Application of iron-gallic acid metal organic framework nano-enzyme in antibacterial and protective products

Abstract

The invention belongs to the technical field of material application and protective articles, and particularly relates to application of iron-gallic acid metal organic framework nano-enzyme in antibacterial and protective products, and the iron-gallic acid metal organic framework nano-enzyme has light enhanced antibacterial property and broad-spectrum antibacterial property. The compound shows excellent inactivation efficiency on gram negative bacteria and gram positive bacteria. It is found for the first time that the Fe-GA metal organic framework nano-enzyme has light-enhanced bactericidal activity and has a remarkable sterilization effect on gram-negative bacteria and gram-positive bacteria, and the sterilization rate is gt; 99.9% by weight; the composite material is loaded on a base material to prepare an antibacterial layer, the antibacterial performance is remarkable, repeatability is achieved, the composite material can be used for preparing protective products such as masks and protective clothing, spontaneous sterilization can be achieved under visible light, the antibacterial performance of the protective products can be improved, the service life of the protective products can be prolonged, the long-acting antibacterial effect is achieved, and wide application prospects are achieved.

Description

Technical Field

[0001] The present invention belongs to the technical field of material application and protective products, and specifically relates to the application of an iron-gallate metal organic framework nanozyme in antibacterial and protective products. Background Art

[0002] Infectious diseases caused by a variety of pathogenic bacteria pose a serious long-term threat to personal health and public safety. In order to cut off the transmission chain of infectious diseases, the World Health Organization and local authorities strongly recommend wearing personal protective equipment, such as medical masks. The protection mechanisms of existing functional personal protective equipment usually hinder the transport of pathogenic particles through Brownian diffusion, interception, inertial collision, gravity sedimentation, and electrostatic adsorption. However, these strategies are difficult to effectively cut off the secondary transmission of pathogens because pathogens accumulate on fabrics and survive for several days during use. This directly or indirectly increases the risk of contact transmission and infection. Therefore, most personal protective equipment is not reusable. The disposable nature of these products and their lack of ability to spontaneously inactivate bacteria limit their further application, which poses a challenge to the development of new functional personal protective equipment that can cope with complex environments.

[0003] Nanozymes are nanomaterials with catalytic activity similar to that of biological enzymes. Among them, nanozymes with peroxidase-like activity can catalyze H 2 O 2 Decomposition produces reactive oxygen species (ROS), thereby achieving the purpose of spontaneous sterilization. Interestingly, nanozymes with OXD-like activity can capture oxygen and water vapor in the air to produce ROS without any external stimulation or energy input. However, compared with other enzymes with strong reaction capabilities, OXD-like enzymes have a weaker ability to produce ROS, which limits their antibacterial ability. There are currently no reports on the use of gallic acid-metal organic framework materials in protective equipment. Summary of the invention

[0004] The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide an application of an iron-gallate metal organic framework nanozyme in antibacterial and protective products.

[0005] In order to achieve the above-mentioned purpose, the present invention provides an application of an iron-gallate metal-organic framework nanozyme in antibacterial activities. The iron-gallate metal-organic framework nanozyme has light-enhanced antibacterial properties, that is, visible light or sunlight irradiation can significantly enhance the antibacterial properties of the iron-gallate metal-organic framework nanozyme.

[0006] Furthermore, the Fe-gallate metal-organic framework nanozymes have broad-spectrum antibacterial properties and show excellent inactivation efficiency against Gram-negative bacteria (Escherichia coli, Pseudomonas aeruginosa, and extended-spectrum β-lactamase Escherichia coli) and Gram-positive bacteria (Staphylococcus aureus, drug-resistant Staphylococcus aureus, and Bacillus subtilis).

[0007] Furthermore, the iron-gallate metal organic framework nanozyme is a spiny sea urchin-like structure.

[0008] The present invention also provides the use of iron-gallate metal organic framework nanozyme in the preparation of protective products, and uses the iron-gallate metal organic framework nanozyme as an antibacterial material to prepare a protective product with a long-lasting antibacterial effect.

[0009] Furthermore, the protective products include masks, protective clothing, protective shoes, gloves, helmets, glasses, earplugs, face shields, and hand and foot covers.

[0010] Furthermore, the prepared protective product with long-lasting antibacterial effect can be used for a long time under sunlight and has a good spontaneous sterilization effect.

[0011] Furthermore, the iron-gallate metal organic framework nanozyme is loaded on a substrate to obtain an iron-gallate metal organic framework nanozyme antibacterial layer for preparing protective products.

[0012] Furthermore, the substrate is non-woven fabric, nylon mesh, glass fiber cloth, etc.

[0013] Furthermore, the iron-gallate metal-organic framework nanozyme antibacterial layer can sterilize itself spontaneously and is reusable.

[0014] Furthermore, the protective product with long-lasting antibacterial effect is prepared by adding iron-gallate metal organic framework nanozyme antibacterial material to the existing protective product, or adding an iron-gallate metal organic framework nanozyme antibacterial layer to the existing protective product, or using the iron-gallate metal organic framework nanozyme antibacterial layer as raw material using the existing method.

[0015] Furthermore, the mask is made by replacing the middle layer of the existing mask with an iron-gallic acid metal organic framework nanozyme antibacterial layer.

[0016] The iron-gallate metal organic framework nanozyme antibacterial layer is prepared by a "roll-to-roll" hot pressing process, and the specific preparation method is as follows:

[0017] The substrate was cleaned with anhydrous ethanol and dried at 60°C for 3 hours; 0.1-1g of iron-gallic acid metal-organic framework nanozyme was dissolved in 1-10mL of isopropanol, and the mixed solution was evenly coated on the substrate to completely cover it, and the coated surface was hot-pressed with a hot press; after rolling back and forth several times, it was cleaned with anhydrous ethanol, and then placed in a vacuum drying oven and dried at 60°C for 3 hours to obtain an antibacterial layer of iron-gallic acid metal-organic framework nanozyme.

[0018] The preparation method of the iron-gallic acid (Fe-GA) metal organic framework nanozyme of the present invention comprises the following steps:

[0019] S1: 0.3-0.5g FeCl 2 ·4H 2 O is dissolved in 3.0 mL-6.0 mL of anhydrous ethanol to obtain a mixed solution A;

[0020] S2: Dissolve 0.9-1.02 g of gallic acid in 30-40 mL of DMF to obtain a mixed solution B;

[0021] S3: fully mixing the mixed solution A and the mixed solution B to obtain a mixed solution C;

[0022] S4: heating the mixed solution C in a sealed state at 140-180° C. for 18-24 hours;

[0023] S5: After the reaction is completed, cool to room temperature, and then use anhydrous ethanol for multiple centrifugal washings. After the last centrifugation, take the precipitate, put it into a vacuum drying oven, and dry it for 6-12 hours at a drying temperature of 45-60°C to obtain Fe-GA.

[0024] In the Fe-GA metal organic framework nanozyme of the present invention, visible light-mediated carrier migration and oxidase-like activity synergistically promote the generation of reactive oxygen species. In this case, a trace amount of Fe-GA (200 μg mL -1 ) showed excellent inactivation efficiency against Gram-negative bacteria (Escherichia coli, Pseudomonas aeruginosa, extended-spectrum β-lactamase Escherichia coli) and Gram-positive bacteria (Staphylococcus aureus, drug-resistant Staphylococcus aureus and Bacillus subtilis) without the addition of any chemical additives.

[0025] The Fe-GA metal organic framework nanozyme of the present invention is used to prepare long-term sterilization protection products. Without adding any chemical additives, it can quickly kill Gram-negative bacteria (Escherichia coli, Pseudomonas aeruginosa, extended-spectrum β-lactamase Escherichia coli), Gram-positive bacteria (Staphylococcus aureus, drug-resistant Staphylococcus aureus and Bacillus subtilis) and the above 6 kinds of bacteria mixtures after 20 minutes of illumination, even under sunlight, and exhibit excellent mechanical properties, reusability (15 cycles) and biocompatibility. In addition, the protective products prepared with Fe-GA metal organic framework nanozymes can effectively improve the service life of protective products, overcome the disposable characteristics of existing protective products, and thus achieve long-term sterilization. In addition, the Fe-GA metal organic framework nanozyme of the present invention can achieve spontaneous inactivation of bacteria, reduce the risk of secondary infection of diseases, and avoid secondary pollution to the environment after the protective products are discarded.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] (1) The Fe-GA provided by the present invention synergistically enhances the production of reactive oxygen species through visible light-mediated carrier migration and oxidase-like activity, autonomously captures water and oxygen in the air without adding any chemical additives, and achieves excellent antibacterial effects (>99.9%) against 6 types of bacteria.

[0028] (2) Fe-GA nanozymes are loaded on non-woven fabrics or other substrates and made into an antibacterial layer through a roll-to-roll hot pressing process. The disinfection efficiency of the simulated broad-spectrum microbial aerosol is >99.99% within 20 minutes of irradiation with visible light or sunlight.

[0029] (3) The Fe-GA / NWF provided by the present invention has good and excellent mechanical properties, particle attachment stability, reusability (15 cycles) and biocompatibility, overcoming the shortcomings of existing masks, protective clothing, etc. that cannot be used for a long time and lack spontaneous sterilization, and can effectively extend the service life of antibacterial protective products, thereby achieving a long-term antibacterial effect.

[0030] (4) The Fe-GA / NWF preparation process provided by the present invention is simple, the instrument method is simple and easy to operate, it can be mass-produced, and can be extended to other different types of substrates.

[0031] The present invention discovers for the first time that Fe-GA metal organic framework nanozyme has light-enhanced bactericidal properties, and has significant sterilization effects on both Gram-negative bacteria and Gram-positive bacteria, with a sterilization rate of >99.9%; it is loaded onto a substrate to prepare an antibacterial layer, which has significant and repeatable antibacterial properties, can be used to prepare protective products such as masks and protective clothing, can spontaneously sterilize under visible light or sunlight, can improve the antibacterial properties and service life of protective products, achieve a long-lasting antibacterial effect, and has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 These are SEM and TEM images of the Fe-GA metal organic framework nanozyme involved in the present invention, wherein the inset is a TEM image.

[0033] Figure 2 These are the XRD and XPS diagrams of the Fe-GA metal organic framework nanozyme involved in the present invention, wherein a is the XRD diagram and b is the XPS diagram.

[0034] Figure 3 The figure shows the physical object and SEM image of Fe-GA / NWF involved in the present invention.

[0035] Figure 4 This is the XRD diagram of Fe-GA / NWF involved in the present invention.

[0036] Figure 5 The diagram is a result diagram of the antibacterial experiment of the Fe-GA metal organic framework nanozyme on Escherichia coli and Staphylococcus aureus with and without light, wherein a is a photo of the bacterial plate incubation after the experiment; b is the statistical result of the bacterial inactivation rate of Escherichia coli; and c is the statistical result of the bacterial inactivation rate of Staphylococcus aureus.

[0037] Figure 6 The figures are the antibacterial experimental results of the Fe-GA metal organic framework nanozyme involved in the present invention against drug-resistant Staphylococcus aureus, Bacillus subtilis, extended-spectrum β-lactamase Escherichia coli, and Pseudomonas aeruginosa, wherein a is a photo of the bacterial plate incubation after the experiment; and b is the statistical result of the bacterial survival rate.

[0038] Figure 7 The present invention relates to antibacterial performance diagrams of Fe-GA / NWF against 6 kinds of bacteria, wherein a is a diagram of bacterial plate incubation in the flushing solution after the experiment, and b is a diagram of bacterial plate incubation on Fe-GA / NWF and NWF after flushing.

[0039] Figure 8 These are experimental diagrams of the antibacterial effect of Fe-GA / NWF on mixed bacteria involved in the present invention, wherein a is a diagram of bacterial plate incubation in the flushing solution, and b is a diagram of bacterial plate incubation on Fe-GA / NWF and NWF after flushing.

[0040] Fig. 9 It is a cyclic antibacterial performance diagram of Fe-GA / NWF involved in the present invention and a photo of each cyclic bacterial plate incubation, wherein the horizontal axis 0-15 is the number of cycles, 0 is equivalent to the bacterial concentration without Fe-GA / NWF treatment, and # represents a bacterial concentration of 0.

[0041] Fig.10 This is a physical picture of the Fe-GA / NWF involved in the present invention applied to a mask.

[0042] Fig.11 This is a graph showing the antibacterial experimental results of Fe-GA / NWF applied to masks involved in the present invention, wherein a is a photo of bacterial plate incubation in the flushing solution, b is a graph showing the bacterial colony count in the flushing solution, and # represents a bacterial concentration of 0.

[0043] Fig.12 This is a diagram showing the antibacterial test results of Fe-GA / NWF used as the outer layer of personal protective clothing in the present invention, wherein a is a real picture and b is a picture showing the antibacterial results.

[0044] Fig.13 This is a graph showing the antibacterial performance results of other Fe-GA loaded substrates of the present invention, wherein a is a nylon mesh and b is a glass fiber cloth.

[0045] Fig.14 This is a graph showing the particle adhesion stability performance results of Fe-GA / NWF involved in the present invention. DETAILED DESCRIPTION

[0046] The technical solutions in the embodiments of the present invention will be described clearly and completely below in conjunction with the accompanying drawings in the embodiments of the present invention.

[0047] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods; the materials, reagents, etc. used, unless otherwise specified, can be obtained from commercial channels.

[0048] Embodiment 1:

[0049] This embodiment relates to a method for preparing an iron-gallic acid metal organic framework nanozyme. The nanozyme is prepared by a simple hydrothermal method using ferrous chloride tetrahydrate and gallic acid as raw materials. The specific steps are as follows:

[0050] S1: weigh 0.5g FeCl 2 ·4H 2 O was dissolved in 4.0 mL of anhydrous ethanol to obtain a mixed solution A;

[0051] S2: Weigh 0.9 g of gallic acid and dissolve it in 40 mL of N,N-dimethylformamide (DMF) to obtain a mixed solution B;

[0052] S3: Mix the mixed solution A and the mixed solution B, and oscillate them using a vortex machine for 2 minutes to allow them to react fully, thereby obtaining a mixed solution C;

[0053] S4: The mixed solution C was then transferred to a Teflon-lined stainless steel autoclave and heated in a sealed container at 165 °C for 20 h;

[0054] S5: After the reaction is completed, cool to room temperature, use anhydrous ethanol to wash by centrifugation for 5 times, take the precipitate after the last centrifugation, put it into a vacuum drying oven, dry it at 45°C, and dry it for 12 hours to obtain iron-gallic acid metal organic framework nanozyme (Fe-GA for short).

[0055] The SEM and TEM morphologies of Fe-GA prepared in this example are as follows: Figure 1 As shown. Figure 1 It can be seen that Fe-GA presents a spiny sea urchin-like structure, which gives it more exposed active sites, thereby improving the catalytic performance.

[0056] The XRD and XPS spectra of Fe-GA in this example are as follows Figure 2 As shown. Figure 2 As shown in a, the X-ray diffraction pattern is very consistent with the simulated pattern obtained from the single crystal X-ray diffraction structure, indicating that Fe-GA has a high phase purity. Figure 2 As shown in b, the peaks at 711.6, 718.0, and 725.9 eV correspond to Fe(III)2p 3 / 2 、Fe(III)2p 3 / 2 Satellite peaks and Fe(III)2p 1 / 2 The peaks at 709.5, 714.7, and 723.3 eV correspond to Fe(II)2p 3 / 2 、Fe(II)2p 3 / 2 Satellite peaks and Fe(II)2p 1 / 2 These results indicate that both Fe(II) and Fe(III) states coexist in Fe-GA.

[0057] Embodiment 2:

[0058] This embodiment relates to a method for preparing an iron-gallate metal organic framework nanozyme, and the specific steps are as follows:

[0059] S1: Weigh 0.397g FeCl 2 ·4H 2 O was dissolved in 5.0 mL of anhydrous ethanol to obtain a mixed solution A;

[0060] S2: Weigh 1.02 g of gallic acid and dissolve it in 40 mL of DMF to obtain a mixed solution B;

[0061] S3: Mix the mixed solution A and the mixed solution B, and oscillate them using a vortex machine for 2 minutes to allow them to react fully, thereby obtaining a mixed solution C;

[0062] S4: The mixed solution C was then transferred to a Teflon-lined stainless steel autoclave and heated in a sealed container at 140 °C for 24 h;

[0063] S5: After the reaction is completed, cool to room temperature, use anhydrous ethanol to wash by centrifugation for 5 times, take the precipitate after the last centrifugation, put it into a vacuum drying oven, dry it at 60°C, and dry it for 6 hours to obtain iron-gallic acid metal organic framework nanozyme (Fe-GA for short).

[0064] Embodiment 3:

[0065] This embodiment relates to a method for preparing an iron-gallate metal organic framework nanozyme, and the specific steps are as follows:

[0066] S1: Weigh 0.3g FeCl 2 ·4H 2 O was dissolved in 6.0 mL of anhydrous ethanol to obtain a mixed solution A;

[0067] S2: Weigh 0.9 g of gallic acid and dissolve it in 30 mL of DMF to obtain a mixed solution B;

[0068] S3: Mix the mixed solution A and the mixed solution B, and oscillate them using a vortex machine for 2 minutes to allow them to react fully, thereby obtaining a mixed solution C;

[0069] S4: The mixed solution C was then transferred to a Teflon-lined stainless steel autoclave and heated in a sealed container at 180 °C for 18 h;

[0070] S5: After the reaction is completed, cool to room temperature, use anhydrous ethanol to wash by centrifugation for 5 times, take the precipitate after the last centrifugation, put it into a vacuum drying oven, dry it at a temperature of 58°C, and dry it for 9 hours to obtain iron-gallic acid metal organic framework nanozyme (Fe-GA for short).

[0071] Embodiment 4:

[0072] The present embodiment relates to a method for preparing an antibacterial layer of an iron-gallic acid metal organic framework nanozyme, which is obtained by coating the iron-gallic acid metal organic framework nanozyme on a non-woven fabric. The specific steps are: all non-woven fabrics (NWF) are washed with anhydrous ethanol and dried at 60°C for 3 hours; 0.15g of the iron-gallic acid metal organic framework nanozyme prepared by the hydrothermal method in Example 1-3 is dissolved in 6mL of isopropanol, and ultrasonicated for half an hour to mix it evenly to obtain a mixed solution; the mixed solution is evenly coated on the washed non-woven fabric (6×6cm) to completely cover it, and the coated surface is hot-pressed by a MSK-HRP-01 hot press (the upper and lower roller temperatures are between 60-70°C, and the rotation speed is 10-20rpmmin -1 ); after rolling back and forth several times, wash with anhydrous ethanol to remove unreacted materials; then put it into a vacuum drying oven and dry it at 60°C for 3 hours to obtain a non-woven fabric coated with iron-gallic acid metal organic framework nanozyme, that is, an antibacterial layer, referred to as Fe-GA / NWF.

[0073] In this embodiment, the thickness of each antibacterial layer is 1-3 mm, and the loading amount of the iron-gallate metal organic framework nanozyme is (0.50-0.95) mg cm -2 .

[0074] The physical picture and SEM picture of Fe-GA / NWF prepared in this example are as follows Figure 3 As shown. Figure 3 It can be seen that the hot pressing process did not change the morphology of the nonwoven fabric, and Fe-GA was successfully loaded onto the nonwoven fabric.

[0075] The prepared Fe-GA / NWF was characterized by XRD patterns and compared with the XRD patterns of pure NWF and the simulated patterns of Fe-GA derived from single crystal X-ray diffraction structure. Figure 4 As shown. Figure 4 It can be seen that Fe-GA / NWF shows an obvious diffraction peak, which belongs to the original Fe-GA, indicating that Fe-GA is successfully loaded on the nonwoven fabric.

[0076] Embodiment 5:

[0077] This embodiment involves the antibacterial performance experiment of iron-gallate metal organic framework nanozyme (Fe-GA) and iron-gallate metal organic framework nanozyme antibacterial layer (Fe-GA / NWF).

[0078] 1. Antibacterial experiment of Fe-GA

[0079] Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) were selected for antibacterial experiments. 3-4 colonies were inoculated into fresh LB medium and then incubated at 37°C overnight until the logarithmic phase. Using a McFarland turbidimeter, the bacterial concentration was adjusted to 1×10 8 CFU mL -1 Then, the bacterial solution was diluted to 1×10 6 CFUmL -1 For the experiment, a 1 mL antibacterial experimental system was prepared: 100 μL of bacterial suspension was mixed with an appropriate amount of Fe-GA, and the remaining part was supplemented with a sterile 0.9 wt% NaCl aqueous solution and mixed thoroughly (the final concentrations of Fe-GA were 0, 50, 100, and 200 μg mL -1 ). In the illumination group (Fe-GA+Light), a xenon lamp (using visible light to simulate sunlight) with a 430nm cutoff filter was used to irradiate the antibacterial experimental system for 20 minutes (the vertical distance from the light source to the sample was 5 cm); then after incubation at 37°C for 30 minutes, it was diluted 10 times with a sterile 0.9wt% NaCl aqueous solution; 100μL of the dilution was inoculated on an agar plate, cultured overnight at 37°C, and counted using the plate counting method. The antibacterial experimental system containing different concentrations of Fe-GA was placed in the dark for 20 minutes as the dark group (Fe-GA+Dark). The antibacterial results are shown in the figure. Figure 5 shown.

[0080] from Figure 5 It can be seen that for Staphylococcus aureus and Escherichia coli, the presence of Fe-GA can reduce the survival rate of bacteria under dark conditions; but under light conditions, the presence of Fe-GA can significantly reduce the survival rate of bacteria. -1 The Fe-GA dosage can reduce the survival rate of Staphylococcus aureus and Escherichia coli by 2-4 orders of magnitude. In the presence of Fe-GA, the bacterial survival rate in the light group was significantly lower than that in the dark group, indicating that visible light irradiation can enhance the antibacterial effect of Fe-GA and Fe-GA has light-enhanced antibacterial properties.

[0081] The above method was further used to conduct antibacterial experiments on drug-resistant Staphylococcus aureus (MRSA), Bacillus subtilis (B. subtilis), extended-spectrum β-lactamase Escherichia coli (ESBLE.coli) and Pseudomonas aeruginosa (P. aeruginosa), which can cause respiratory infections or are common in daily environments. The concentration of Fe-GA in the antibacterial system of the experimental group (Fe-GA+Light) was 200 μg mL -1; There was no Fe-GA in the antibacterial system of the control group (control+light); both the experimental group and the control group were irradiated with visible light. The results are as follows Figure 6 As shown. Figure 6 It can be seen that without using any chemical additives, the inactivation efficiency of Fe-GA on drug-resistant Staphylococcus aureus, Bacillus subtilis, extended-spectrum β-lactamase Escherichia coli, and Pseudomonas aeruginosa within 20 minutes of illumination time was more than 99.9%, indicating that Fe-GA has broad-spectrum antibacterial properties.

[0082] 2. Antibacterial experiment of Fe-GA / NWF

[0083] Six different bacterial strains were selected as model organisms, including drug-resistant Staphylococcus aureus, Bacillus subtilis, extended-spectrum β-lactamase Escherichia coli, Pseudomonas aeruginosa, Escherichia coli, and Staphylococcus aureus, for antibacterial testing. Three to four colonies were inoculated into fresh LB medium and then cultured overnight at 37°C to the logarithmic phase. The bacterial solution was diluted to 1 × 10 using a sterile 0.9% NaCl solution using a McFarland turbidimeter. 8 CFU mL -1 . 100 μL of a single bacterial suspension was dropped onto Fe-GA / NWF (2×2 cm) or pure nonwoven fabric (NWF). After the bacterial suspension was added, Fe-GA / NWF was immediately exposed to a 300 W xenon lamp with a 430 nm cutoff filter for 20 minutes (the distance between the sample and the light was maintained at 5 cm); then, the bacteria-treated Fe-GA / NWF and NWF were placed in a 37°C incubator for incubation for 30 minutes; after the incubation, Fe-GA / NWF and NWF were rinsed with 0.9% NaCl solution, that is, Fe-GA / NWF and NWF were immersed in 3 mL of sterile 0.9% NaCl solution and vortexed for 10-15 seconds to wash away the bacteria on Fe-GA / NWF and NWF; the bacteria were enriched by centrifugation (3000 rpm, 5 min), the supernatant was removed to leave the precipitate, and finally resuspended in 1 mL of sterile 0.9% NaCl, the resuspension was diluted 10 times continuously, and then 100 μL of the dilution was inoculated on LB agar plates and incubated in a 37°C incubator overnight to detect bacteria in the rinse solution ( Figure 7 The washed Fe-GA / NWF and NWF were placed on LB agar plates and incubated in a 37°C incubator overnight. Photos were taken ( Figure 7 (b) The presence of residual live bacteria on Fe-GA / NWF was demonstrated in a semi-quantitative manner.

[0084] from Figure 7a It can be seen that there are almost no bacteria in the rinsing fluid of the Fe-GA / NWF+light group, indicating that these 6 types of bacteria are almost completely inactivated after Fe-GA / NWF and light treatment (inactivation rate>99.99%). Figure 7 b It can be seen that after the washed Fe-GA / NWF was cultured on solid culture medium for 24 hours, no obvious bacterial residue was observed on Fe-GA / NWF, while a large number of surviving bacteria were still on NWF. This indicates that the excellent antibacterial efficacy of Fe-GA / NWF does not depend on physical barriers or adhesion, but is mainly attributed to the destructive damage to bacterial cells caused by light-enhanced ROS production.

[0085] In this example, the bacteria-treated Fe-GA / NWF was placed under outdoor sunlight for 20 minutes according to the above method, and the statistical sterilization rate was >99.9%, indicating that the sterilization effect of Fe-GA / NWF under sunlight was significant.

[0086] In this example, the six fresh bacterial cultures were mixed in a volume ratio of 1:1:1:1:1 to simulate the complex bacterial environment in real life. Antibacterial experiments were carried out according to the above method. The results are as follows: Figure 8 As shown. Figure 8 It can be seen that there are no viable bacteria in the rinsing solution of the Fe-GA / NWF+light group, and no bacteria remain on the Fe-GA / NWF after rinsing, indicating that the mixed bacteria treated with Fe-GA / NWF are almost completely inactivated after 20 minutes of light exposure (inactivation rate >99.99%).

[0087] This example also carried out a cyclic antibacterial experiment on Fe-GA / NWF, and the specific operation was as follows:

[0088] The experimental process is similar to the plate antibacterial test. The concentration of the bacterial suspension used in the reaction system is 1×10 8 CFUmL -1 After each round of antibacterial experiments, the Fe-GA / NWF tested in each round was soaked in water for half an hour, then dried with a baking lamp, and then the next round of antibacterial experiments was carried out.

[0089] The cyclic antibacterial performance diagram of Fe-GA / NWF in this example and the photos of each cycle of bacterial plate incubation are shown in Figure 2. Fig. 9 As shown. Fig. 9 It can be seen that the concentration of surviving bacteria in Fe-GA / NWF after the 15th antibacterial treatment was less than 1×10 5 CFU mL -1 , which is significantly lower than the original bacterial concentration, indicating that Fe-GA / NWF still has an obvious antibacterial effect after 15 cycles, which further proves the reusability of Fe-GA / NWF.

[0090] Embodiment 6:

[0091] This embodiment relates to the application of the Fe-GA / NWF antibacterial layer in protective products, including masks and protective clothing.

[0092] 1. The specific operation of the antibacterial layer applied to the antibacterial experiment of the mask is as follows:

[0093] Use scissors to gently cut open the commercial KN95 mask, which includes a first layer of non-woven fabric, a middle layer, and a second layer of non-woven fabric. Pull out the middle layer and place Fe-GA / NWF between the first and second layers of non-woven fabric as the middle layer, which is the Fe-GA / NWF mask ( Fig.10 ). Inject 4 mL of E. coli suspension (1×10 6 CFU mL -1 ), simulating the aerosol generation process. Spray at least 1mL of E. coli aerosol on the outermost layer (i.e., the first layer) of the manufactured antibacterial mask and ordinary commercial mask, and then irradiate under a 300w xenon lamp with a 430nm cutoff filter for 20 minutes, and then incubate in a 37°C incubator for 30 minutes; rinse each layer of the mask with 5mL of sterile 0.9% NaCl solution, and oscillate with a vortexer for 10-15 seconds, enrich the bacteria by centrifugation (3000rpm, 5 minutes), remove the supernatant to leave the precipitate, and finally resuspend in 1mL of sterile 0.9% NaCl; dilute the resuspension 10 times continuously, and then inoculate 100μL of the dilution onto the LB agar plate, incubate overnight in a 37°C incubator, and detect the bacterial concentration in the rinse solution of each layer of the mask ( Fig.11 b). Place the rinsed masks on LB agar plates and incubate them in a 37°C incubator overnight ( Fig.11 a), semi-quantitatively demonstrating the viable bacteria remaining on the mask.

[0094] In this example, Fe-GA / NWF was sandwiched between two layers of non-woven fabrics of commercial masks as an intermediate layer to evaluate the simulated aerosol disinfection ability of the Fe-GA / NWF mask and compare it with the commercial KN95 mask. Fig.11 It can be seen that when the E. coli aerosol is about 10 6 CFU mL -1 When exposed to visible light for 20 minutes, bacteria attached to the surface of both masks to varying degrees. However, most of the bacteria on the middle and second layers of the KN95 mask survived and were unable to block and inactivate microbial aerosols. In contrast, no surviving bacteria were observed on Fe-GA / NWF and its covered areas, effectively preventing further invasion of microbial aerosols.

[0095] This example also tested the light antibacterial experiment of Fe-GA / NWF as the outer layer of protective clothing. Fe-GA / NWF was covered on the surface of the protective clothing, and the part not covered with Fe-GA / NWF was used as a control ( Fig.12 a), the result is as follows Fig.12 As shown in b. Fig.12 b It can be seen that there is almost no bacterial adhesion on the Fe-GA / NWF surface after 20 min of illumination.

[0096] This example also verifies the feasibility of light antibacterial by loading Fe-GA on other substrates (nylon net and glass fiber cloth, recorded as Fe-GA / Nylon net, Fe-GA / Fiberglass cloth) using the "roll-to-roll" hot pressing process, and the substrate without Fe-GA loading + light is used as the control group. The bacteria in the flushing liquid were detected according to the above antibacterial experimental method. The results are as follows Fig.13 As shown. Fig.13 It can be seen that there are no viable bacteria in the rinsing solutions of Fe-GA / Nylon net and Fe-GA / Fiberglass cloth, indicating that Fe-GA is suitable for constructing antibacterial interfaces on the surfaces of various substrates and has antibacterial effects.

[0097] This example experimentally tests the particle adhesion stability of the Fe-GA / NWF antibacterial layer. The specific experimental operation is as follows:

[0098] S1: The Fe-GA / NWF sample was placed on the inlet side of a polyurethane gas tube (inner diameter 8 mm), and the detector fabric was placed on the outlet side. Air was pumped at a specific speed (1-5 m s -1 ) flowed through the gas tube for 5 minutes. The specific speed is the continuous airflow rate, simulating normal human breathing (1-3m s -1 ), sneezing (4ms -1 ) and cough (5m s -1 ) at the airflow conditions. The airflow rate was measured using a gas flow meter. After the test, the detector fabric was imaged to estimate the number of Fe-GA particles separated ( Fig.14 a).

[0099] S2: Only place the Fe-GA / NWF sample on the inlet side of the polyurethane gas tube and allow air to flow at a specific speed (1-5ms -1 ) through Fe-GA / NWF for 5 minutes. The detached particles were blown into deionized water connected to the outlet, and the amount of Fe in the water was measured by ICP-MS, and the separation rate of Fe-GA from Fe-GA / NWF was calculated using the following formula ( Fig.14 b).

[0100] Fe-GA detachment rate=(C Fe ×V) / m×100%

[0101] Among them, C Fe is the concentration of Fe element in deionized water measured by ICP-MS, V is the volume of deionized water that receives the particles, and m is the mass of Fe-GA loaded on the non-woven fabric.

[0102] from Fig.14 a It can be seen that after continuous ventilation at all tested airflow rates, almost no Fe-GA particles were detected on the corresponding detector fabrics. Fig.14 b It can be seen that the separation rate of Fe-GA particles from Fe-GA / NWF is always less than 0.20%, which is almost negligible. Therefore, Fe-GA / NWF exhibits excellent adhesion stability for use as personal protective equipment.

[0103] This embodiment also detects the mechanical properties, wear resistance and other properties of Fe-GA / NWF. The results show that after adding Fe-GA, the tensile strength, Young's modulus and elongation at break of the non-woven fabric are all improved, indicating that strength, stiffness and elasticity are all enhanced. The ultimate strain at break of Fe-GA / NWF is higher than that of ordinary NWF, which may be due to the enhanced ductility of Fe-GA / NWF. On the other hand, the sample can be twisted, bent and unfolded 100 times, and the weight loss is negligible. In addition, after the wear resistance test and the mechanical stirring test of the combination of simulated collision and extrusion conditions, Fe-GA / NWF has no obvious structural damage and weight loss, which shows that the Fe-GA coating has a strong affinity for the substrate, ensuring that Fe-GA / NWF maintains good catalytic ability, and Fe-GA / NWF can be used as a fabric to prepare masks, protective clothing, gloves or other antibacterial products.

Claims

1. An application of an iron-gallate metal organic framework nanozyme in antibacterial applications, characterized in that: Iron-gallate metal-organic framework nanozymes have light-enhanced antibacterial properties, that is, visible light or sunlight irradiation can significantly enhance the antibacterial properties of iron-gallate metal-organic framework nanozymes.

2. The use of the iron-gallate metal organic framework nanozyme in antibacterial applications according to claim 1, characterized in that: The iron-gallate metal-organic framework nanozymes have broad-spectrum antibacterial properties and show excellent inactivation efficiency against both Gram-negative and Gram-positive bacteria.

3. The use of the iron-gallate metal organic framework nanozyme in antibacterial applications according to claim 1, characterized in that: The iron-gallate metal organic framework nanozyme is a spiny sea urchin-like structure.

4. An application of an iron-gallate metal organic framework nanozyme in the preparation of protective products, characterized in that: Iron-gallate metal-organic framework nanozymes are used as antibacterial materials to prepare protective products.

5. The use of the iron-gallate metal organic framework nanozyme in the preparation of protective products according to claim 4, characterized in that: The protective products include masks, protective clothing, protective shoes, gloves, helmets, glasses, earplugs, face masks and hand and foot covers.

6. The use of the iron-gallate metal organic framework nanozyme in the preparation of protective products according to claim 4, characterized in that: The iron-gallate metal organic framework nanozyme is loaded on a substrate to obtain an iron-gallate metal organic framework nanozyme antibacterial layer, which is used to prepare protective products.

7. The use of the iron-gallate metal organic framework nanozyme in the preparation of protective products according to claim 6, characterized in that: The substrate is non-woven fabric, nylon mesh or glass fiber cloth.

8. The use of the iron-gallate metal organic framework nanozyme in the preparation of protective products according to claim 6, characterized in that: The iron-gallate metal-organic framework nanozyme antibacterial layer can sterilize spontaneously and is reusable.

9. The use of the iron-gallate metal organic framework nanozyme in the preparation of protective products according to claim 6, characterized in that: The iron-gallate metal organic framework nanozyme antibacterial layer is prepared by a "roll-to-roll" hot pressing process, and the specific preparation method is as follows: The substrate is cleaned with anhydrous ethanol and dried; the iron-gallate metal-organic framework nanozyme is dissolved in isopropanol, and the mixed solution is evenly coated on the substrate to completely cover it, and the coated surface is hot-pressed by a hot press; after rolling back and forth several times, it is cleaned with anhydrous ethanol and dried to obtain an iron-gallate metal-organic framework nanozyme antibacterial layer.

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