A wound repair material and a method of making the same

Abstract

The application discloses a wound repairing material and a preparation method thereof, and relates to the technical field of medical materials. The wound repairing material comprises the following raw materials in parts by weight: 50-60 parts of bioactive glass, 15-30 parts of chitosan, 10-20 parts of functional material, and 300-450 parts of deionized water. The intermediate 1 is generated by the reaction of oleamide propyl dimethylamine and 4-chlorobutanol, the intermediate 2 is generated by the reaction of the intermediate 1 and 5,10,15,20-tetra(4-carboxyphenyl)porphyrin, and the functional material is generated by the reaction of the intermediate 2 and 4,4'-{[6-((1-carboxyl-2-mercaptoethyl)amino)-1,3,5-triazine-2,4-diyl]bis(nitrene)}bis[4-(2-carboxyethyl)heptanedioic acid] under the action of a photoinitiator. The wound repairing material prepared by the application has excellent antibacterial performance and hemostatic performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of medical materials, in particular to a wound repair material and a preparation method thereof. BACKGROUND

[0002] Wound repair, especially the repair of chronic refractory wounds (such as diabetic foot ulcers, deep pressure sores, and burn residual wounds), is a common problem in clinical practice. Chronic refractory wounds are often accompanied by bacterial infection, biofilm formation, persistent inflammation, and impaired tissue regeneration. The currently used wound repair materials are mainly hydrogels and sponges. These materials need to be directly pressed onto bleeding wounds during use and are not suitable for bleeding wounds that cannot be pressed. In contrast, powder wound repair materials have small volume and good dispersibility, and are more suitable for treating some bleeding wounds that cannot be pressed or bandaged. In addition, for some deep interstitial wounds (such as diabetic foot ulcers) with biofilm infection, bacteria are prone to colonization and form biofilms, and traditional antibiotics are difficult to penetrate. Therefore, photodynamic therapy to achieve sterilization is a relatively more effective way. However, the current wound repair materials still have the defects of insufficient photodynamic antibacterial performance and poor hemostatic effect. Therefore, it is of great significance to provide a powder wound repair material that integrates photodynamic antibacterial and rapid hemostatic functions for the treatment of chronic refractory wounds.

[0003] Chinese patent with publication number CN105381500A discloses a functional wound repair material and a preparation method thereof. The wound repair material is prepared by compounding bioactive glass, silver nitrate, antibiotics, and degradable polymer with water. The components are as follows: bioactive glass 7-14 parts, silver nitrate 0.5-0.7 parts, antibiotics 0.2-0.6 parts, degradable polymer 15-25 parts, and deionized water 80-160 parts. The functional wound repair material disclosed in the invention loads silver ions and antibiotics. Silver ions and antibiotics each have bactericidal properties. In addition, silver ions can increase the generation of oxygen free radicals and increase the permeability of bacterial cell membranes, making it easier for antibiotics to enter bacteria and play a synergistic effect. Therefore, the functional wound repair material disclosed in the invention has strong antibacterial properties and can solve the problem of existing wound repair materials that easily adhere to bacteria, leading to infection and thus unsatisfactory treatment effect. However, its hemostatic performance is still insufficient. SUMMARY

[0004] In view of the deficiencies of the prior art, the present application aims to provide a wound repair material and a preparation method thereof.

[0005] To achieve the above-mentioned purpose, the present application realizes the following technical solutions:

[0006] A wound repairing material, comprising the following raw materials in parts by weight: bioactive glass 50-60 parts, chitosan 15-30 parts, functional material 10-20 parts, deionized water 300-450 parts.

[0007] The functional material is prepared by the following method:

[0008] S1: oleamide propyl dimethylamine reacts with 4-chlorobutanol to generate intermediate 1, and the reaction equation is as follows:

[0009]

[0010] S2: intermediate 1 reacts with 5,10,15,20-tetrakis(4-carboxyphenyl) porphyrin to generate intermediate 2, and the reaction equation is as follows:

[0011]

[0012] S3: intermediate 2 reacts with 4,4'-{[6-((1-carboxy-2-mercaptoethyl)amino)-1,3,5-triazine-2,4-diyl]bis(nitrene)}bis[4-(2-carboxyethyl)heptanedioic acid] under the action of a photoinitiator to generate a modified synergist, and the reaction equation is as follows:

[0013]

[0014] In step S1, the molar ratio of the oleamide propyl dimethylamine to 4-chlorobutanol is 1:(1.05-1.1).

[0015] In step S2, the molar ratio of the intermediate 1 to 5,10,15,20-tetrakis(4-carboxyphenyl) porphyrin is (4.05-4.1):1.

[0016] In step S3, the molar ratio of the intermediate 2 to 4,4'-{[6-((1-carboxy-2-mercaptoethyl)amino)-1,3,5-triazine-2,4-diyl]bis(nitrene)}bis[4-(2-carboxyethyl)heptanedioic acid] is 1:(4.1-4.2).

[0017] The reaction time of step S1 is 22-24h.

[0018] The reaction solvent of step S1 is an ethanol aqueous solution.

[0019] The reaction time of step S2 is 17-18h, and the reaction temperature is 25-30℃; the reaction solvent is anhydrous DMF.

[0020] The reaction temperature of step S3 is room temperature; the reaction solvent is anhydrous tetrahydrofuran.

[0021] In step S3, the photoinitiator is 2,2-dimethoxy-2-phenylacetophenone.

[0022] A preparation method of a wound repair material, comprising the following steps:

[0023] (1) Take by weight parts: bioactive glass 50-60 parts, chitosan 15-30 parts, functional material 10-20 parts, deionized water 300-450 parts;

[0024] (2) Stir and mix the deionized water and chitosan, add the bioactive glass and functional filler, homogenize, freeze-dry, and after grinding and sterilization, the wound repair material is obtained.

[0025] Due to the above technical scheme, the beneficial effects of the present application include:

[0026] The wound repair material prepared by the present application has high bacteriostatic rate and short blood clotting time, and exhibits excellent antibacterial performance and hemostatic performance. The added functional material improves the antibacterial performance of the wound repair material through the photodynamic sterilization effect of the porphyrin ring structure and the membrane damage effect of the quaternary ammonium salt structure; the carboxyl groups improve the hemostatic performance of the wound repair material by coordinating with Fe 2+ The hemostatic performance of the wound repair material is improved. DETAILED DESCRIPTION

[0027] The present application will be further described below in conjunction with examples, but the present application is not limited to these examples.

[0028] Example 1 Preparation of 4,4'-{[6-((1-carboxy-2-mercaptoethyl)amino)-1,3,5-triazine-2,4-diyl]bis(nitrilo)}bis[4-(2-carboxyethyl)heptanedioic acid]:

[0029] N1: Under nitrogen protection, 300ml anhydrous acetonitrile, 0.1mol cyanuric chloride, 0.205mol 4-amino-4-(2-carboxyethyl)heptanedioic acid were stirred and mixed, 0.205mol N,N-diisopropyl ethylamine was added, 0℃ reaction for 6h, then warmed to 25℃ for 8h, slowly added 0.1M hydrochloric acid to adjust the pH of the solution to 2 under ice bath, after stirring, filtered, the filter cake was washed with deionized water until neutral, vacuum dried at 60℃ for 8h, to obtain intermediate A; the reaction equation is as follows:

[0030]

[0031] The nuclear magnetic resonance hydrogen spectrum data are as follows: 1 H NMR (400 MHz, Chloroform- d) δ 11.61 (s, 6H),6.44 (s, 2H), 2.40 (s, 12H), 1.91 (s, 12H);

[0032] N2: 300 ml of anhydrous DMF, 0.1 mol of intermediate A, 0.11 mol of L-cysteine were stirred and mixed, 0.11 mol of N,N-diisopropyl ethylamine was added, and the mixture was reacted at 65°C for 16 h. After cooling to room temperature, the pH of the solution was adjusted to 2 by slowly adding 0.1M hydrochloric acid, and after sufficient stirring, the filter cake was washed with deionized water until neutral, and vacuum dried at 70°C for 10 h to obtain 4,4'-{[6-((1-carboxy-2-mercaptoethyl)amino)-1,3,5-triazin-2,4-diyl]bis(nitrilo)}bis[4-(2-carboxyethyl)heptanedioic acid]; the reaction equation is as follows:

[0033]

[0034] The nuclear magnetic resonance hydrogen spectrum data are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 11.61 (s, 6H),10.88 (s, 1H), 7.13 (d, J = 0.5 Hz, 1H), 6.32 (s, 2H), 4.72 (d, J = 0.6 Hz,1H), 3.22-3.06 (m, 2H), 2.43 (s, 1H), 2.40 (s, 12H), 1.89 (s, 12H).

[0035] Example 2: Preparation of functional material:

[0036] S1: 300 ml of 70wt% aqueous ethanol solution, 0.1 mol of oleamide propyl dimethylamine, 0.105 mol of 4-chlorobutanol were stirred and mixed, and the temperature was raised to reflux, and the reaction was carried out for 22 h. After cooling to room temperature, 150 ml of a mixed solution of ethyl acetate and anhydrous ethanol (V 乙酸乙酯 :V 无水乙醇 =8:2) was recrystallized, and vacuum dried at 60°C for 12 h to obtain intermediate 1; the nuclear magnetic resonance hydrogen spectrum data are as follows: 1 H NMR (400 MHz, DMSO- d 6) δ 7.63 (d, J = 7.4 Hz, 1H), 5.37 (s, 2H), 4.25(t, J = 5.0 Hz, 1H), 3.50 (d, J = 5.0 Hz, 2H), 3.37 (d, J = 8.7 Hz, 4H), 3.15(d, J = 1.5 Hz, 2H), 3.14 (s, 6H), 2.11 (s, 2H), 2.05 (s, 2H),1.74 (s, 2H), 1.55 (d, J = 12.6 Hz, 4H), 1.34-1.25 (m, 20H), 0.89 (s, 3H);

[0037] S2: 1000 ml of anhydrous DMF, 0.405 mol of intermediate 1, 0.1 mol of 5,10,15,20-tetra(4-carboxyphenyl)porphyrin were stirred and mixed, 400 ml of a mixed solution containing 0.42 mol of dicyclohexyl carbodiimide and 0.08 mol of 4-dimethylamino pyridine were slowly added dropwise under ice bath, 3 h after dropping, continue to keep under ice bath for 3 h, then warm up to 25 °C for 18 h, filter, add 800 ml of cold ether to the filtrate, stir to precipitate, filter, filter cake is washed with 5 °C ice water (3 x 200 ml), recrystallized with 300 ml of a mixed solution of ethyl acetate and methanol (V 乙酸乙酯 :V 甲醇 = 4: 1) recrystallization, 65 °C vacuum drying for 12 h, to obtain intermediate 2; the nuclear magnetic resonance hydrogen spectrum data are as follows: 1 H NMR (400 MHz, Chloroform- d) δ 9.86 (s, 1H), 9.80 (s, 1H), 8.07-7.97 (m, 8H), 7.77-7.62 (m, 8H), 7.49 (s, 2H), 7.40 (s, 2H), 7.13 (s, 2H), 6.79 (s, 2H), 6.54 (d, J = 0.6 Hz, 4H), 5.35 (s, 8H), 4.32 (s, 8H), 3.40 (d, J = 7.0 Hz, 16H), 3.19 (d, J = 0.5 Hz, 8H), 3.15 (s, 24H), 2.15 (s, 8H), 2.07 (s, 8H), 2.02 (s, 16H), 1.94-1.85 (m, 12H), 1.81 (d, J = 12.4 Hz, 4H), 1.54 (s, 8H), 1.35-1.26 (m, 80H), 0.90 (s, 12H);

[0038] S3: Under the protection of nitrogen, 1500 ml of anhydrous tetrahydrofuran, 0.1 mol of intermediate 2, 0.41 mol of 4,4'-{[6-((1-carboxy-2-mercaptoethyl)amino)-1,3,5-triazine-2,4-diyl]bis(nitrilo)}bis[4-(2-carboxyethyl)heptanedioic acid], 0.6 g of 2,2-dimethoxy-2-phenylacetophenone, stirring and mixing, irradiating under 100 W of 365 nm ultraviolet light at room temperature for 30 min, 40°C, 3h of reduced pressure distillation, adding 800 ml of n-hexane, stirring to precipitate, filtering, 60°C vacuum drying for 12h, to obtain a functional material; its nuclear magnetic resonance hydrogen spectrum data are as follows: 1 H NMR (400 MHz, Chloroform- d) δ 11.61 (s, 24H), 11.08 (s, 4H), 9.88 (s, 1H), 9.80 (s, 1H), 8.07-7.96 (m, 8H), 7.78-7.69 (m,8H), 7.69-7.63 (m, 4H), 7.49 (s, 2H), 7.40 (s, 2H), 7.13 (s, 2H), 6.79 (s,2H), 6.54 (d, J = 0.6 Hz, 4H), 6.32 (s, 8H), 4.80 (dd, J = 11.3, 0.5 Hz, 4H), 4.32 (d, J = 1.2 Hz, 8H), 3.43-3.36 (m, 16H), 3.33-3.17 (m, 16H), 3.15 (s,24H), 2.75 (s, 4H), 2.40 (s, 48H), 2.15 (s, 8H), 2.07 (d, J = 1.4 Hz, 8H),1.94-1.77 (m, 64H), 1.56-1.42 (m, 24H), 1.35-1.26 (m, 88H), 0.90 (s, 12H).

[0039] Example 3: Preparation of functional materials:

[0040] S1: Mix 300 ml of 70 wt% ethanol aqueous solution, 0.1 mol of oleamide propyl dimethylamine, and 0.108 mol of 4-chlorobutanol. Heat to reflux and react for 23 h. Cool to room temperature and distill under reduced pressure at 60 °C for 3 h. Distill using 150 ml of a mixture of ethyl acetate and anhydrous ethanol (V... 乙酸乙酯 :V 无水乙醇 Recrystallize (8:2) and dry under vacuum at 60°C for 12 h to obtain intermediate 1;

[0041] S2: Under nitrogen protection, 1000 ml of anhydrous DMF, 0.408 mol of intermediate 1, and 0.1 mol of 5,10,15,20-tetra(4-carboxyphenyl)porphyrin were stirred and mixed. Under ice bath conditions, 400 ml of a mixed solution containing 0.4 mol of dicyclohexylcarbodiimide and 0.08 mol of 4-dimethylaminopyridine was slowly added dropwise over 3 hours. The mixture was then kept at ice bath conditions for another 3 hours, followed by a reaction at 25°C for 18 hours. After filtration, 800 ml of cold diethyl ether was added to the filtrate, and the mixture was stirred to precipitate the precipitate. The precipitate was filtered, and the filter cake was washed with 300 ml of a mixture of ethyl acetate and methanol (V...). 乙酸乙酯 :V 甲醇 Recrystallize (4:1) and dry under vacuum at 65°C for 12 h to obtain intermediate 2;

[0042] S3: 1500 ml of anhydrous tetrahydrofuran, 0.1 mol of intermediate 2, 0.415 mol of 4,4'-{[6-((1-carboxy-2-mercaptoethyl)amino)-1,3,5-triazine-2,4-diyl]bis(nitrilo)}bis[4-(2-carboxyethyl)heptanedioic acid], 0.6 g of 2,2-dimethoxy-2-phenylacetophenone were stirred and uniformly mixed under nitrogen protection, irradiated under 100 W of 365 nm ultraviolet light at room temperature for 30 min, distilled at 40°C under reduced pressure for 3 h, 800 ml of n-hexane was added to stir and precipitate, filtered, and vacuum dried at 60°C for 12 h to obtain the functional material.

[0043] Example 4: Preparation of a functional material

[0044] S1: 300 ml of 70 wt% aqueous ethanol solution, 0.1 mol of oleamide propyl dimethylamine, and 0.11 mol of 4-chlorobutanol were stirred and uniformly mixed, heated to reflux, reacted for 24 h, cooled to room temperature, distilled at 40°C under reduced pressure for 3 h, recrystallized with 150 ml of a mixed solution of ethyl acetate and anhydrous ethanol (V 乙酸乙酯 :V 无水乙醇 = 8:2), and vacuum dried at 60°C for 12 h to obtain intermediate 1;

[0045] S2: 1000 ml of anhydrous DMF, 0.41 mol of intermediate 1, and 0.1 mol of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin were stirred and uniformly mixed under nitrogen protection, 400 ml of a mixed solution containing 0.42 mol of dicyclohexyl carbodiimide and 0.08 mol of 4-dimethylamino pyridine was slowly added dropwise under ice bath, 3 h after dropping, continued to be incubated under ice bath for 3 h, then heated to 30°C and reacted for 17 h, filtered, 800 ml of cold diethyl ether was added to the filtrate, stirred to precipitate, filtered, the filter cake was washed with 5°C ice water (3 x 200 ml), recrystallized with 300 ml of a mixed solution of ethyl acetate and methanol (V 乙酸乙酯 :V 甲醇 = 4:1), and vacuum dried at 65°C for 12 h to obtain intermediate 2;

[0046] S3: 1500 ml of anhydrous tetrahydrofuran, 0.1 mol of intermediate 2, 0.42 mol of 4,4'-{[6-((1-carboxy-2-mercaptoethyl)amino)-1,3,5-triazine-2,4-diyl]bis(nitrilo)}bis[4-(2-carboxyethyl)heptanedioic acid], 0.6 g of 2,2-dimethoxy-2-phenylacetophenone were stirred and uniformly mixed under nitrogen protection, irradiated under 100 W of 365 nm ultraviolet light at room temperature for 30 min, distilled at 40°C under reduced pressure for 3 h, 800 ml of n-hexane was added to stir and precipitate, filtered, and vacuum dried at 60°C for 12 h to obtain the functional material.

[0047] Example 5 Preparation of wound repair material:

[0048] (1) Weigh by weight: bioactive glass 50g, chitosan 15g, functional material (prepared in Example 2) 10g, deionized water 300g;

[0049] (2) Mix deionized water with chitosan, stir at 500 rpm for 2h, add bioactive glass and functional filler, place in high pressure homogenizer, cycle homogenization 5 times under 20MPa pressure, freeze-dry at-50℃ for 24h to obtain block solid, then place in planetary ball mill, use 5mm diameter grinding balls and 3mm grinding balls, weight ratio of 5mm grinding balls to 3mm grinding balls is 2:1, ball-to-material ratio is 15:1, grind at 500 rpm for 30min, sterilize by γ-ray (irradiation dose 25kGy) for 2h, to obtain wound repair material.

[0050] Example 6 Preparation of wound repair material:

[0051] (1) Weigh by weight: bioactive glass 55g, chitosan 25g, functional material (prepared in Example 3) 15g, deionized water 380g;

[0052] (2) Mix deionized water with chitosan, stir at 500 rpm for 2h, add bioactive glass and functional filler, place in high pressure homogenizer, cycle homogenization 4 times under 30MPa pressure, freeze-dry at-50℃ for 24h to obtain block solid, then place in planetary ball mill, use 5mm diameter grinding balls and 3mm grinding balls, weight ratio of 5mm grinding balls to 3mm grinding balls is 2:1, ball-to-material ratio is 15:1, grind at 500 rpm for 30min, sterilize by γ-ray (irradiation dose 25kGy) for 2h, to obtain wound repair material.

[0053] Example 7 Preparation of wound repair material:

[0054] (1) Weigh by weight: bioactive glass 60g, chitosan 30g, functional material (prepared in Example 4) 20g, deionized water 450g;

[0055] (2) Mix deionized water with chitosan, stir at 500 rpm for 2h, add bioactive glass and functional filler, place in high pressure homogenizer, cycle homogenization 3 times under 40MPa pressure, freeze-dry at-50℃ for 24h to obtain block solid, then place in planetary ball mill, use 5mm diameter grinding balls and 3mm grinding balls, weight ratio of 5mm grinding balls to 3mm grinding balls is 2:1, ball-to-material ratio is 15:1, grind at 500 rpm for 30min, sterilize by γ-ray (irradiation dose 25kGy) for 2h, to obtain wound repair material.

[0056] Comparative Example 1

[0057] The raw material composition and the preparation method of the wound repair material are basically the same as those of Example 6, except that the functional material is replaced with equal weight of the functional material prepared by the following method:

[0058] The preparation method of the functional material is basically the same as that of Example 3, except that the oleamide propyl dimethylamine in step S1 is replaced with equal molar amount of dimethylaminopropyl methacrylamide.

[0059] Comparative Example 2

[0060] The raw material composition and the preparation method of the wound repair material are basically the same as those of Example 6, except that the functional material is replaced with equal weight of the functional material prepared by the following method:

[0061] The preparation method of the functional material is basically the same as that of Example 3, except that the 5,10,15,20-tetrakis(4-carboxyphenyl) porphyrin in step S2 is replaced with equal molar amount of 4,4',4'',4'''-(parylene-2,5,8,11- tetrayl) tetrabenzoic acid.

[0062] Comparative Example 3

[0063] The raw material composition and the preparation method of the wound repair material are basically the same as those of Example 6, except that the functional material is replaced with equal weight of the functional material prepared by the following method:

[0064] The preparation method of the functional material is basically the same as that of Example 3, except that the 5,10,15,20-tetrakis(4-carboxyphenyl) porphyrin in step S2 is replaced with equal molar amount of 5,10-di(4-carboxyphenyl)-10,20-diphenyl-porphyrin (CAS No.: 142168-26-1).

[0065] Comparative Example 4

[0066] The raw material composition and the preparation method of the wound repair material are basically the same as those of Example 6, except that the functional material is replaced with equal weight of the functional material prepared by the following method:

[0067] The preparation method of the functional material is basically the same as that of Example 3, except that the 4,4'-{[6-((1-carboxy-2-mercaptoethyl)amino)-1,3,5-triazine-2,4-diyl]bis(nitrilo)}bis[4-(2-carboxyethyl)heptanedioic acid] in step S3 is replaced with equal molar amount of L-cysteine.

[0068] The bioactive glass used in the embodiments and comparative examples of this application is medical grade HQ-BG45s-D1, produced by Kunshan Overseas Chinese Science and Technology New Materials Co., Ltd.; the number average molecular weight of chitosan is 10kDa.

[0069] The wound repair materials prepared in Examples 5-7 and Comparative Examples 1-4 were tested for antibacterial properties and in vitro coagulation properties. The test results are shown in Table 1.

[0070] Antibacterial performance test: Staphylococcus aureus was selected as the test strain. Individual colonies were picked from the test strain and diluted with physiological saline to a bacterial concentration of 10. 8 CFU / ml. 100 μl of bacterial suspension was added to sterile LB liquid medium, followed by 1 g of the wound repair materials prepared in Examples 5-7 and Comparative Examples 1-4, respectively. The mixture was placed on a constant-temperature shaker and shaken at 250 rpm for 1 h at 37°C. After dilution with 9 ml of PBS buffer (0.1 M, pH=7.4), the diluted bacterial suspension was quantitatively inoculated into culture dishes containing sterile agar medium (AGAR). The cultures were incubated at 37°C for 48 h, and bacterial counts were performed. The control group consisted of wound repair materials prepared without the addition of functional materials (the raw material composition and preparation method of the wound repair materials were basically the same as in Example 6, except that no functional materials were added). According to the formula... (W: Antibacterial rate, %; A: Viable bacterial concentration of the control group after 48 hours, CFU / ml; B: Viable bacterial concentration of the wound repair materials prepared in Examples 5-7 and Comparative Examples 1-4 after 48 hours, CFU / ml) The antibacterial rate was calculated.

[0071] In vitro coagulation performance test: 40 mg of the wound repair materials prepared in Examples 5-7 and Comparative Examples 1-4 were placed into vacuum blood collection tubes containing 10 mg of heparin anticoagulant, respectively. Vacuum blood collection tubes containing 10 mg of heparin anticoagulant without wound repair material were used as a control. The tubes were incubated at 37°C for 1 hour. Then, 1 mL of venous blood from a healthy person was drawn from each vacuum blood collection tube. The tubes were tilted 30° every 5 seconds, and the flow of blood within the tubes was observed until the blood completely coagulated. The time required from the addition of blood to complete coagulation at the bottom of the blood collection tube was recorded as the dynamic coagulation time.

[0072] Table 1

[0073]

[0074] As can be seen from the data in Table 1, the wound repair materials prepared in Examples 5-7 of this application have a high antibacterial rate and a short clotting time, exhibiting excellent antibacterial and hemostatic properties.

[0075] The wound repair material prepared in the application has excellent antibacterial performance and hemostatic performance, mainly because the functional material added contains a porphyrin ring, a quaternary ammonium salt, a long-chain alkyl structure and multiple carboxyl groups. Among them, the porphyrin ring structure produces reactive oxygen under light, which can accurately kill bacteria and biofilm, realizing the photodynamic antibacterial effect; the quaternary ammonium salt structure has a positive charge, which can destroy the bacterial cell membrane through electrostatic action; the long-chain alkyl can enhance the affinity of the molecule to the bacterial membrane / biofilm, promote the directional enrichment of the quaternary ammonium salt and the porphyrin ring to the bacteria, and improve the antibacterial performance of the wound repair material through the dual action of photodynamic and membrane destruction. A large number of carboxyl groups in the functional material can dissociate into -COO - , which can combine with Fe 2+ in hemoglobin to form a glue block to close the end of the capillary, thereby realizing the rapid hemostasis of the wound repair material, and the hydration of the carboxyl group can enhance the moisture retention of the material. The functional material used in Comparative Example 2 lacks a porphyrin ring structure and cannot produce reactive oxygen under light, resulting in poor photodynamic antibacterial performance compared with the embodiment; the functional material used in Comparative Example 4 has fewer carboxyl groups in the structure, which has weaker ability to combine with Fe 2+ in hemoglobin, resulting in poor hemostatic performance of the wound repair material compared with the embodiment.

[0076] The above is only a preferred embodiment of the application and is not intended to limit the application; however, for ordinary skilled persons in the art, some minor changes, modifications and equivalent changes made to the above disclosed technical content without departing from the scope of the technical solution of the application are equivalent embodiments of the application; at the same time, any equivalent changes, modifications and evolution of the above embodiments made according to the essential technology of the application are still within the protection scope of the technical solution of the application.

Claims

1. A wound repair material, characterized in that, The raw materials include the following parts by weight: 50-60 parts of bioactive glass, 15-30 parts of chitosan, 10-20 parts of functional materials, and 300-450 parts of deionized water. The functional material is prepared by the following method: S1: Oleamide propyl dimethylamine reacts with 4-chlorobutanol to generate intermediate 1. S2: Intermediate 1 reacts with 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin to generate intermediate 2. S3: Intermediate 2 reacts with 4,4'-{[6-((1-carboxy-2-mercaptoethyl)amino)-1,3,5-triazine-2,4-diyl]bis(nitrilo-2-dimethyl)}bis[4-(2-carboxyethyl)pimelic acid] under the action of a photoinitiator to generate functional materials.

2. The wound repair material according to claim 1, characterized in that, In step S1, the molar ratio of oleamide propyl dimethylamine to 4-chlorobutanol is 1:(1.05-1.1).

3. The wound repair material according to claim 1, characterized in that, In step S2, the molar ratio of intermediate 1 to 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin is (4.05-4.1):

1.

4. The wound repair material according to claim 1, characterized in that, In step S3, the molar ratio of intermediate 2 to 4,4'-{[6-((1-carboxy-2-mercaptoethyl)amino)-1,3,5-triazine-2,4-diyl]bis(nitrilo-2-dimethyl)}bis[4-(2-carboxyethyl)pimelic acid] is 1:(4.1-4.2).

5. The wound repair material according to claim 1, characterized in that, The reaction time for step S1 is 22-24 hours.

6. The wound repair material according to claim 1, characterized in that, The reaction solvent in step S1 is an aqueous solution of ethanol.

7. The wound repair material according to claim 1, characterized in that, The reaction time for step S2 is 17-18 hours, and the reaction temperature is 25-30℃; the reaction solvent is anhydrous DMF.

8. The wound repair material according to claim 1, characterized in that, The reaction temperature in step S3 is room temperature; the reaction solvent is anhydrous tetrahydrofuran.

9. The wound repair material according to claim 1, characterized in that, In step S3, the photoinitiator is 2,2-dimethoxy-2-phenylacetophenone.

10. A method for preparing a wound repair material according to any one of claims 1-9, characterized in that, Includes the following steps: (1) Weigh out the following by weight: 50-60 parts of bioactive glass, 15-30 parts of chitosan, 10-20 parts of functional materials, and 300-450 parts of deionized water; (2) Mix deionized water and chitosan, add bioactive glass and functional filler, homogenize and freeze dry, and then grind and sterilize to obtain wound repair material.

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