A selective sterilization material and its preparation method and application

Abstract

The application discloses a kind of selective sterilization material and its preparation method and application, the selective sterilization material has the following repeat structural unit shown in formula I: In formula I, Y is at least one of group A, OH;Group A is selected from at least one of imidazole salt cation, pyridine salt cation, pyrrole salt cation, quaternary ammonium salt cation, quaternary phosphonium salt cation, piperidine salt cation, wherein, N or P in A is connected with main chain;In selective sterilization material, the substitution degree of A is 0.40-1.0.The sterilization material of the application introduces cationic group on polysaccharide side chain by deoxidation process, so that the prepared sterilization material has high selective sterilization capacity, selectively kills bacteria at low concentration, and has no harm to normal cells, and has important practical value.

Description

Technical Field

[0001] This invention belongs to the field of natural polymers and antibacterial materials technology, specifically relating to a selective sterilization material, its preparation method, and its application. Background Technology

[0002] Bacterial infections pose a significant threat to human health. Cationic polymers have attracted considerable attention due to their unique "membrane-breaking bactericidal" mechanism. These materials interact electrostatically with the negatively charged bacterial cell membranes (phospholipids, lipopolysaccharides, or teichosaccharides) on the surface of the bacterial cell through positively charged side groups (such as quaternary ammonium salts, quaternary phosphonium salts, or imidazole salts). This interaction causes the material to adsorb and disrupt the integrity of the bacterial cell membrane, leading to the leakage of intracellular substances and ultimately killing the bacteria. However, cationic polymers often exhibit high cytotoxicity to mammalian cells, significantly limiting their clinical application in the medical field. Developing novel antibacterial materials that can efficiently kill various bacteria without damaging normal cells is crucial for achieving treatment without side effects. Summary of the Invention

[0003] To address the aforementioned technical problems, the present invention provides a selective sterilization material, wherein the selective sterilization material comprises a polymer having repeating structural units as shown in Formula I below:

[0004] Formula I in: In Formula I, Y is at least one of the groups A and OH; Group A is selected from at least one of imidazole salt cations, pyridinium salt cations, pyrrole salt cations, quaternary ammonium salt cations, quaternary phosphonium salt cations, and piperidine salt cations, wherein N or P in A is attached to the main chain; In the polymer, the degree of substitution of A is 0.40-1.0.

[0005] According to an embodiment of the invention, in the polymer, the degree of substitution of A is, for example, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1.0.

[0006] According to an embodiment of the present invention, A is selected from at least one of the following groups:

[0007] R are the same or different, and are independently selected from H and C. 1-10 Alkyl, -(C 1-10 alkylene)-OH, -(C 1-10 (alkylene)-C 6-12 Aryl; * represents a connection key.

[0008] According to an embodiment of the present invention, R may be the same or different, and is independently selected from H and C. 1-6 Alkyl, -(C 1-6 alkylene)-OH, -(C 1-6 (alkylene)-C 6-10 Aryl; for example selected from H, methyl, ethyl, propyl, butyl, pentyl, hexyl, -ethylene-OH or -(C 1-4 (alkylene)-phenyl.

[0009] According to an embodiment of the present invention, the degree of aggregation of the repeating structural unit shown in Formula I is 100-3000, and exemplarily 100, 220, 500, 600, 650, 810, 1000, 1500, 2000 or 3000.

[0010] According to an embodiment of the present invention, the main chain of the selective bactericidal material is derived from at least one of cellulose, starch, dextran, pullulan, lentinan, black fungus polysaccharide, kelp polysaccharide, and guar gum, wherein the main chain of the selective bactericidal material refers to a compound in which all Y groups are OH.

[0011] This invention also provides a method for preparing the above-mentioned selective sterilization material: the method includes: (1) A hydroxyl-containing polymer solution is mixed with p-toluenesulfonyl chloride and reacted to obtain a p-toluenesulfonated polymer; The hydroxyl-containing polymer is selected from at least one of cellulose, starch, dextran, pullulan, lentinan, black fungus polysaccharide, kelp polysaccharide, and guar gum; (2) The selective sterilization material is prepared by mixing the p-toluenesulfonated polymer solution with a compound containing an A group and heating the mixture.

[0012] According to an embodiment of the present invention, in step (1), the hydroxyl-containing polymer solution is obtained by dissolving the hydroxyl-containing polymer in solvent 1, wherein solvent 1 is selected from ionic liquids and optionally contains or does not contain amide solvents; For example, the ionic liquid includes, but is not limited to, one of the following substances: 1-ethyl-3-methylimidazolium chloride ionic liquid, 1-ethyl-3-methylimidazolium bromide ionic liquid, 1-allyl-3-methylimidazolium chloride ionic liquid (AmimCl), 1-allyl-3-methylimidazolium bromide ionic liquid, 1-butyl-3-methylimidazolium chloride ionic liquid (BmimCl), 1-butyl-3-methylimidazolium bromide ionic liquid, 1-ethyl-3-methylimidazolium acetate ionic liquid (EmimAc), 1-allyl-3-methylimidazolium acetate ionic liquid, 1-butyl-3-methylimidazolium acetate ionic liquid, N The ionic liquids are: 1-ethylpyridine chloride, N-ethylpyridine bromide, 1,3-dimethylimidazolium dimethyl phosphate, 1-ethyl-3-methylimidazolium diethyl phosphate, 3-methylimidazolium carboxylate, N-methylpyridine carboxylate, 1-ethyl-3-methylimidazolium carboxylate, and 1-butyl-3-methylimidazolium carboxylate; preferably, 1-allyl-3-methylimidazolium chloride (AmimCl), 1-butyl-3-methylimidazolium chloride (BmimCl), or 1-ethyl-3-methylimidazolium acetate (EmimAc). For example, the amide solvent is selected from N,N -Dimethylformamide (DMF) and N,N At least one of dimethylacetamide; preferably N,N -Dimethylformamide (DMF); Preferably, the solvent 1 is selected from a mixture of ionic liquid and amide solvent. For example, the mass ratio of the two can be 4:(0-4), preferably 4:(0-2), and exemplary ratios are 4:0, 4:0.5, 4:0.5, 4:1, and 4:2.

[0013] According to an embodiment of the present invention, in step (1), the mass concentration of the hydroxyl-containing polymer solution is 2-20 wt%, preferably 3-15 wt%, for example 3 wt%, 5 wt%, 8 wt%, 10 wt%, 12 wt%, or 15 wt%.

[0014] According to an embodiment of the present invention, in step (1), the mass ratio of the hydroxyl-containing polymer to p-toluenesulfonyl chloride in the hydroxyl-containing polymer solution is 1:1-10, preferably 1:2-6, for example 1:2, 1:3, 1:4, 1:5 or 1:6.

[0015] According to an embodiment of the present invention, in step (1), the temperature of the mixing reaction is 0-25°C, preferably 0-15°C; the time of the mixing reaction is 10-48h, for example 16-28h.

[0016] According to an embodiment of the present invention, in step (1), after the mixing reaction, a post-processing step can be performed: the product after the mixing reaction is completed is precipitated (for example, precipitated in a mixed solvent of ethanol and water), filtered, and the solid is washed and dried to obtain a solid p-toluenesulfonated polymer.

[0017] According to an embodiment of the present invention, in step (2), the p-toluenesulfonated polymer solution is obtained by dissolving the solid p-toluenesulfonated polymer in step (1) in solvent 2. For example, solvent 2 is selected from at least one of sulfone solvents and amide solvents, such as dimethyl sulfoxide (DMSO). N, N -Dimethylformamide (DMF) and N,N At least one of dimethylacetamide; preferably N,N -Dimethylformamide (DMF).

[0018] According to an embodiment of the present invention, in step (2), the mass concentration of the p-toluenesulfonated polymer solution is 2-20 wt%, preferably 3-15 wt%, for example 3 wt%, 5 wt%, 8 wt%, 10 wt%, 12 wt%, 14 wt%, or 15 wt%.

[0019] According to an embodiment of the present invention, in step (2), the temperature of the heating reaction is 50-120°C, preferably 60-100°C; the heating reaction time is 10-48h, preferably 18-28h.

[0020] According to an embodiment of the present invention, in step (2), the compound containing the A group is selected from at least one of the following compounds;

[0021] R has the meanings described above.

[0022] Preferably, the compound containing the A group is selected from imidazole, N-alkylimidazolium (e.g., NC). 1-6 Alkyl imidazoles, preferably N-methylimidazolium, N-ethylimidazolium, or N-propylimidazolium), pyridines, and N-alkylpyridines (e.g., NC... 1-6 Alkylpyridine, preferably at least one of N-methylpyridine, N-ethylpyridine, N-propylpyridine, pyrrole, amine compounds (e.g., ethanolamine, N,N-dimethylbenzylamine, N,N-dimethylethylamine, etc.), alkylphosphine (e.g., tributylphosphine), and piperidine.

[0023] According to an embodiment of the present invention, in step (2), the mass ratio of the solute p-toluenesulfonated polymer to the compound containing the A group in the p-toluenesulfonated polymer solution is 1:1-40, preferably 1:1-20, for example 1:2, 1:3, 1:4, 1:5, 1:6, 1:10, 1:12, 1:14, 1:16, 1:18 or 1:20.

[0024] According to an embodiment of the present invention, in step (2), after the heating reaction is completed, a post-processing step is also included: precipitating the product after the heating reaction (e.g., precipitating in ethanol), filtering, taking the solid for washing and drying, and obtaining selective sterilization material.

[0025] The present invention also provides the application of the above-mentioned selective sterilization material in the preparation of antibacterial materials.

[0026] The beneficial effects of this invention are: The sterilization material of this invention introduces cationic groups into the polysaccharide side chain through a deoxygenation process, which enables the prepared sterilization material to have high selective bactericidal ability. It can selectively kill bacteria at low concentrations (1-70 μg / mL) without harming normal cells, and has important practical value.

[0027] The selective sterilization material of this invention is effective against Escherichia coli (E. coli). E. coil ) and Staphylococcus aureus ( S. aureus It has excellent sterilization effect. Attached Figure Description

[0028] Figure 1 The image shows the hydrogen nuclear magnetic resonance spectrum of the deoxycellulose dimethyl ethyl quaternary ammonium salt in Example 1.

[0029] Figure 2 This is a photograph of the hemolysis test of deoxycellulose dimethyl ethyl quaternary ammonium salt in Example 1.

[0030] Figure 3 The image shows the hydrogen nuclear magnetic resonance spectrum of the deoxycellulose dimethylbenzyl quaternary ammonium salt in Example 2.

[0031] Figure 4 This is a colony diagram of bacteria after co-culturing deoxycellulose dimethyl benzyl quaternary ammonium salt with bacteria in Example 2.

[0032] Figure 5 The image shows the hydrogen nuclear magnetic resonance spectrum of the deoxygenated lentinan imidazole salt from Example 3.

[0033] Figure 6 This is a photograph of the hemolysis test of deoxygenated lentinan imidazole salt in Example 3.

[0034] Figure 7 This is a photograph of the hemolysis test of deoxystarch 2-hydroxyethyl quaternary ammonium salt in Example 4. Detailed Implementation

[0035] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention, and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0036] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0037] In Examples 1-5, the hydrogen nuclear magnetic resonance spectra were obtained using a Bruker AV400 nuclear magnetic resonance spectrometer, with deuterated dimethyl sulfoxide (DMSO-d6) as the solvent. The scanning electron microscope images were taken using a Gemini 500 instrument. The instrument used for colony culture was a SONY α7 digital camera.

[0038] Example 1 The preparation of deoxycellulose dimethyl ethyl quaternary ammonium salt includes the following steps: (1) 1.62 g of cellulose was added to 20 g of AmimCl and stirred vigorously at 80 °C for 2 h to obtain a cellulose solution. 5.72 g of p-toluenesulfonyl chloride was added to the above solution and reacted at 0 °C for 24 h. After the reaction was completed, the reaction solution was poured into a mixed solvent of ethanol / water (v / v = 1 / 1) to precipitate. The precipitate was washed three times with ethanol and then dried at 60 °C for 12 h to obtain cellulose p-toluenesulfonate with a degree of substitution of 1.0. (2) Add 1 g of cellulose p-toluenesulfonate to 20 g of DMSO and stir at 80 °C for 0.5 h. After the cellulose p-toluenesulfonate is completely dissolved, add 2.35 g of N,N-dimethylethylamine to the solution and react at 80 °C for 24 h. Pour the reaction solution into ethanol to precipitate, wash three times with ethanol, and dry the sample at 60 °C for 12 h to obtain deoxycellulose dimethylethyl quaternary ammonium salt with a degree of substitution of 1.0-.

[0039] The degree of substitution of the deoxycellulose dimethyl ethyl quaternary ammonium salt prepared in this embodiment is 1.0, and its nuclear magnetic resonance (NMR) spectrum (H1N) is as follows: 1 The H-NMR results are as follows Figure 1 As shown.

[0040] Bacteria in mid-logarithmic growth phase were collected and diluted with PBS to approximately 10⁶ CFU / mL. The bacterial suspension was mixed with a PBS solution of deoxycellulose dimethyl ethyl quaternary ammonium salt (final concentration: 70 μg / mL) and incubated at 37 °C for 2 h. The PBS-treated group served as a control. After incubation, the bacterial suspension was serially diluted and plated, incubated at 37 °C for 18 h, and then colony counting was performed. The effects of deoxycellulose dimethyl ethyl quaternary ammonium salt on *Escherichia coli* (…) E. coil ) and Staphylococcus aureus ( S. aureus The inhibition rate was 99.9%.

[0041] Testing the blood compatibility of deoxycellulose dimethyl ethyl quaternary ammonium salt: Test group: Whole blood was centrifuged at 2000 rpm for 10 min to separate red blood cells. The supernatant was discarded, and the red blood cells were washed with PBS at least 3 times until the supernatant was colorless. Then, a 2% v / v red blood cell suspension was prepared with PBS. Next, a 10 mg / mL solution of deoxycellulose dimethyl ethyl quaternary ammonium salt was prepared with PBS, and the PBS solution of deoxycellulose dimethyl ethyl quaternary ammonium salt (final concentration: 70 μg / mL) was added to the red blood cell suspension. The sample was incubated at 37 °C for 1 h. After incubation, the sample was centrifuged at 2000 rpm for 10 min. The supernatant was transferred to a 96-well plate, and the OD value was measured at 540 nm using a microplate reader. The hemolysis rate was calculated to be 0.80% based on the OD value.

[0042] Control (negative) group: The difference between the control (negative) group and the above test group is that the PBS solution of deoxycellulose dimethyl ethyl quaternary ammonium salt was replaced with PBS solution.

[0043] Control (positive) group: The difference between the control (positive) group and the above test group is that the PBS solution of deoxycellulose dimethyl ethyl quaternary ammonium salt was replaced with the PBS solution of 1% Triton X-100.

[0044] Hemolysis test photos as shown Figure 2 As shown, from Figure 2 As can be seen, the material of this invention does not cause hemolysis of red blood cells and has good biocompatibility; Figure 2 The experimental diagram shows the hemolysis test conducted using the sterilization material of this invention.

[0045] Example 2 The preparation of deoxycellulose dimethyl benzyl quaternary ammonium salt includes the following steps: (1) 1.62 g of cellulose was added to 20 g of AmimCl and stirred vigorously at 80 °C for 2 h to obtain a cellulose solution. 5.20 g of p-toluenesulfonyl chloride was added to the above solution and reacted at 0 °C for 24 h. After the reaction was completed, the reaction solution was poured into an ethanol / water (v / v = 1 / 1) mixed solvent to precipitate. The precipitate was washed three times with ethanol and then dried at 60 °C for 12 h to obtain cellulose p-toluenesulfonate with a degree of substitution of 0.92. (2) Add 1 g of cellulose p-toluenesulfonate to 20 g of DMSO and stir at 80 °C for 0.5 h. After the cellulose p-toluenesulfonate is completely dissolved, add 4.00 g of N,N-dimethylbenzylamine to the solution and react at 80 °C for 24 h. Pour the reaction solution into ethanol to precipitate, wash three times with ethanol, and dry the sample at 60 °C for 12 h to obtain deoxycellulose dimethylbenzyl quaternary ammonium salt with a degree of substitution of 0.92.

[0046] The degree of substitution of the deoxycellulose dimethylbenzyl quaternary ammonium salt prepared in this embodiment is 0.92, and its nuclear magnetic resonance hydrogen spectrum (NMR spectrum) is as follows: 1 The H-NMR results are as follows Figure 3 As shown.

[0047] Bacteria in mid-logarithmic growth phase were collected and diluted with PBS to approximately 10⁶ CFU / mL. The bacterial suspension was mixed with a PBS solution of deoxycellulose dimethylbenzyl quaternary ammonium salt (final concentration: 20 μg / mL) and incubated at 37 °C for 2 h. The PBS-treated group served as a control. After incubation, the bacterial suspension was serially diluted and plated on plates, incubated at 37 °C for 18 h, and then colony counting was performed. The effects of deoxycellulose dimethylbenzyl quaternary ammonium salt on *Escherichia coli* (…) E. coil ) and Staphylococcus aureus ( S. aureus The inhibition rate was 99.9%, such as Figure 4 As shown.

[0048] Blood compatibility testing of deoxycellulose dimethylbenzyl quaternary ammonium salt: Whole blood was centrifuged at 2000 rpm for 10 min to separate red blood cells. The supernatant was discarded, and the red blood cells were washed with PBS at least three times until the supernatant was colorless. Then, a 2% v / v red blood cell suspension was prepared with PBS. A 10 mg / mL solution of deoxycellulose dimethylbenzyl quaternary ammonium salt was then added to the red blood cell suspension in PBS (final concentration of deoxycellulose dimethylbenzyl quaternary ammonium salt: 50 μg / mL). The sample was incubated at 37 °C for 1 h. After incubation, the sample was centrifuged at 2000 rpm for 10 min. The supernatant was transferred to a 96-well plate, and the OD value was measured at 540 nm using a microplate reader. The hemolysis rate was calculated to be 3.30% based on the OD value.

[0049] Example 3 The preparation of deoxygenated lentinan imidazole salt includes the following steps: (1) 1.62 g of lentinan was added to 20 g of AmimCl and stirred vigorously at 80 °C for 2 h to obtain a lentinan solution. 5.20 g of p-toluenesulfonyl chloride was added to the above solution and reacted at 0 °C for 24 h. After the reaction was completed, the reaction solution was poured into an ethanol / water (v / v = 1 / 1) mixed solvent to precipitate. The precipitate was washed three times with ethanol and then dried at 60 °C for 12 h to obtain lentinan p-toluenesulfonate with a degree of substitution of 0.70. (2) Add 1 g of lentinan p-toluenesulfonate to 20 g of DMSO and stir at 80 °C for 0.5 h. After the lentinan p-toluenesulfonate is completely dissolved, add 12.00 g of N-methylimidazole to the solution and react at 80 °C for 24 h. Pour the reaction solution into ethanol to precipitate, wash three times with ethanol, and dry the sample at 60 °C for 12 h to obtain deoxylentinan imidazole salt with a degree of substitution of 0.70.

[0050] The degree of substitution of the deoxygenated lentinan imidazole salt obtained in this embodiment is 0.70, and its nuclear magnetic resonance (NMR) 1H spectrum (… 1 The H-NMR results are as follows Figure 5 As shown.

[0051] Bacteria in mid-logarithmic growth phase were collected and diluted with PBS to approximately 10⁶ CFU / mL. The bacterial suspension was mixed with a PBS solution of deoxylentinan imidazole salt (final concentration: 70 μg / mL) and incubated at 37 °C for 2 h. The PBS-treated group served as a control. After incubation, the bacterial suspension was serially diluted and plated, incubated at 37 °C for 18 h, and then colony counting was performed. The effect of deoxylentinan imidazole salt on *Escherichia coli* (…) E. coil ) and Staphylococcus aureus ( S. aureus The inhibition rate was 99.9%.

[0052] Blood compatibility testing of deoxylentinan imidazole salt: Whole blood was centrifuged at 2000 rpm for 10 min to separate red blood cells. The supernatant was discarded, and the red blood cells were washed with PBS at least 3 times until the supernatant was colorless. Then, a 2% v / v red blood cell suspension was prepared with PBS. A 10 mg / mL solution of deoxylentinan imidazole salt was then added to the red blood cell suspension (final concentration of deoxylentinan imidazole salt: 70 μg / mL). The sample was incubated at 37 °C for 1 h. After incubation, the sample was centrifuged at 2000 rpm for 10 min. The supernatant was transferred to a 96-well plate, and the OD value was measured at 540 nm using a microplate reader. The hemolysis rate was calculated to be 1.40% based on the OD value. (Image of hemolysis test is shown below.) Figure 6 As shown.

[0053] Example 4 The preparation of deoxy starch 2-hydroxyethyl quaternary ammonium salt includes the following steps: (1) 1.62 g of starch was added to 20 g of AmimCl and stirred vigorously at 80 °C for 2 h to obtain a starch solution. 5.20 g of p-toluenesulfonyl chloride was added to the above solution and reacted at 0 °C for 24 h. After the reaction was completed, the reaction solution was poured into a mixed solvent of ethanol / water (v / v = 1 / 1) to precipitate. The precipitate was washed three times with ethanol and then dried at 60 °C for 12 h to obtain starch p-toluenesulfonate with a degree of substitution of 0.83. (2) Add 1 g of starch p-toluenesulfonate to 20 g of DMSO and stir at 80 °C for 0.5 h. After the starch p-toluenesulfonate is completely dissolved, add 20.00 g of ethanolamine to the solution and react at 80 °C for 24 h. Pour the reaction solution into ethanol to precipitate, wash three times with ethanol, and dry the sample at 60 °C for 12 h to obtain deoxy starch 2-hydroxyethyl quaternary ammonium salt with a degree of substitution of 0.83.

[0054] The degree of substitution of the deoxygenated starch 2-hydroxyethyl quaternary ammonium salt prepared in this embodiment is 0.83.

[0055] Bacteria in mid-logarithmic growth phase were collected and diluted with PBS to approximately 10⁶ CFU / mL. The bacterial suspension was mixed with a PBS solution of deoxystarch-2-hydroxyethyl quaternary ammonium salt (final concentration: 40 μg / mL) and incubated at 37 °C for 2 h. The PBS-treated group served as a control. After incubation, the bacterial suspension was serially diluted and plated on plates, incubated at 37 °C for 18 h, and then colony counting was performed. The effect of deoxystarch-2-hydroxyethyl quaternary ammonium salt on *Escherichia coli* (…) E. coil ) and Staphylococcus aureus ( S. aureus The inhibition rate was 99.9%.

[0056] Blood compatibility testing of deoxystarch-2-hydroxyethyl quaternary ammonium salt: Whole blood was centrifuged at 2000 rpm for 10 min to separate red blood cells. The supernatant was discarded, and the red blood cells were washed with PBS at least 3 times until the supernatant was colorless. Then, a 2% v / v red blood cell suspension was prepared with PBS. A 10 mg / mL solution of deoxystarch-2-hydroxyethyl quaternary ammonium salt was then added to the red blood cell suspension (final concentration of deoxystarch-2-hydroxyethyl quaternary ammonium salt: 50 μg / mL). The sample was incubated at 37 °C for 1 h. After incubation, the sample was centrifuged at 2000 rpm for 10 min. The supernatant was transferred to a 96-well plate, and the OD value was measured at 540 nm using a microplate reader. The hemolysis rate was calculated to be 1.06% based on the OD value. (Image of hemolysis test is shown below.) Figure 7 As shown.

[0057] Example 5 The preparation of deoxystarch pyridinium salt includes the following steps: (1) 1.62 g of starch was added to 20 g of AmimCl and stirred vigorously at 80 °C for 2 h to obtain a starch solution. 5.20 g of p-toluenesulfonyl chloride was added to the above solution and reacted at 0 °C for 24 h. After the reaction was completed, the reaction solution was poured into a mixed solvent of ethanol / water (v / v = 1 / 1) to precipitate. The precipitate was washed three times with ethanol and then dried at 60 °C for 12 h to obtain starch p-toluenesulfonate with a degree of substitution of 0.83. (2) Add 1 g of starch p-toluenesulfonate to 20 g of DMSO and stir at 80 °C for 0.5 h. After the starch p-toluenesulfonate is completely dissolved, add 12.00 g of pyridine to the solution and react at 80 °C for 24 h. Pour the reaction solution into ethanol to precipitate, wash three times with ethanol, and dry the sample at 60 °C for 12 h to obtain deoxy starch pyridine salt with a degree of substitution of 0.83.

[0058] Bacteria in mid-log phase were collected and diluted with PBS to approximately 10⁶ CFU / mL. The bacterial suspension was mixed with a PBS solution of deoxystarch pyridinium salt (final concentration: 70 μg / mL) and incubated at 37 °C for 2 h. The PBS-treated group served as a control. After incubation, the bacterial suspension was serially diluted and plated, incubated at 37 °C for 18 h, and then colony counting was performed. The effect of deoxystarch pyridinium salt on *Escherichia coli* (…) E. coil ) and Staphylococcus aureus ( S. aureus The inhibition rate was 99.9%.

[0059] Blood compatibility testing of deoxystarch pyridinium salt: Whole blood was centrifuged at 2000 rpm for 10 min to separate red blood cells. The supernatant was discarded, and the red blood cells were washed with PBS at least 3 times until the supernatant was colorless. Then, a 2% v / v red blood cell suspension was prepared with PBS. A 10 mg / mL solution of deoxystarch pyridinium salt was then added to the red blood cell suspension (final concentration of deoxystarch pyridinium salt: 70 μg / mL). The sample was incubated at 37 °C for 1 h. After incubation, the sample was centrifuged at 2000 rpm for 10 min. The supernatant was transferred to a 96-well plate, and the OD value was measured at 540 nm using a microplate reader. The hemolysis rate was calculated to be 1.20% based on the OD value.

[0060] Example 6 The preparation of deoxyglucan tributylphosphonium salt includes the following steps: (1) 1.62 g of dextran was added to 20 g of AmimCl and stirred vigorously at 80 °C for 2 h to obtain a dextran solution. 5.20 g of p-toluenesulfonyl chloride was added to the above solution and reacted at 0 °C for 24 h. After the reaction was completed, the reaction solution was poured into a mixed solvent of ethanol / water (v / v = 1 / 1) to precipitate. The precipitate was washed three times with ethanol and then dried at 60 °C for 12 h to obtain a dextran p-toluenesulfonate with a degree of substitution of 0.78. (2) Add 1 g of dextran p-toluenesulfonate to 20 g of DMSO and stir at 80 °C for 0.5 h. After the dextran p-toluenesulfonate is completely dissolved, add 6.50 g of tributylphosphine to the solution and react at 80 °C for 24 h. Pour the reaction solution into ethanol to precipitate, wash three times with ethanol, and dry the sample at 60 °C for 12 h to obtain deoxydextran tributylphosphonium salt with a degree of substitution of 0.78.

[0061] Bacteria in mid-logarithmic growth phase were collected and diluted with PBS to approximately 10⁶ CFU / mL. The bacterial suspension was mixed with a PBS solution of deoxyglucan tributylphosphonium salt (final concentration: 10 μg / mL) and incubated at 37 °C for 2 h. The PBS-treated group served as a control. After incubation, the bacterial suspension was serially diluted and plated, incubated at 37 °C for 18 h, and then colony counting was performed. The effects of deoxyglucan tributylphosphonium salt on *Escherichia coli* (…) E. coil ) and Staphylococcus aureus ( S. aureus The inhibition rate was 99.9%.

[0062] Blood compatibility testing of deoxyglucan tributylphosphonium salt: Whole blood was centrifuged at 2000 rpm for 10 min to separate red blood cells. The supernatant was discarded, and the red blood cells were washed with PBS at least three times until the supernatant was colorless. Then, a 2% v / v red blood cell suspension was prepared with PBS. A 10 mg / mL solution of deoxyglucan tributylphosphonium salt was then added to the red blood cell suspension (final concentration of deoxyglucan tributylphosphonium salt: 10 μg / mL). The sample was incubated at 37 °C for 1 h. After incubation, the sample was centrifuged at 2000 rpm for 10 min. The supernatant was transferred to a 96-well plate, and the OD value was measured at 540 nm using a microplate reader. The hemolysis rate was calculated to be 4.50% based on the OD value.

[0063] The embodiments of the present invention have been described above by way of example. However, the scope of protection of the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made by those skilled in the art within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A selective sterilization material, characterized in that, The selective sterilization material comprises a polymer having repeating structural units as shown in Formula I below: Formula I in: In Formula I, Y is at least one of the groups A and OH; Group A is selected from at least one of imidazole salt cations, pyridinium salt cations, pyrrole salt cations, quaternary ammonium salt cations, quaternary phosphonium salt cations, and piperidine salt cations, wherein N or P in A is attached to the main chain; In the polymer, the degree of substitution of A is 0.40-1.

0.

2. The sterilization material according to claim 1, characterized in that, A is selected from at least one of the following groups: R are the same or different, and are independently selected from H and C. 1-10 Alkyl, -(C 1-10 alkylene)-OH, -(C 1-10 (alkylene)-C 6-12 Aryl; * represents a connection key; Preferably, R are the same or different, and are independently selected from H and C. 1-6 Alkyl, -(C 1-6 alkylene)-OH, -(C 1-6 (alkylene)-C 6-10 Aryl; for example selected from H, methyl, ethyl, propyl, butyl, pentyl, hexyl, -ethylene-OH or -(C 1-4 (alkylene)-phenyl.

3. The sterilization material according to claim 1, characterized in that, The degree of aggregation of the repeating structural unit shown in Formula I is 100-3000; Preferably, the main chain of the selective bactericidal material is derived from at least one of cellulose, starch, dextran, pullulan, lentinan, black fungus polysaccharide, kelp polysaccharide, and guar gum, wherein the main chain of the selective bactericidal material refers to a compound in which all Y groups are OH.

4. The method for preparing the sterilization material according to any one of claims 1-3, characterized in that, The method includes: (1) A hydroxyl-containing polymer solution is mixed with p-toluenesulfonyl chloride and reacted to obtain a p-toluenesulfonated polymer; The hydroxyl-containing polymer is selected from at least one of cellulose, starch, dextran, pullulan, lentinan, black fungus polysaccharide, kelp polysaccharide, and guar gum; (2) The sterilization material is prepared by mixing the p-toluenesulfonated polymer solution with a compound containing an A group and heating the mixture.

5. The method according to claim 4, characterized in that, In step (1), the hydroxyl-containing polymer solution is obtained by dissolving the hydroxyl-containing polymer in solvent 1, wherein solvent 1 is selected from ionic liquids and optionally contains or does not contain amide solvents; For example, the ionic liquid is selected from at least one of the following substances: 1-ethyl-3-methylimidazolium chloride ionic liquid, 1-ethyl-3-methylimidazolium bromide ionic liquid, 1-allyl-3-methylimidazolium chloride ionic liquid, 1-allyl-3-methylimidazolium bromide ionic liquid, 1-butyl-3-methylimidazolium chloride ionic liquid, 1-butyl-3-methylimidazolium bromide ionic liquid, 1-ethyl-3-methylimidazolium acetate ionic liquid, 1-allyl-3-methylimidazolium chloride ionic liquid, 1-butyl-3-methylimidazolium bromide ionic liquid, 1-ethyl-3-methylimidazolium acetate ionic liquid, 1-allyl-3-methylimidazolium chloride ionic liquid, 1-ethyl ... Acetate ionic liquid, 1-butyl-3-methylimidazolium acetate ionic liquid, N-ethylpyridine chloride ionic liquid, N-ethylpyridine bromide ionic liquid, 1,3-dimethylimidazolium dimethyl phosphate ionic liquid, 1-ethyl-3-methylimidazolium diethyl phosphate ionic liquid, 3-methylimidazolium carboxylate ionic liquid, N-methylpyridine carboxylate ionic liquid, 1-ethyl-3-methylimidazolium carboxylate ionic liquid, 1-butyl-3-methylimidazolium carboxylate ionic liquid; The amide solvent is selected from... N,N -dimethylformamide and N,N At least one of dimethylacetamide; Preferably, in step (1), the mass concentration of the polymer solution is 2-20 wt%.

6. The method according to claim 4, characterized in that, In step (1), the mass ratio of the hydroxyl-containing polymer to p-toluenesulfonyl chloride in the hydroxyl-containing polymer solution is 1:1-10; Preferably, in step (1), the temperature of the mixing reaction is 0-25℃ and the time of the mixing reaction is 10-48h.

7. The method according to claim 4, characterized in that, In step (2), the p-toluenesulfonated polymer solution is obtained by dissolving the solid p-toluenesulfonated polymer from step (1) in solvent 2. For example, solvent 2 is selected from at least one of sulfone solvents and amide solvents, such as dimethyl sulfoxide. N, N -dimethylformamide and N,N At least one of dimethylacetamide; Preferably, in step (2), the mass concentration of the p-toluenesulfonated polymer solution is 2-20 wt%; Preferably, in step (2), the temperature of the heating reaction is 50-120℃; and the heating reaction time is 10-48h.

8. The method according to claim 4, characterized in that, In step (2), the compound containing the A group is selected from at least one of the following compounds; R has the meanings described above; Preferably, the compound containing the A group is selected from imidazole, N-alkylimidazolium (e.g., NC). 1-6 Alkyl imidazoles, preferably N-methylimidazolium, N-ethylimidazolium, or N-propylimidazolium), pyridines, and N-alkylpyridines (e.g., NC... 1-6 Alkylpyridine, preferably at least one of N-methylpyridine, N-ethylpyridine, N-propylpyridine, pyrrole, amine compounds (e.g., ethanolamine, N,N-dimethylbenzylamine, N,N-dimethylethylamine, etc.), alkylphosphine (e.g., tributylphosphine), and piperidine.

9. The method according to claim 4, characterized in that, In step (2), the mass ratio of the solute p-toluenesulfonated polymer to the compound containing the A group in the p-toluenesulfonated polymer solution is 1:1-40.

10. The use of the sterilizing material according to any one of claims 1-3 in the preparation of antimicrobial materials.

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