Preparation method of antibacterial fabric synergistically antibacterial by sulfur dioxide gas and nitrogen mustard

Abstract

The invention discloses a preparation method of a sulfur dioxide gas synergistic nitrogen mustard antibacterial fabric, belonging to the technical field of fabric antibacterial. The preparation method is as follows: N-phenyldiethanolamine and phosphorus oxychloride are synthesized to obtain intermediate 1; intermediate 1 and p-aminobenzoic acid are synthesized to obtain intermediate 2; intermediate 2 and p-aminophenol are synthesized to obtain intermediate 3; intermediate 3 and 2,4-dinitrobenzenesulfonyl chloride are synthesized to obtain 4-(4-((4-bis(2-chloroethyl)amino)phenyl)diazenyl)benzamide)phenyl 2,4-dinitrobenzenesulfonate; 4-(4-((4-bis(2-chloroethyl)amino)phenyl)diazenyl)benzamide)phenyl 2,4-dinitrobenzenesulfonate, 2-methylimidazole and zinc nitrate hexahydrate are assembled into nanoparticles on the fabric to obtain a sulfur dioxide gas synergistic nitrogen mustard antibacterial fabric, and the antibacterial fabric can accelerate the decomposition of nanoparticles and improve the antibacterial effect.

Description

Technical Field

[0001] The invention belongs to the technical field of antibacterial fabrics, and in particular relates to a method for preparing sulfur dioxide gas-coordinated nitrogen mustard antibacterial fabric. Background Art

[0002] In a dark and humid environment, with food residues, grease and dandruff, etc., clothes are always moldy and mildewed inadvertently in life, which not only makes clothes black and yellow, affecting their appearance, but also seriously endangers human health. Bacteria and mold can produce a variety of toxins, often causing skin diseases, and in severe cases, respiratory diseases, and may even cause cancer.

[0003] Metal ions are used as antibacterial factors to finish the fabrics so that the fabrics have good antibacterial effects. For example, CN1920163A discloses a method for preparing nano antibacterial fabrics, which uses high molecular polymers as dispersants and auxiliary binders, metal ions as antibacterial factors, and nitrogen azole organic matter as anchors for metal ions on fabric fibers, and combines with metal ions by coordination bonds to form nanoparticles on the fibers, so that the fabrics have excellent antibacterial properties. Most bacteria have a weakly alkaline growth environment and the bacterial cells are generally neutral environments, while nanoparticles are more easily decomposed in an acidic environment, and metal ions are also easily precipitated in an alkaline environment, which is not conducive to the decomposition of nanoparticles, greatly delaying the release rate of metal ions in the nanoparticles and reducing the antibacterial effect.

[0004] Professor Wu Fugen of Southeast University mentioned in Antibacterial gas therapy: Strategies, advances, and prospects. that SO2 is not only an environmental pollutant, but also an endogenous gas transmitter similar to NO, CO and H2S. Endogenous SO2 can regulate vascular and cardiac function, and can also damage biological macromolecules when overexpressed. It can also induce various types of cell stress, such as imbalance of redox homeostasis and damage to DNA. In addition, the widespread use of sulfites as preservatives in the food industry also shows that they have the ability to inhibit microorganisms. There are no reports in the prior art on the application of sulfur dioxide and sulfites in fabric antibacterial. Summary of the invention

[0005] In view of the shortcomings of the prior art, the purpose of the present invention is to provide a method for preparing sulfur dioxide gas synergistic with nitrogen mustard antibacterial fabric. By adding sulfur dioxide donors to the nanoparticles on the fabric, a weakly acidic environment can be formed, which further accelerates the decomposition of the nanoparticles and accelerates antibacterial effect.

[0006] To achieve the above objectives, the present invention adopts the following technical scheme: a method for preparing sulfur dioxide gas synergistic with nitrogen mustard antibacterial fabric, comprising the following steps:

[0007] (1) Cool N-phenyldiethanolamine in an ice-water bath, slowly add phosphorus oxychloride, stir evenly, then heat under reflux. After the reaction is completed, add saturated brine and ethyl acetate, separate the liquid, retain the organic phase, and obtain intermediate 1 after purification;

[0008] (2) Dissolve p-aminobenzoic acid and sodium nitrite in deionized water, add concentrated hydrochloric acid and stir to obtain a mixed solution; dissolve intermediate 1 obtained in step (1) in absolute ethanol, add it to the mixed solution and stir, react at room temperature for 2 h, filter after the reaction is completed, and obtain intermediate 2 after purification;

[0009] (3) Mix p-aminophenol, intermediate 2 obtained in step (2), 0-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, and N,N-diisopropylethylamine in N,N-dimethylformamide and stir to react. After the reaction is completed, add ethyl acetate, extract and separate the liquid, purify, and dry to obtain intermediate 3;

[0010] (4) Add triethylamine to the ethyl acetate solution of intermediate 3 and stir at 0 °C. Slowly add the ethyl acetate solution of 2,4-dinitrobenzenesulfonyl chloride, stir under nitrogen protection. After the reaction is completed, add deionized water and ethyl acetate, extract and separate the liquid, retain the organic phase, purify, and dry to obtain 4-(4-((4-bis(2-dichloroethyl)amino)phenyl)diazenyl)benzamide)phenyl 2,4-dinitrobenzenesulfonate;

[0011] (5) Mix the mixed solution obtained by dissolving 4-(4-((4-bis(2-dichloroethyl)amino)phenyl)diazenyl)benzamide)phenyl 2,4-dinitrobenzenesulfonate obtained in step (4) in ethyl acetate with the methanol solution of 2-methylimidazole to obtain solution a. Dissolve zinc nitrate hexahydrate in methanol to obtain solution b. Immerse the fabric in solution a and solution b in sequence, and dry to obtain a sulfur dioxide gas synergistic nitrogen mustard antibacterial fabric.

[0012] Further, in step (1), the temperature of the heating under reflux reaction is 110 °C and the time is 1 h.

[0013] Further, in step (1), the molar ratio of N-phenyldiethanolamine to phosphorus oxychloride is 11:52.

[0014] Further, in step (2), the mass ratio of intermediate 1, p-aminobenzoic acid, and sodium nitrite is 5:3:2.

[0015] Further, in step (3), the mass ratio of p-aminophenol, intermediate 2, 0-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, and N,N-diisopropylethylamine is 32.75:300:342:152.

[0016] Further, in step (4), the mass ratio of intermediate 3 to 2,4-dinitrobenzenesulfonyl chloride is 115:106.4.

[0017] Further, in step (5), the mass fraction of the ethyl acetate solution of 4-(4-((4-bis(2-dichloroethyl)amino)phenyl)diazenyl)benzamide)phenyl 2,4-dinitrobenzenesulfonate is 0.038% - 0.28%, the mass fraction of the methanol solution of 2-methylimidazole is 0.43%, and the mass fraction of the methanol solution of zinc nitrate hexahydrate is 0.13%; the mass ratio of 4-(4-((4-bis(2-dichloroethyl)amino)phenyl)diazenyl)benzamide)phenyl 2,4-dinitrobenzenesulfonate, 2-methylimidazole, and zinc nitrate hexahydrate is 1 - 10:41:15.

[0018] Further, in step (5), the mass fraction of the ethyl acetate solution of 4-(4-((4-bis(2-dichloroethyl)amino)phenyl)diazenyl)benzamide)phenyl 2,4-dinitrobenzenesulfonate is 0.19%, the mass fraction of the methanol solution of 2-methylimidazole is 0.43%, and the mass fraction of the methanol solution of zinc nitrate hexahydrate is 0.043% - 0.43%; the mass ratio of 4-(4-((4-bis(2-dichloroethyl)amino)phenyl)diazenyl)benzamide)phenyl 2,4-dinitrobenzenesulfonate, 2-methylimidazole, and zinc nitrate hexahydrate is 5:41:15 - 50.

[0019] The sulfur dioxide gas synergistic nitrogen mustard antibacterial fabric prepared by the above preparation method.

[0020] Compared with the prior art, the beneficial effects of the present invention are:

[0021] (1) A sulfur dioxide supply drug 4-(4-((4-bis(2-dichloroethyl)amino)phenyl)diazenyl)benzamide)phenyl 2,4-dinitrobenzenesulfonate was prepared from 2,4-dinitrobenzenesulfonyl chloride and N-phenyldiethanolamine, which can simultaneously provide sulfur dioxide gas and nitrogen mustard; and after being wrapped with zinc ions and 2-methylimidazole, it can be fixed on the surface of fabric fibers and react with glutathione in bacteria to release sulfur dioxide gas; the synthesis steps of the sulfur dioxide gas synergistic nitrogen mustard antibacterial fabric of the present invention are simple and the cost is low, so it is suitable for large-scale production;

[0022] (2) The nanoparticles on the fabric fibers contain abundant zinc ions. When the excessive zinc ions reach the surface of bacteria, since the cell membrane is negatively charged, the zinc ions can adsorb onto the surface of the cell membrane by Coulomb force, further penetrate the cell wall, resulting in the outflow of cytoplasm and hindering cell reproduction. At the same time, through the reaction of glutathione in the bacteria with the sulfonate groups in the nanoparticles, sulfur dioxide gas is released, forming sulfite and bisulfite radicals in the bacteria. The sulfite and bisulfite radicals form a weak acidic environment in the cell body, and this weak acidic environment also facilitates the accelerated decomposition of the undissolved nanoparticles, accelerating the release of sulfur dioxide gas and disrupting the redox balance in the bacteria. And when the nanoparticles decompose, they will release nitrogen mustard drugs, which alkylate with the DNA of the bacteria, inhibit the synthesis of bacterial DNA, and synergistically induce the death of bacteria with sulfur dioxide. Description of the Drawings

[0023] Figure 1 It is the synthetic chemical equation diagram (a) and its hydrogen spectrum diagram (b) of 4-(4-((4-bis(2-dichloroethyl)amino)phenyl)diazenyl)benzamide)phenyl 2,4-dinitrobenzenesulfonate in Example 1;

[0024] Figure 2 It is the SEM diagram of the nanoparticles in-situ grown on the fabric fibers in Example 1;

[0025] Figure 3 It is the ultraviolet absorption spectrum diagram of 4-(4-((4-bis(2-dichloroethyl)amino)phenyl)diazenyl)benzamide)phenyl 2,4-dinitrobenzenesulfonate in Example 1;

[0026] Figure 4 It is the detection diagram of the sulfur dioxide release performance of the nanoparticles in Example 1;

[0027] Figure 5 It is the comparison diagram of the antibacterial effects of the antibacterial fabric, the ZIF-8 in-situ grown fabric, and the ordinary fabric in Example 1. Detailed Description of the Embodiments

[0028] The present invention will be further described in detail below with reference to the drawings and specific embodiments, but it should not be construed as a limitation of the present invention. Without departing from the spirit and essence of the present invention, any modification or replacement of the methods, steps or conditions of the present invention belongs to the scope of the present invention. The experimental methods without specific conditions and the reagents without specific formulations in the embodiments are all according to the conventional conditions in the art.

[0029] The N-phenyldiethanolamine, phosphorus oxychloride, ethyl acetate, p-aminobenzoic acid, sodium nitrite, concentrated hydrochloric acid, absolute ethanol, p-aminophenol, 0-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, N,N-diisopropylethylamine, N,N-dimethylformamide, triethylamine, 2,4-dinitrobenzenesulfonyl chloride, 2-methylimidazole and zinc nitrate hexahydrate used in the present invention are all common chemical raw materials for preparation and can be directly ordered online from reagent suppliers.

[0030] The sulfur dioxide gas synergistic nitrogen mustard antibacterial fabric of the present invention is prepared by in-situ growth method to grow nanoparticles formed by the sulfur dioxide supply drug 4-(4-((4-bis(2-chloroethyl)amino)phenyl)diazenyl)benzamide)phenyl 2,4-dinitrobenzenesulfonate, 2-methylimidazole and zinc ions on the fabric fibers.

[0031] The sulfur dioxide gas synergistic nitrogen mustard antibacterial fabric of the present invention can utilize the reaction between glutathione in bacteria and sulfonate groups to release sulfur dioxide, disrupt the redox balance in bacteria. At the same time when the nanoparticles decompose, the released nitrogen mustard can inhibit bacterial reproduction. In addition, the abundant zinc ions in the nanoparticles can cause the outflow of bacterial cytoplasm. Under the action of the three, effective antibacterial can be achieved. Moreover, the synthetic raw materials of the antibacterial fabric of the present invention are inexpensive, the preparation process is simple, and it is easy to mass-produce.

[0032] Example 1

[0033] The sulfur dioxide gas synergistic nitrogen mustard antibacterial fabric of this example is prepared by the following method:

[0034] (1) Synthesize intermediate 1 from N-phenyldiethanolamine and phosphorus oxychloride

[0035] Put 2 g (11 mmol) of N-phenyldiethanolamine into a round-bottom flask, cool it in an ice-water bath, slowly add 4.5 mL (52 mmol) of phosphorus oxychloride (POCl3), stir evenly with a magnetic stirrer, then transfer the round-bottom flask to reflux at 110 °C for 1 h; add 15 mL of saturated brine and 15 mL of ethyl acetate to the solution after the reaction, separate the layers, retain the organic phase, and then use column chromatography to purify to obtain intermediate 1;

[0036] (2) Synthesize intermediate 2 from intermediate 1 and p-aminobenzoic acid

[0037] Dissolve 0.6 g of p-aminobenzoic acid and 0.4 g of sodium nitrite in 10 mL of deionized water, add 1.4 mL of concentrated hydrochloric acid with a mass fraction of 36%, stir for 20 min to obtain a mixed solution; take 1 g of the intermediate product 1 obtained in step (1) and dissolve it in 30 mL of absolute ethanol. After dissolving evenly, add it to the mixed solution and stir for 2 h; after the reaction, filter out the orange-red solid and purify it by recrystallization to prepare the intermediate product 2;

[0038] (3) Synthesize intermediate product 3 from intermediate product 2 and p-aminophenol

[0039] Mix 32.75 mg of p-aminophenol, 300 mg of intermediate product 2, 342 mg of 0-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate (HATU), and 205 mL of 152 mg of N,N-diisopropylethylamine (DIPEA) and dissolve them in 9 mL of N,N-dimethylformamide (DMF), and stir magnetically for 12 h; after the reaction, add 30 mL of deionized water, shake well, add 30 mL of ethyl acetate (EA) for extraction and liquid separation, retain the organic phase, purify it by column chromatography method, and dry to obtain intermediate product 3;

[0040] (4) Synthesize compound 4-(4-((4-bis(2-dichloroethyl)amino)phenyl)diazenyl)benzamide)phenyl 2,4-dinitrobenzenesulfonate from intermediate product 3 and 2,4-dinitrobenzenesulfonyl chloride

[0041] Add 0.1 mL of 72.8 mg of triethylamine (TEA) to 10 mL of an ethyl acetate solution containing 115 mg of intermediate product 3, stir at 0 °C for 10 min, slowly add 10 mL of an ethyl acetate solution containing 106.4 mg of 2,4-dinitrobenzenesulfonyl chloride, and stir under nitrogen protection for 12 h; after the reaction, add 30 mL of deionized water, shake well, add 30 mL of ethyl acetate (EA) for extraction and liquid separation, retain the organic phase, purify it by column chromatography method, and dry to obtain an orange-red solid, namely 4-(4-((4-bis(2-dichloroethyl)amino)phenyl)diazenyl)benzamide)phenyl 2,4-dinitrobenzenesulfonate; among them, the concentration of intermediate product 3 in the ethyl acetate solution of intermediate product 3 is 11.5 mg / mL; the concentration of 2,4-dinitrobenzenesulfonyl chloride in the ethyl acetate solution of 2,4-dinitrobenzenesulfonyl chloride is 10.64 mg / mL; the mass ratio of intermediate product 3 to 2,4-dinitrobenzenesulfonyl chloride is 115:106.4; the dosage of triethylamine is 63.3% of the mass of intermediate product 3;

[0042] (5) Assemble 4-(4-((4-bis(2-dichloroethyl)amino)phenyl)diazenyl)benzamide)phenyl 2,4-dinitrobenzenesulfonate, 2-methylimidazole, and zinc nitrate hexahydrate into nanoparticles on the fabric fiber by in-situ growth

[0043] Dissolve 5 mg of 4-(4-((4-bis(2-dichloroethyl)amino)phenyl)diazenyl)benzamide)phenyl 2,4-dinitrobenzenesulfonate in 3 mL of ethyl acetate to obtain an ethyl acetate solution of 4-(4-((4-bis(2-dichloroethyl)amino)phenyl)diazenyl)benzamide)phenyl 2,4-dinitrobenzenesulfonate with a mass fraction of 0.19%. Take 41 mg of 2-methylimidazole and dissolve it in 12 mL of methanol to obtain a methanol solution of 2-methylimidazole with a mass fraction of 0.43%. Then mix the ethyl acetate solution of 4-(4-((4-bis(2-dichloroethyl)amino)phenyl)diazenyl)benzamide)phenyl 2,4-dinitrobenzenesulfonate with the methanol solution of 2-methylimidazole evenly to obtain solution a; dissolve 15 mg of zinc nitrate hexahydrate in 15 mL of methanol to obtain a methanol solution of zinc nitrate hexahydrate with a mass fraction of 0.13%, that is, solution b; cut a white fabric with a grammage of 21.5 g / m 2 Put the white fabric into solution a and solution b in sequence and soak for 20 min, and the soaking area is 1 cm 2 , repeat 5 times, take out the soaked fabric and dry it in an oven.

[0044] Example 2

[0045] The difference between the preparation method of the sulfur dioxide gas synergistic nitrogen mustard antibacterial fabric in this example and that in Example 1 is that in step (5), dissolve 1 mg of 4-(4-((4-bis(2-dichloroethyl)amino)phenyl)diazenyl)benzamide)phenyl 2,4-dinitrobenzenesulfonate in 3 mL of ethyl acetate to obtain an ethyl acetate solution of 4-(4-((4-bis(2-dichloroethyl)amino)phenyl)diazenyl)benzamide)phenyl 2,4-dinitrobenzenesulfonate with a mass fraction of 0.038%. Take 41 mg of 2-methylimidazole and dissolve it in 12 mL of methanol to obtain a methanol solution of 2-methylimidazole with a mass fraction of 0.43%. Then mix the ethyl acetate solution of 4-(4-((4-bis(2-dichloroethyl)amino)phenyl)diazenyl)benzamide)phenyl 2,4-dinitrobenzenesulfonate with the methanol solution of 2-methylimidazole evenly to obtain mixed solution a. The other steps are the same.

[0046] Example 3

[0047] The preparation method of the sulfur dioxide gas synergistic nitrogen mustard antibacterial fabric in this example is different from that in Example 1 in that: in step (5), 10 mg of 4-(4-((4-bis(2-dichloroethyl)amino)phenyl)diazenyl)benzamide)phenyl 2,4-dinitrobenzenesulfonate is dissolved in 3 mL of ethyl acetate to obtain an ethyl acetate solution of 4-(4-((4-bis(2-dichloroethyl)amino)phenyl)diazenyl)benzamide)phenyl 2,4-dinitrobenzenesulfonate with a mass fraction of 0.28%. 41 mg of 2-methylimidazole is dissolved in 12 mL of methanol to obtain a methanol solution of 2-methylimidazole with a mass fraction of 0.43%. Then, the ethyl acetate solution of 4-(4-((4-bis(2-dichloroethyl)amino)phenyl)diazenyl)benzamide)phenyl 2,4-dinitrobenzenesulfonate is mixed with the methanol solution of 2-methylimidazole to obtain a uniform mixed solution a. Other steps are the same.

[0048] Example 4

[0049] The preparation method of the sulfur dioxide gas synergistic nitrogen mustard antibacterial fabric in this example is different from that in Example 1 in that: in step (5), 5 mg of zinc nitrate hexahydrate is dissolved in 15 mL of methanol to obtain a methanol solution of zinc nitrate hexahydrate with a mass fraction of 0.043%, that is, solution b. Other steps are the same.

[0050] Example 5

[0051] The preparation method of the sulfur dioxide gas synergistic nitrogen mustard antibacterial fabric in this example is different from that in Example 1 in that: in step (5), 50 mg of zinc nitrate hexahydrate is dissolved in 15 mL of methanol to obtain a methanol solution of zinc nitrate hexahydrate with a mass fraction of 0.43%, that is, solution b. Other steps are the same.

[0052] Figure 1 It is the synthesis chemical equation diagram of 4-(4-((4-bis(2-dichloroethyl)amino)phenyl)diazenyl)benzamide)phenyl 2,4-dinitrobenzenesulfonate in Example 1 and its hydrogen spectrum diagram.

[0053] The performance test of Example 1 is as follows:

[0054] 1. Morphology determination of nanoparticles on the antibacterial fabric

[0055] Figure 2 It is the SEM diagram of the nanoparticles in-situ grown on the fabric fibers in Example 1.

[0056] From Figure 2 It can be seen that nanoparticles will grow on the fabric fibers after the in-situ growth treatment, and the nanoparticles are evenly distributed on the fabric fibers.

[0057] 2. Determination of the properties of 2,4-dinitrobenzenesulfonic acid 4-(4-((4-bis(2-(bis(2-chloroethyl)amino)phenyl)diazenyl)benzoyl)aminophenyl) ester

[0058] Through Figure 3 the ultraviolet absorption spectrum of 2,4-dinitrobenzenesulfonic acid 4-(4-((4-bis(2-(bis(2-chloroethyl)amino)phenyl)diazenyl)benzoyl)aminophenyl) ester in Figure 3 , it can be analyzed that the characteristic peak at 250 nm is formed by the absorption of ultraviolet light by the Π electron cloud on the benzene ring in the structure of 2,4-dinitrobenzenesulfonic acid 4-(4-((4-bis(2-(bis(2-chloroethyl)amino)phenyl)diazenyl)benzoyl)aminophenyl) ester, resulting in an electronic transition; the characteristic peak at 420 nm is the characteristic peak of the -N=N- structure in the structure of 2,4-dinitrobenzenesulfonic acid 4-(4-((4-bis(2-(bis(2-chloroethyl)amino)phenyl)diazenyl)benzoyl)aminophenyl) ester.

[0059] 3. Detection of the sulfur dioxide release performance of nanoparticles

[0060] Dissolve 5 mg of 2,4-dinitrobenzenesulfonic acid 4-(4-((4-bis(2-(bis(2-chloroethyl)amino)phenyl)diazenyl)benzoyl)aminophenyl) ester in 3 mL of ethyl acetate to obtain a solution of 2,4-dinitrobenzenesulfonic acid 4-(4-((4-bis(2-(bis(2-chloroethyl)amino)phenyl)diazenyl)benzoyl)aminophenyl) ester in ethyl acetate, and mix it evenly with a solution of 41 mg of 2-methylimidazole in 12 mL of methanol to obtain solution a; dissolve 15 mg of zinc nitrate hexahydrate in 15 mL of methanol to obtain a solution of zinc nitrate hexahydrate in methanol, that is, solution b; mix solution a and solution b evenly, stir magnetically overnight, then centrifuge at 8000 rpm, wash three times with deionized water, and dry to prepare nanoparticles (NPs).

[0061] Prepare a 10 mL nanoparticle mixture with a concentration of 0.5 mg / mL and a pH of 5.0 (containing 5 μmol / L of 7-(diethylamino)coumarin-3-carboxaldehyde DEACA), and add 20 equivalents of glutathione (GSH), denoted as GSH + DEACA + NPs.

[0062] Prepare a 10 mL nanoparticle mixture with a concentration of 0.5 mg / mL and a pH of 5.0, and add 20 equivalents of GSH, denoted as GSH + NPs.

[0063] Prepare a 10 mL solution of 5 μmol / L of 7-(diethylamino)coumarin-3-carboxaldehyde DEACA with a pH of 5.0, and add 20 equivalents of GSH, denoted as GSH + DEACA.

[0064] Detect the fluorescence intensities of GSH + DEACA + NPs, GSH + NPs, and GSH + DEACA at 483 nm (excitation wavelength is 390 nm, slit is 5 nm / 5 nm).

[0065] Through Figure 4 It can be seen that the GSH + NPs group has no fluorescence, the GSH + DEACA group has weak fluorescence. Since DEACA itself has weak fluorescence, when nanoparticles are added, the GSH + DEACA + NPs group has strong fluorescence, which proves that after the nanoparticles are decomposed, GSH reacts with sulfonate to generate sulfur dioxide.

[0066] 4. Antibacterial Performance Detection

[0067] Prepare the antibacterial fabric in Example 1, denoted as fabric + NPs. Prepare the fabric with in-situ growth of ZIF-8: Dissolve 41 mg of 2-methylimidazole in 12 mL of methanol to obtain solution a; dissolve 15 mg of zinc nitrate hexahydrate in 15 mL of methanol to obtain solution b; sequentially place the cut white fabric into solution a and solution b and soak for 20 min, repeat 5 times, take out the soaked fabric, and dry it in an oven to prepare a fabric without 4-(4-((4-bis(2-dichloroethyl)amino)phenyl)diazenyl)benzamide)phenyl 2,4-dinitrobenzenesulfonate, only with in-situ growth of ZIF-8, denoted as fabric + ZIF-8.

[0068] Perform antibacterial performance detection (MIC method) on three kinds of fabrics: ordinary fabric, fabric + ZIF-8, and fabric + NPs. After washing the three kinds of fabrics, inoculate the cultivated Escherichia coli and Staphylococcus aureus. After 48 h, elute the bacteria from the three kinds of fabrics with a neutralizing solution, and use the dilution plate method to measure Escherichia coli and Staphylococcus aureus in the eluates of different fabrics and perform viable cell counting on them.

[0069] Through Figure 5 It can be seen that the ordinary fabric has no antibacterial ability; the fabric + ZIF-8 group can effectively reduce the survival rates of Staphylococcus aureus and Escherichia coli because there are a large number of zinc ions in ZIF-8, which can inhibit the growth of bacteria; the fabric + NPs group can greatly reduce the survival rate of bacteria and has the best effect among the three groups because NPs not only have the antibacterial effect of zinc ions but also have sulfur dioxide gas synergistically with nitrogen mustard to inhibit the growth of bacteria.

[0070] For the survival rates of Staphylococcus aureus and Escherichia coli of the antibacterial fabrics in Examples 1 to 5, the results are shown in Table 1. It can be seen from Table 1 that the antibacterial fabrics of the present invention can reduce the survival rate of bacteria.

[0071] Table 1 Survival rates of Staphylococcus aureus and Escherichia coli of the antibacterial fabrics in Examples 1 to 5

[0072] Example 1 Example 2 Example 3 Example 4 Example 5 Survival rate of Staphylococcus aureus (%) 18.2 25.3 19.7 23.8 17.7 Survival rate of Escherichia coli (%) 16.4 24.6 18.8 21.3 16.8

Claims

1. A preparation method of a sulfur dioxide gas synergistic nitrogen mustard antibacterial fabric, characterized in that, It includes the following steps: (1) Cool N-phenyldiethanolamine in an ice-water bath, slowly add phosphorus oxychloride, stir evenly, then heat for reflux reaction. After the reaction is completed, add saturated brine and ethyl acetate, separate the layers, and retain the organic phase. After purification, intermediate 1 is obtained; (2) Dissolve p-aminobenzoic acid and sodium nitrite in deionized water, add concentrated hydrochloric acid and stir to obtain a mixed solution; Dissolve intermediate 1 obtained in step (1) in absolute ethanol, add it to the mixed solution and stir, react at room temperature for 2 h. After the reaction is completed, filter, and after purification, intermediate 2 is obtained; (3) Mix p-aminophenol, intermediate 2 obtained in step (2), 0-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, and N,N-diisopropylethylamine in N,N-dimethylformamide and stir for reaction. After the reaction is completed, add ethyl acetate, extract and separate the layers, purify, and after drying, intermediate 3 is obtained; (4) Add triethylamine to the ethyl acetate solution of intermediate 3 and stir at 0 °C. Slowly add the ethyl acetate solution of 2,4-dinitrobenzenesulfonyl chloride, stir under nitrogen protection. After the reaction is completed, add deionized water and ethyl acetate, extract and separate the layers, retain the organic phase, purify, and after drying, 4-(4-((4-bis(2-dichloroethyl)amino)phenyl)diazenyl)benzamide)phenyl 2,4-dinitrobenzenesulfonate is obtained; (5) Mix the mixed solution obtained by dissolving 4-(4-((4-bis(2-dichloroethyl)amino)phenyl)diazenyl)benzamide)phenyl 2,4-dinitrobenzenesulfonate obtained in step (4) in ethyl acetate with the methanol solution of 2-methylimidazole to obtain solution a. Dissolve zinc nitrate hexahydrate in methanol to obtain solution b. Immerse the fabric in solution a and solution b in sequence, and dry to obtain a sulfur dioxide gas synergistic nitrogen mustard antibacterial fabric.

2. The preparation method according to claim 1, characterized in that, In step (1), the temperature of the heating reflux reaction is 110 °C and the time is 1 h.

3. The preparation method according to claim 1, characterized in that, In step (1), the molar ratio of N-phenyldiethanolamine to phosphorus oxychloride is 11:

52.

4. The preparation method according to claim 1, characterized in that, In step (2), the mass ratio of intermediate 1, p-aminobenzoic acid, and sodium nitrite is 5:3:

2.

5. The preparation method according to claim 1, characterized in that, In step (3), the mass ratio of p-aminophenol, intermediate 2, 0-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, and N,N-diisopropylethylamine is 32.75:300:342:

152.

6. The preparation method according to claim 1, characterized in that, In step (4), the mass ratio of intermediate 3 to 2,4-dinitrobenzenesulfonyl chloride is 115:106.

4.

7. The preparation method according to claim 1, characterized in that, In step (5), the mass fraction of the ethyl acetate solution of 4-(4-((4-bis(2-dichloroethyl)amino)phenyl)diazenyl)benzamide)phenyl 2,4-dinitrobenzenesulfonate is 0.038% to 0.28%, the mass fraction of the methanol solution of 2-methylimidazole is 0.43%, and the mass fraction of the methanol solution of zinc nitrate hexahydrate is 0.13%; the mass ratio of 4-(4-((4-bis(2-dichloroethyl)amino)phenyl)diazenyl)benzamide)phenyl 2,4-dinitrobenzenesulfonate, 2-methylimidazole, and zinc nitrate hexahydrate is 1 to 10:41:

15.

8. The preparation method according to claim 1, wherein In step (5), the mass fraction of the ethyl acetate solution of 4-(4-((4-bis(2-dichloroethyl)amino)phenyl)diazenyl)benzamide)phenyl 2,4-dinitrobenzenesulfonate is 0.19%, the mass fraction of the methanol solution of 2-methylimidazole is 0.43%, and the mass fraction of the methanol solution of zinc nitrate hexahydrate is 0.043% to 0.43%; the mass ratio of 4-(4-((4-bis(2-dichloroethyl)amino)phenyl)diazenyl)benzamide)phenyl 2,4-dinitrobenzenesulfonate, 2-methylimidazole, and zinc nitrate hexahydrate is 5:41:15 to 50.

9. A sulfur dioxide gas synergistic nitrogen mustard antibacterial fabric prepared by the preparation method according to any one of claims 1 to 8.

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