogue described in the second aspect in killing foodborne pathogenic bacteria.

[0015] Compared with the prior art, the method provided by the present invention has at least the following beneficial effects:

[0016] (1) The present invention rapidly synthesizes a novel modified Prussian blue analogue by microwave assistance. Its preparation method is simple, the synthesis time is short, no complex instrument and equipment are required, and the energy consumption is low, and it is expected to be used for industrial production;

[0017] (2) The novel material of the modified Prussian blue analogue prepared by the present invention has an open framework structure, a high specific surface area, a large pore volume, and prominent rich active sites, which significantly improves its enzyme-like catalytic activity and has obvious advantages of high-efficiency antibacterial and no bacterial drug resistance;

[0018] (3) The novel material of the modified Prussian blue analogue prepared by the present invention has powerful structural stability, photothermal properties, broad-spectrum antibacterial properties, and the outstanding characteristic of no antibiotic residue. It exhibits strong light absorption ability in the near-infrared region, can effectively convert light energy into heat energy, and cause protein denaturation of bacterial membrane thermal damage. This process does not require the addition of antibiotics and is an environmentally friendly and safe advantageous material. Description of the Drawings

[0019] Figure 1 It is a scanning electron microscope characterization diagram of the Prussian blue analogue and the modified Prussian blue analogue prepared in the preferred embodiment of the present invention;

[0020] Figure 2 It is a comparison diagram of the A 2 O 2 ) values in the system catalyzed by the Prussian blue analogue and the modified Prussian blue analogue prepared in the preferred embodiment and the comparative example of the present invention; 652 value comparison diagram;

[0021] Figure 3 It is a temperature comparison diagram of the Prussian blue analogue and the modified Prussian blue analogue prepared in the preferred embodiment and the comparative example of the present invention after being irradiated with near-infrared light;

[0022] Figure 4 It is a comparison diagram of the methylene blue (MB) degradation efficiency of the Prussian blue analogue and the modified Prussian blue analogue prepared in the preferred embodiment and the comparative example of the present invention;

[0023] Figure 5 It is an antibacterial effect diagram of the modified Prussian blue analogue prepared in the preferred embodiment of the present invention. Detailed Embodiments

[0024] The endpoints and any values within the ranges disclosed herein are not limited to the exact ranges or values, and these ranges or values can be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0025] The principles involved in the present invention include:

[0026] The modified Prussian blue analogue prepared by the present invention has photothermal properties and peroxidase-like activity. First, under the irradiation of near-infrared light (NIR), it converts light energy into heat energy to achieve photothermal sterilization. The significant light absorption in the near-infrared region proves the catalytic activity driven by light. Second, the special Fe of the modified Prussian blue analogue2+ and Fe 3+ The alternating chemical composition is an excellent catalyst for the Fenton reaction. Fe 2+ can catalyze the decomposition of H 2 O 2 in cells to generate hydroxyl radicals, while Fe 2+ oxidizes to form Fe 3+ which can be reduced back to Fe 2 O 2 under the action of H 2+ and generate more hydroxyl radicals. Hydroxyl radicals have a strong inhibitory effect on microorganisms. Therefore, hydrogen peroxide is converted into hydroxyl radicals under the catalysis of the catalase-like activity of the modified Prussian blue analogue, thereby achieving chemodynamic sterilization.

[0027] As described above, the first aspect of the present invention provides a method for preparing a modified Prussian blue analogue, the method comprising the following steps:

[0028] (1) Dissolve a nickel source, a manganese source and sodium citrate in water to obtain a mixture I;

[0029] (2) Contact-react a potassium ferricyanide solution with the mixture I, and then successively carry out aging, water washing, alcohol washing and first drying to obtain a Prussian blue analogue;

[0030] (3) Disperse the Prussian blue analogue in a mixed solution of sulfuric acid and ethylene glycol to obtain a mixture II;

[0031] (4) Carry out microwave treatment on the mixture II, and obtain a modified Prussian blue analogue after purification and second drying.

[0032] Preferably, in step (3), the mixed solution of sulfuric acid and ethylene glycol is a product obtained by mixing ethylene glycol with a sulfuric acid solution having a concentration of 96-98 wt% in a volume ratio of 1:1. In this preferred case, it is more conducive to uniform etching, removing surface crystal defects and improving structural stability.

[0033] Preferably, in step (2), the potassium ferricyanide solution is a product obtained by dissolving potassium ferricyanide in water; and

[0034] in the potassium ferricyanide solution, the concentration of potassium ferricyanide is 1-3 mM.

[0035] Preferably, in step (1), the molar ratio of the amounts of the nickel source, the manganese source to the sodium citrate is 1:0.5-1.5:1.5-2.5.

[0036] Preferably, the nickel source is Ni(NO 3 ) 2 ·6H2 O.

[0037] Preferably, the manganese source is Mn(NO 3 ) 2 ·4H 2 O.

[0038] Preferably, the sodium citrate is Na 3 C 6 H 5 O 7 ·2H 2 O.

[0039] Preferably, in step (2), the contact reaction is carried out under stirring, and at least satisfies: the temperature is 15 - 40 °C, the rotation speed is 500 - 1000 rpm, and the time is 10 - 30 min.

[0040] It should be noted that in step (2) of the present invention, the aging is carried out by conventional operations in the art, for example, it can be achieved by standing still.

[0041] Preferably, in step (2), the aging time is 10 - 48 h, the number of water washing times is 2 - 5 times, and the number of alcohol washing times is 1 - 5 times.

[0042] Preferably, in step (2), the first drying method is vacuum drying or oven drying, and the drying time is 12 - 48 h and the temperature is 40 - 80 °C.

[0043] Preferably, in step (4), the microwave treatment conditions at least satisfy: the time is 1 - 8 min and the power is 100 - 750 W.

[0044] Preferably, in step (4), the purification is carried out by water purification or alcohol purification, and the number of purification times is 1 - 5 times.

[0045] Preferably, in step (4), the second drying method is vacuum drying or oven drying, and the drying time is 5 - 20 h and the temperature is 40 - 80 °C.

[0046] As described above, the second aspect of the present invention provides a modified Prussian blue analogue prepared by the method described in the first aspect.

[0047] As described above, the third aspect of the present invention provides the application of the modified Prussian blue analogue described in the second aspect in killing foodborne pathogenic bacteria.

[0048] Preferably, the foodborne pathogenic bacteria are selected from at least one of Staphylococcus aureus, Salmonella, and Escherichia coli.

[0049] Preferably, the steps of the application of the present invention include: contacting and mixing the modified Prussian blue analogue and the foodborne pathogenic bacterium, and then irradiating the mixture of the modified Prussian blue analogue and the foodborne pathogenic bacterium with near-infrared light having a wavelength of 808 nm and a power of 2.8 W / cm 2 for 5 - 10 min.

[0050] Preferably, the steps of the application of the present invention further include:

[0051] S1. Incubating the mixture of the modified Prussian blue analogue and the foodborne pathogenic bacterium in a constant temperature incubator at 35 - 40 °C for 2 - 4 h to obtain an incubated bacterial solution;

[0052] S2. Irradiating the incubated bacterial solution with near-infrared light having a wavelength of 808 nm and a power of 2.8 W / cm 2 for 5 - 10 min to complete sterilization.

[0053] Preferably, in the mixture of the modified Prussian blue analogue and the foodborne pathogenic bacterium, the ratio of the weight of the modified Prussian blue analogue to the total number of colonies of the foodborne pathogenic bacterium is 400 - 600:10 4 -10 7 .

[0054] It should be noted that in the present invention, the unit of the weight of the modified Prussian blue analogue is μg, and the unit of the total number of colonies of the foodborne pathogenic bacterium is CFU.

[0055] The present invention is described in detail below by way of examples. Unless otherwise specified, the raw materials used are all ordinary commercially available products.

[0056] In the present invention, unless otherwise specified, the "room temperature" means a temperature of 25 - 30 °C.

[0057] Nickel source: Ni(NO 3 ) 2 ·6H 2 O.

[0058] Manganese source: Mn(NO 3 ) 2 ·4H 2 O.

[0059] Sodium citrate: Na 3 C 6 H 5 O 7 ·2H 2 O.

[0060] Potassium ferricyanide solution: An aqueous solution of potassium ferricyanide with a concentration of 2 mM.

[0061] Mixed solution of sulfuric acid and ethylene glycol: A mixed solution of ethylene glycol and a sulfuric acid solution with a concentration of 98 wt% in a volume ratio of 1:1.

[0062] Example 1

[0063] This example is used to illustrate that the method for preparing the modified Prussian blue analogue provided by the present invention is carried out according to the following steps:

[0064] (1) Dissolve nickel source (0.001 mol), manganese source and sodium citrate in 50 mL of water in a molar ratio of 1:1:2 to obtain mixture I;

[0065] (2) At room temperature and under magnetic stirring at a speed of 800 rpm, contact 50 mL of potassium ferricyanide solution with mixture I for 15 min, and then successively carry out aging (standing) for 24 h, washing with water 3 times, washing with alcohol 3 times, and first drying (60 °C) for 10 h to obtain Prussian blue analogue (NiMnFe);

[0066] (3) Disperse the Prussian blue analogue in 5 mL of the mixed solution of sulfuric acid and ethylene glycol to obtain mixture II;

[0067] (4) Carry out microwave treatment on mixture II for 3 min (power: 450 W), and then successively carry out water purification 3 times and second drying (60 °C) for 10 h to obtain modified Prussian blue analogue (M-NiMnFe);

[0068] Figure 1 The scanning electron microscope characterization diagrams of NiMnFe and M-NiMnFe are shown. It can be seen from the figures that before microwave treatment, NiMnFe presents an irregular shape and a rough surface, while in M-NiMnFe after microwave treatment, a hollow cubic structure is uniformly presented, which confirms that microwave-assisted acid etching plays a crucial role in the formation of the novel modified Prussian blue analogue.

[0069] Comparative Example 1

[0070] This comparative example is carried out by a method similar to that of Example 1. The difference is that in step (1), no manganese source is used, but nickel source (0.002 mol) and sodium citrate are dissolved in 50 mL of water in a molar ratio of 1:1 to obtain mixture I;

[0071] Finally, Prussian blue analogue (NiFe) is obtained in step (2), and modified Prussian blue analogue (M-NiFe) is obtained in step (4).

[0072] Comparative Example 2

[0073] This comparative example was carried out in a similar manner to Example 1, except that in step (1), instead of using a manganese source and a nickel source, sodium citrate and 0.002 mol of a cobalt source (Co(NO 3 ) 2 ·6H 2 O) were dissolved in 50 mL of water in a molar ratio of 1:1 to obtain mixture I;

[0074] Finally, Prussian blue analog (CoFe) was obtained in step (2), and modified Prussian blue analog (M-CoFe) was obtained in step (4).

[0075] Comparative Example 3

[0076] This comparative example was carried out in a similar manner to Example 1, except that in step (1), instead of using a nickel source, a manganese source (0.002 mol) and sodium citrate were dissolved in 50 mL of water in a molar ratio of 1:1 to obtain mixture I;

[0077] Finally, Prussian blue analog (MnFe) was obtained in step (2), and modified Prussian blue analog (M-MnFe) was obtained in step (4).

[0078] Comparative Example 4

[0079] This comparative example was carried out in a similar manner to Example 1, except that in step (1), instead of using a manganese source, a nickel source (0.001 mol), a cobalt source (Co(NO 3 ) 2 ·6H 2 O) and sodium citrate were dissolved in 50 mL of water in a molar ratio of 1:1:2 to obtain mixture I;

[0080] Finally, Prussian blue analog (NiCoFe) was obtained in step (2), and modified Prussian blue analog (M-NiCoFe) was obtained in step (4).

[0081] Comparative Example 5

[0082] This comparative example was carried out in a similar manner to Example 1, except that in step (1), instead of using a nickel source, a manganese source (0.001 mol), a cobalt source (Co(NO 3 ) 2 ·6H 2 O) and sodium citrate were dissolved in 50 mL of water in a molar ratio of 1:1:2 to obtain mixture I;

[0083] Finally, Prussian blue analog (CoMnFe) was obtained in step (2), and modified Prussian blue analog (M-CoMnFe) was obtained in step (4).

[0084] Test Example 1

[0085] The following tests were carried out on the Prussian blue analogs and modified Prussian blue analogs prepared in the above examples:

[0086] (1) Determination of peroxidase mimicking activity: Mix 100 μL of substrate 3TMB with 100 μL of acetic acid / sodium citrate buffer containing H 2 O 2 . Add Prussian blue analog or modified Prussian blue analog at a dosage of 4.76 μg / mL, and catalyze the reaction at 25 °C for 40 min. Record the absorbance value (A 652 ) at 652 nm. Figure 2 The absorbance values of some Prussian blue analogs and modified Prussian blue analogs after the catalytic reaction are shown. It can be seen from the figure that the average value of the ultraviolet absorption peak of all modified Prussian blue analogs catalyzing the TMB-H 2 O 2 system is 20.07 times that of all Prussian blue analogs. Among them, the absorption peak of the M-NiMnFe group (the system after catalyzing the reaction with M-NiMnFe) is 58.47 times that of the NiMnFe group, proving that its modified Prussian blue analog has more excellent peroxidase-like activity; in addition, the absorption peak of the modified Prussian blue analog NiMnFe is at least 1.75 times that of other binary or ternary metal modified Prussian blue analogs;

[0087] (2) Photothermal performance determination: Mix Prussian blue analog or modified Prussian blue analog with water at a dosage of 0.3 mg / mL to prepare a suspension, and then irradiate it with 808 nm near-infrared light with a power density of 2.8 W cm-2 for 2 min. Record the temperature with an infrared thermal imager. Figure 3 The temperatures of some Prussian blue analogs and modified Prussian blue analogs after near-infrared light irradiation are shown. It can be seen from the figure that the average temperature of all modified Prussian blue analogs is 2.22 times that of all Prussian blue analogs. Among them, the average temperature of M-NiMnFe is 2.30 times that of NiMnFe, proving that its photothermal performance has been significantly improved after microwave treatment;

[0088] (3) Photocatalytic performance: Disperse Prussian blue analog or modified Prussian blue analog in 5 mL of MB solution, stir for 30 min, and reach adsorption equilibrium in the dark. Then add 25 μL of hydrogen peroxide solution (30 wt%) to the reaction system under continuous stirring. After irradiation for 40 min, measure the absorbance (A) at 663 nm with an enzyme-linked immunosorbent assay instrument.663 ) change. The MB degradation efficiency is calculated using the following formula:

[0089] MB degradation efficiency = (1 - C t / C 0 ) × 100%,

[0090] where, C 0 (mg / L): initial MB concentration;

[0091] C t (mg / L): MB concentration after 40 min of irradiation.

[0092] Figure 4 The MB degradation efficiencies of some Prussian analogs and modified Prussian blue analogs are shown. It can be seen from the figure that compared with the average degradation rate (38.08%) of Prussian analogs, the average degradation rate (59.03%) of modified Prussian blue analogs for MB shows higher catalytic efficiency, and among them, the degradation efficiency of modified Prussian blue analog M-NiMnFe for MB is close to 99%.

[0093] Application Example 1

[0094] This application example is used to illustrate the application of the Prussian blue analog prepared by the present invention in killing foodborne pathogenic bacteria. The specific operations include:

[0095] SS1. Take a small amount of Staphylococcus aureus strains and streak them on an LB solid medium (Luria - Bertani solid medium) to isolate single colonies. Pick a single colony from the LB solid medium and disperse it into 30 mL of LB broth medium. Transfer the liquid medium to an incubator at 37°C and shake it on a shaker at a speed of 150 rpm. Take the bacterial suspension after 18 h of culture, take 1 mL of the bacterial solution and centrifuge to obtain bacterial cells. Then wash the cells 3 times with 0.9% sterile physiological saline, redisperse the cell precipitate in a certain volume of sterile physiological saline, and then adjust the absorbance value of the bacterial solution at 600 nm to adjust the bacterial concentration to 1.0×10 6 CFU / mL to obtain a bacterial suspension for storage;

[0096] SS2. Take 1 mL of an aqueous solution of Prussian blue analog (M - NiMnFe) with a concentration of 0.5 mg / mL and add it to 1 mL of bacterial suspensions with bacterial concentrations of 10 4 CFU / mL, 10 5 CFU / mL, and 10 6 CFU / mL respectively, and incubate in a constant temperature incubator at 37°C for 2 h to obtain the incubated bacterial solution;

[0097] SS3. Expose the incubated bacterial solution to near-infrared light with a wavelength of 808 nm and a power of 2.8 W / cm 2 for irradiation to complete sterilization.

[0098] Take 100 μL of the sterilized bacterial solution dilution and spread it on the plate count medium, then place it in an incubator at 37 °C for 12 h, and take pictures and count the visible colony-forming units. Use the bacterial suspension with the corresponding bacterial concentration and without sterilization as the blank group.

[0099] Figure 5 Shows the antibacterial effects of the modified Prussian blue analogue material on bacterial solutions with different concentrations. In the figure, "M-FeNiMn+808nm infrared" represents the M-NiMnFe group, "blank" represents the blank group, "10 4 ", "10 5 ", and "10 6 " respectively represent that the bacterial concentrations of the used bacterial suspensions are 10 4 CFU / mL group, 10 5 CFU / mL group, and 106 CFU / mL group. It can be seen from the figure that, compared with the blank group, the bactericidal effect of the modified Prussian blue analogue prepared by the present invention is significant.

[0100] From the above results, it can be seen that the modified Prussian blue analogue prepared by the method provided by the present invention has photothermal performance and peroxidase-like activity, can achieve the purpose of highly synergistic sterilization for foodborne pathogenic bacteria, and effectively reduces the use of sterilization materials and H 2 O 2 .

[0101] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the technical concept scope of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. A method for preparing a modified Prussian blue analogue, characterized in that: The method comprises the following steps: (1) dissolving a nickel source, a manganese source and sodium citrate in water to obtain a mixture I; (2) contacting the mixture I with a potassium ferrocyanide solution for reaction, and then sequentially aging, washing with water, washing with alcohol, and first drying to obtain a Prussian blue analog; (3) dispersing the Prussian blue analog in a mixed solution of sulfuric acid and ethylene glycol to obtain a mixture II; (4) The mixture II is subjected to microwave treatment, and after purification and a second drying, a modified Prussian blue analogue is obtained.

2. The method according to claim 1, characterized in that: In step (3), the mixed solution of sulfuric acid and ethylene glycol is a product obtained by mixing ethylene glycol and a sulfuric acid solution with a concentration of 96-98 wt % in a dosage volume ratio of 1:

1.

3. The method according to claim 1 or 2, characterized in that: In step (2), the potassium ferrocyanide solution is a product obtained by dissolving potassium ferrocyanide in water; and In the potassium ferrocyanide solution, the concentration of potassium ferrocyanide is 1-3 mM.

4. The method according to claim 1 or 2, characterized in that: In step (1), the molar ratio of the nickel source, the manganese source and the sodium citrate is 1:0.5-1.5:1.5-2.

5.

5. The method according to claim 1 or 2, characterized in that: In step (2), the contact reaction is carried out under stirring conditions and at least meets the following conditions: temperature of 15-40° C., rotation speed of 500-1000 rpm, and time of 10-30 min.

6. The method according to claim 1 or 2, characterized in that: In step (4), the microwave treatment conditions at least meet the following requirements: time is 1-8 min, power is 100-750 W.

7. A modified Prussian blue analogue prepared by the method according to any one of claims 1 to 6.

8. Use of the modified Prussian blue analogue according to claim 7 in killing foodborne pathogenic bacteria.

9. The application according to claim 8, characterized in that: The application comprises: contacting and mixing the modified Prussian blue analogue and the food-borne pathogenic bacteria, and then subjecting the mixed solution of the modified Prussian blue analogue and the food-borne pathogenic bacteria to a wavelength of 808 nm and a power of 2.8 W / cm 2 Irradiate with near-infrared light for 5-10 minutes.

10. The use according to claim 8 or 9, characterized in that: In the mixed solution of the modified Prussian blue analog and the foodborne pathogenic bacteria, the ratio of the weight of the modified Prussian blue analog to the total number of colonies of the foodborne pathogenic bacteria is 400-600:10 4 -10 7 .

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