Preparation method of surface anticoagulant coating of polyester fiber fabric

Abstract

The present application relates to the field of coating, disclose a kind of preparation method of surface anti-blood clotting coating of dacron fiber fabric, comprising: S1: modification is carried out to heparin to introduce aldehyde group, obtain aldehyde group bearing heparin;S2: amino malononitrile p-toluenesulfonate is dissolved in trimethylolammonium hydrochloride buffer with aldehyde group bearing heparin together mixed, obtain anti-blood clotting coating solution;S3: dacron fiber fabric is immersed into anti-blood clotting coating solution, after oscillation incubation, remove, wash, dry, obtain the surface of dacron fiber fabric that uniform deposition has anti-blood clotting coating.The present application first carries out aldehyde group modification to heparin to give its copolymerization ability with amino malononitrile p-toluenesulfonate, then it is mixed with amino malononitrile p-toluenesulfonate under alkaline condition, and is deposited on the surface of dacron fiber fabric by oscillation reaction, and anti-blood clotting coating is prepared.

Description

Technical Field

[0001] This invention relates to the field of coatings, and more particularly to a method for preparing an anticoagulant coating on the surface of polyester fiber fabrics. Background Technology

[0002] Factors such as an aging population, changes in lifestyle, and environmental pollution have led to a year-on-year increase in the incidence of chronic diseases. Treatment for many diseases, including heart disease, diabetes, and arthritis, requires implantable or interventional devices. Medical devices that are in prolonged contact with blood can trigger the host's immune defense mechanisms, potentially leading to thrombosis. When a device comes into contact with blood, proteins in the blood (albumin, fibrinogen, etc.) rapidly adhere to the device's surface. Platelets adhere to and aggregate on the protein membrane, activating clotting factors and producing thrombin. Thrombin binds to fibrinogen, platelets, and other macromolecules, causing blood cells to adhere to the blood vessel wall, ultimately forming a thrombus.

[0003] To improve the blood compatibility of materials and reduce the risk of thrombosis, researchers have developed various anticoagulant coating technologies. These technologies include the construction of bioinert surfaces, release antithrombotic compounds, and immobilized anticoagulant coatings. While these technologies show promise for clinical applications in blood compatibility, several drawbacks limit their long-term use. The limitations of immobilized anticoagulants include their limited mechanism of action and the fact that their disruption of the coagulation cascade does not prevent plasma protein adsorption, which may bind to the anticoagulant and promote the coagulation reaction. The construction of bioinert surfaces, while reducing the adhesion of blood components, does not inhibit the coagulation process, resulting in very limited anticoagulant activity. Furthermore, the lifetime of antithrombotic release materials is limited by their loading capacity, making them prone to explosive depletion.

[0004] Therefore, we constructed an aminomalonitrile / heparin / zinc composite coating, in which heparin has antithrombotic properties, zinc ions resist bacteria, increase the secretion of vascular endothelial growth factor, and promote angiogenesis. This composite coating can function at different stages of the coagulation process, reducing thrombus formation by combining the fixation of anticoagulants with the construction of cell growth surfaces. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention provides a method for preparing an anticoagulant coating on the surface of polyester fiber fabrics. The invention first modifies heparin by aldehyde to impart its ability to copolymerize with aminomalonium p-toluenesulfonate. Then, it mixes heparin and aminomalonium p-toluenesulfonate under alkaline conditions and reacts with a shaking reaction to deposit the coating onto the surface of polyester fiber fabric, thus obtaining an anticoagulant coating and greatly expanding its application areas.

[0006] The specific technical solution of the present invention is as follows: a method for preparing an anticoagulant coating on the surface of polyester fiber fabric, comprising the following steps:

[0007] S1: Modify heparin to introduce aldehyde groups to obtain heparin with aldehyde groups.

[0008] S2: Dissolve aminomalononitrile p-toluenesulfonate and aldehyde heparin together in a tris(hydroxymethyl)aminomethane hydrochloride buffer solution with pH = 8.0-8.8, and adjust the pH of the system to 8-9 with alkali to obtain an anticoagulant coating solution.

[0009] The concentration of aminomalonitrile p-toluenesulfonate in the anticoagulant coating solution is 10-50 g / mL, and the concentration of aldehyde heparin is 0.5-2 mg / mL.

[0010] S3: Immerse the polyester fiber fabric in the anticoagulant coating solution, shake and incubate, then remove it, wash away any residual unpolymerized precipitate or its derivatives on the surface of the polyester fiber fabric, and dry it to obtain a polyester fiber fabric with a uniformly deposited anticoagulant coating on the surface.

[0011] Heparin has anticoagulant properties, so introducing it into an aminomalonium self-polymerized coating can impart anticoagulant efficacy to the coating. However, heparin molecules themselves do not possess groups that can polymerize with aminomalonium. Therefore, in S1, the present invention first modifies heparin by aldehyde modification, introducing heparin into the coating through a Schiff base reaction between the aldehyde and amino groups.

[0012] The modification of heparin by this invention not only endows it with the ability to copolymerize with aminomalononitrile p-toluenesulfonate, but the modification process does not destroy the functional active structure of heparin, so it can almost still maintain its original activity.

[0013] In S2, heparin with aldehyde groups is mixed with aminomalonium p-toluenesulfonate under alkaline conditions to obtain an anticoagulant coating solution; in S3, a copolymerization reaction is carried out on the surface of polyester fiber fabric by impregnation and shaking incubation to construct a coating with anticoagulant function.

[0014] Preferably, in S1, the method for modifying the aldehyde group of heparin is as follows: dissolve 10-20 mg / mL of heparin in water, adjust the pH to 1.5-3, add 0.4-0.8 mg / mL of sodium nitrite to cleave the heparin at 1-10℃ for 2-4 h; adjust the pH to 6.0-7.0 with alkali to terminate the reaction; dialyze in NH4HCO3 solution to obtain a heparin solution with aldehyde group, and freeze-dry it for later use.

[0015] The principle behind this modification is to generate heparin oligomers with active aldehyde groups through nitric acid depolymerization. Heparin consists of a disaccharide containing L-iduronic acid and d-glucosamine residues. However, heterogeneity exists throughout the heparin polymer because the disaccharide undergoes various chemical modifications to produce a series of residues. These sites are sensitive to nitrous acid at room temperature and low pH (1.5-3). When heparin is treated with nitrous acid, it is depolymerized by nitrous acid (HNO2), forming heparin aldehydes at the terminal positions of the oligomers.

[0016] Preferably, in S3, the temperature for the oscillation incubation is 20-30°C, and the time is 8-12 hours.

[0017] Preferably, the process further includes step S4: immersing the polyester fiber fabric with a uniformly deposited anticoagulant coating obtained in step S3 into an antibacterial modification solution containing zinc sulfate, performing a secondary oscillation reaction, and obtaining a secondary modified anticoagulant coating after ultrasonic cleaning and drying; wherein the amino group in the aminomalonitrile p-toluenesulfonate is in excess compared to the aldehyde group in the aldehyde heparin.

[0018] To further impart antibacterial function to the anticoagulant coating, antibacterial elements can be introduced into the coating through an impregnation and shaking reaction (the amino group in aminomalononitrile p-toluenesulfonate can chelate with metals through coordination). Furthermore, to ensure that the anticoagulant coating still contains excess active groups that can react with zinc sulfate, the amino group on aminomalononitrile p-toluenesulfonate needs to be controlled in excess relative to the aldehyde group in heparin with an aldehyde group in S2. The preferred molar ratio of amino to aldehyde groups is (30-200):1.

[0019] More preferably, the temperature of the secondary oscillation reaction is 20-30℃, and the time is 12-24h.

[0020] More preferably, the total concentration of zinc sulfate in the antibacterial modified solution is 60-80 μM.

[0021] Preferably, in S3, the cleaning is ultrasonic cleaning: ultrasonic cleaning with deionized water for at least 15 minutes, with an ultrasonic frequency of 20-35kHz and a power of 100-150W. This step is used to remove polymers with weak bonding strength on the material surface.

[0022] Compared with the prior art, the beneficial effects of the present invention are:

[0023] (1) The present invention first modifies heparin by aldehyde to give it the ability to copolymerize with aminomalonium p-toluenesulfonate, then mixes it with aminomalonium p-toluenesulfonate under alkaline conditions and deposits it on the surface of polyester fiber fabric by oscillation reaction to obtain polyester fiber fabric with anticoagulant function, which can greatly expand its application field.

[0024] (2) The present invention further combines zinc ions on the surface of the anticoagulant coating, which can further endow the anticoagulant coating with antibacterial and anti-infection capabilities, increase the secretion of vascular endothelial growth factor, and promote angiogenesis. Attached Figure Description

[0025] Figure 1 Scanning electron microscope image of polyester fiber fabric;

[0026] Figure 2 Here is a scanning electron microscope image of a polyaminomalonium coating deposited on a polyester fiber fabric in Example 1;

[0027] Figure 3 Here is a scanning electron microscope image of the anticoagulant coating on the polyester fiber fabric in Example 2;

[0028] Figure 4 This is a test diagram of the anticoagulant properties of polyester fiber fabrics.

[0029] Figure 5 Photograph of the antibacterial ring on a polyester fiber fabric; Detailed Implementation

[0030] The present invention will be further described below with reference to embodiments.

[0031] It should be noted that the following detailed descriptions are exemplary and intended to provide further illustration of the invention. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0032] The following examples illustrate specific embodiments of the present invention. However, the embodiments of the present invention are not limited to these examples, and any selections and modifications can be made within the scope of the technical effects to be achieved by the present invention. Unless otherwise specified in the examples and test cases, conventional conditions or conditions recommended by the manufacturer are followed. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0033] Example 1

[0034] A method for preparing a polyaminomalonium coating on a polyester fiber fabric, comprising the following steps:

[0035] Step 1: Prepare buffer solution: Prepare a 0.1M tris(hydroxymethyl)aminomethane buffer solution with pH=8.5.

[0036] Step 2: Pretreatment of polyester fiber fabric: The prepared polyester fiber fabric (PET, 20D / 12F) was sequentially treated with acetone, anhydrous ethanol, and ultrasonically for 30 minutes each time; then ultrasonically cleaned with deionized water for 20 minutes each time; the ultrasonic frequency was 35kHz and the power was 150W; during the treatment, the temperature of the mixture was maintained at 25℃ using an ice-water bath. Finally, the polyester fiber fabric was dried at 65℃ for 4 hours under normal pressure and ventilation conditions.

[0037] Step 3: Preparation of polyaminomalonium coating: Add 1g of aminomalonium p-toluenesulfonate to Tris buffer solution (50ml, pH=8.5) to prepare an AMN solution with a concentration of 20mg / mL; after complete dissolution, adjust the pH of the aminomalonium solution to 8.5 using 2M sodium hydroxide; immerse the cleaned polyester fiber fabric in the aminomalonium solution, place it in a water bath constant temperature shaker for 10h for deposition, after deposition, remove it and ultrasonically clean it with deionized water for 50min (ultrasonic frequency 35kHz, power 150W), and dry it for later use.

[0038] Figure 2 Scanning electron microscope image of a polyaminomalonium coating deposited on a polyester fiber fabric.

[0039] Example 2

[0040] Step 1: Prepare buffer solution: Prepare a 0.1M tris(hydroxymethyl)aminomethane buffer solution with pH=8.5.

[0041] Step 2: Pretreatment of polyester fiber fabric: The prepared polyester fiber fabric (PET, 20D / 12F) was sequentially treated with acetone, anhydrous ethanol, and ultrasonically for 30 minutes each time; then ultrasonically cleaned with deionized water for 20 minutes each time; the ultrasonic frequency was 35kHz and the power was 150W; during the treatment, the temperature of the mixture was maintained at 25℃ using an ice-water bath. Finally, the polyester fiber fabric was dried at 65℃ for 4 hours under normal pressure and ventilation conditions.

[0042] Step 3: Preparation of Aldehydeheparin: Heparin was dissolved in deionized water at a concentration of 15 mg / mL, and glacial acetic acid was added to adjust the pH to 3. Then, 0.6 mg / mL sodium nitrite was added to the solution to cleave the heparin at 5°C for 3 hours. The reaction was then terminated by adjusting the pH to 6.5 with sodium hydroxide. The purified aldehydeheparin (Hep-CHO) solution was obtained by dialyzing in 0.15 mol / L NH4HCO3 solution and freeze-dried for later use.

[0043] Step 4: Preparation of the anticoagulant coating: Add 1g of aminomalononitrile p-toluenesulfonate and 50mg of aldehyde heparin to Tris buffer solution (50mL, pH=8.5). The final concentrations of aminomalononitrile p-toluenesulfonate and aldehyde heparin are 20mg / mL and 1mg / mL, respectively. After mixing thoroughly, adjust the pH to 8.5 using 2M sodium hydroxide. Then, immerse the cleaned polyester fiber fabric in the impregnation solution and react it in a 25℃ water bath constant temperature shaker for 10h. After that, ultrasonically clean it with deionized water for 60min (ultrasonic frequency 35kHz, power 150W), remove it and dry it for later use.

[0044] Example 3

[0045] Step 1: Prepare buffer solution: Prepare a 0.1M tris(hydroxymethyl)aminomethane buffer solution with pH=8.5.

[0046] Step 2: Pretreatment of polyester fiber fabric: The prepared polyester fiber fabric (PET, 20D / 12F) was sequentially treated with acetone, anhydrous ethanol, and ultrasonically for 30 minutes each time; then ultrasonically cleaned with deionized water for 20 minutes each time; the ultrasonic frequency was 35kHz and the power was 150W; during the treatment, the temperature of the mixture was maintained at 25℃ using an ice-water bath. Finally, the polyester fiber fabric was dried at 65℃ for 4 hours under normal pressure and ventilation conditions.

[0047] Step 3: Preparation of Aldehydeheparin: Heparin was dissolved in deionized water at a concentration of 15 mg / mL, and glacial acetic acid was added to adjust the pH to 3. Then, 0.6 mg / mL sodium nitrite was added to the solution to cleave the heparin at 5°C for 3 hours. The reaction was then terminated by adjusting the pH to 6.5 with sodium hydroxide. The purified aldehydeheparin (Hep-CHO) solution was obtained by dialyzing in 0.15 mol / L NH4HCO3 solution and freeze-dried for later use.

[0048] Step 4: Preparation of the anticoagulant coating: Add 1g of aminomalononitrile p-toluenesulfonate and 50mg of aldehyde heparin to Tris buffer solution (50mL, pH=8.5). The final concentrations of aminomalononitrile p-toluenesulfonate and aldehyde heparin are 20mg / mL and 1mg / mL, respectively. After mixing thoroughly, adjust the pH to 8.5 using 2M sodium hydroxide. Then, immerse the cleaned polyester fiber fabric in the impregnation solution and react it in a 25℃ water bath constant temperature shaker for 10h. After that, ultrasonically clean it with deionized water for 60min (ultrasonic frequency 35kHz, power 150W), remove it and dry it for later use.

[0049] Step 5: Preparation of antibacterial and anticoagulant coating: First, prepare a 70 μM zinc sulfate solution under dark conditions. Then, immerse the polyester fiber fabric with the anticoagulant coating in the zinc sulfate solution and incubate for 24 hours. After obtaining the antibacterial and anticoagulant coating, ultrasonically clean and dry it with deionized water for later use.

[0050] Example 4

[0051] Step 1: Prepare buffer solution: Prepare a 0.1M tris(hydroxymethyl)aminomethane buffer solution with pH=8.5.

[0052] Step 2: Pretreatment of polyester fiber fabric: The prepared polyester fiber fabric (PET, 20D / 12F) was sequentially treated with acetone, anhydrous ethanol, and ultrasonically for 30 minutes each time; then ultrasonically cleaned with deionized water for 20 minutes each time; the ultrasonic frequency was 35kHz and the power was 150W; during the treatment, the temperature of the mixture was maintained at 25℃ using an ice-water bath. Finally, the polyester fiber fabric was dried at 65℃ for 4 hours under normal pressure and ventilation conditions.

[0053] Step 3: Preparation of Aldehydeheparin: Heparin was dissolved in deionized water at a concentration of 15 mg / mL, and glacial acetic acid was added to adjust the pH to 3. Then, 0.6 mg / mL sodium nitrite was added to the solution to cleave the heparin at 5°C for 3 hours. The reaction was then terminated by adjusting the pH to 6.5 with sodium hydroxide. The purified aldehydeheparin (Hep-CHO) solution was obtained by dialyzing in 0.15 mol / L NH4HCO3 solution and freeze-dried for later use.

[0054] Step 4: Preparation of the anticoagulant coating: Add 1g of aminomalononitrile p-toluenesulfonate and 100mg of aldehyde heparin to Tris buffer solution (50mL, pH=8.5). The final concentrations of aminomalononitrile p-toluenesulfonate and aldehyde heparin are 20mg / mL and 2mg / mL, respectively. After mixing thoroughly, adjust the pH to 8.5 using 2M sodium hydroxide. Then, immerse the cleaned polyester fiber fabric in the impregnation solution and react it in a 25℃ water bath constant temperature shaker for 10h. After that, ultrasonically clean it with deionized water for 60min (ultrasonic frequency 35kHz, power 150W), remove it and dry it for later use.

[0055] Step 5: Preparation of antibacterial and anticoagulant coating: First, prepare a 70 μM zinc sulfate solution under dark conditions. Then, immerse the polyester fiber fabric with the anticoagulant coating in the zinc sulfate solution and incubate for 24 hours. After obtaining the antibacterial and anticoagulant coating, ultrasonically clean and dry it with deionized water for later use.

[0056] Example 5

[0057] Step 1: Prepare buffer solution: Prepare a 0.1M tris(hydroxymethyl)aminomethane buffer solution with pH=8.5.

[0058] Step 2: Pretreatment of polyester fiber fabric: The prepared polyester fiber fabric (PET, 20D / 12F) was sequentially treated with acetone, anhydrous ethanol, and ultrasonically for 30 minutes each time; then ultrasonically cleaned with deionized water for 20 minutes each time; the ultrasonic frequency was 35kHz and the power was 150W; during the treatment, the temperature of the mixture was maintained at 25℃ using an ice-water bath. Finally, the polyester fiber fabric was dried at 65℃ for 4 hours under normal pressure and ventilation conditions.

[0059] Step 3: Preparation of Aldehydeheparin: Heparin was dissolved in deionized water at a concentration of 15 mg / mL, and glacial acetic acid was added to adjust the pH to 3. Then, 0.6 mg / mL sodium nitrite was added to the solution to cleave the heparin at 5°C for 3 hours. The reaction was then terminated by adjusting the pH to 6.5 with sodium hydroxide. The purified aldehydeheparin (Hep-CHO) solution was obtained by dialyzing in 0.15 mol / L NH4HCO3 solution and freeze-dried for later use.

[0060] Step 4: Preparation of the anticoagulant coating: Add 2g of aminomalononitrile p-toluenesulfonate and 100mg of aldehyde heparin to Tris buffer solution (50mL, pH=8.5). The final concentrations of aminomalononitrile p-toluenesulfonate and aldehyde heparin are 40mg / mL and 2mg / mL, respectively. After mixing thoroughly, adjust the pH to 8.5 using 2M sodium hydroxide. Then, immerse the cleaned polyester fiber fabric in the impregnation solution and react it in a 25℃ water bath constant temperature shaker for 10h. After that, ultrasonically clean it with deionized water for 60min (ultrasonic frequency 35kHz, power 150W), remove it and dry it for later use.

[0061] Step 5: Preparation of antibacterial and anticoagulant coating: First, prepare a 70 μM zinc sulfate solution under dark conditions. Then, immerse the polyester fiber fabric with the anticoagulant coating in the zinc sulfate solution and incubate for 24 hours. After obtaining the antibacterial and anticoagulant coating, ultrasonically clean and dry it with deionized water for later use.

[0062] Example 6

[0063] Step 1: Prepare buffer solution: Prepare a 0.1M tris(hydroxymethyl)aminomethane buffer solution with pH=8.5.

[0064] Step 2: Pretreatment of polyester fiber fabric: The prepared polyester fiber fabric (PET, 20D / 12F) was sequentially treated with acetone, anhydrous ethanol, and ultrasonically for 30 minutes each time; then ultrasonically cleaned with deionized water for 20 minutes each time; the ultrasonic frequency was 35kHz and the power was 150W; during the treatment, the temperature of the mixture was maintained at 25℃ using an ice-water bath. Finally, the polyester fiber fabric was dried at 65℃ for 4 hours under normal pressure and ventilation conditions.

[0065] Step 3: Preparation of Aldehydeheparin: Heparin was dissolved in deionized water at a concentration of 15 mg / mL, and glacial acetic acid was added to adjust the pH to 3. Then, 0.6 mg / mL sodium nitrite was added to the solution to cleave the heparin at 5°C for 3 hours. The reaction was then terminated by adjusting the pH to 6.5 with sodium hydroxide. The purified aldehydeheparin (Hep-CHO) solution was obtained by dialyzing in 0.15 mol / L NH4HCO3 solution and freeze-dried for later use.

[0066] Step 4: Preparation of the anticoagulant coating: Add 2.5g of aminomalononitrile p-toluenesulfonate and 100mg of aldehyde heparin to Tris buffer solution (50mL, pH=8.5). The final concentrations of aminomalononitrile p-toluenesulfonate and aldehyde heparin are 50mg / mL and 2mg / mL, respectively. After mixing thoroughly, adjust the pH to 8.5 using 2M sodium hydroxide. Then, immerse the cleaned polyester fiber fabric in the impregnation solution and react it in a 25℃ water bath constant temperature shaker for 10h. After that, ultrasonically clean it with deionized water for 60min (ultrasonic frequency 35kHz, power 150W), remove it and dry it for later use.

[0067] Step 5: Preparation of antibacterial and anticoagulant coating: First, prepare an 80 μM zinc sulfate solution under dark conditions. Then, immerse the polyester fiber fabric with the anticoagulant coating in the zinc sulfate solution and incubate for 24 hours. After obtaining the antibacterial and anticoagulant coating, ultrasonically clean and dry it with deionized water for later use.

[0068] Example 7

[0069] Step 1: Prepare buffer solution: Prepare a 0.1M tris(hydroxymethyl)aminomethane buffer solution with pH=8.5.

[0070] Step 2: Pretreatment of polyester fiber fabric: The prepared polyester fiber fabric (PET, 20D / 12F) was sequentially treated with acetone, anhydrous ethanol, and ultrasonically for 30 minutes each time; then ultrasonically cleaned with deionized water for 20 minutes each time; the ultrasonic frequency was 35kHz and the power was 150W; during the treatment, the temperature of the mixture was maintained at 25℃ using an ice-water bath. Finally, the polyester fiber fabric was dried at 65℃ for 4 hours under normal pressure and ventilation conditions.

[0071] Step 3: Preparation of Aldehydeheparin: Heparin was dissolved in deionized water at a concentration of 15 mg / mL, and glacial acetic acid was added to adjust the pH to 3. Then, 0.6 mg / mL sodium nitrite was added to the solution to cleave the heparin at 5°C for 3 hours. The reaction was then terminated by adjusting the pH to 6.5 with sodium hydroxide. The purified aldehydeheparin (Hep-CHO) solution was obtained by dialyzing in 0.15 mol / L NH4HCO3 solution and freeze-dried for later use.

[0072] Step 4: Preparation of the anticoagulant coating: Add 1g of aminomalononitrile p-toluenesulfonate and 50mg of aldehyde heparin to Tris buffer solution (50mL, pH=8.5). The final concentrations of aminomalononitrile p-toluenesulfonate and aldehyde heparin are 20mg / mL and 1mg / mL, respectively. After mixing thoroughly, adjust the pH to 8.5 using 2M sodium hydroxide. Then, immerse the cleaned polyester fiber fabric in the impregnation solution and react it in a 25℃ water bath constant temperature shaker for 10h. After that, ultrasonically clean it with deionized water for 60min (ultrasonic frequency 35kHz, power 150W), remove it and dry it for later use.

[0073] Step 5: Preparation of antibacterial and anticoagulant coating: First, prepare an 80 μM zinc sulfate solution under dark conditions. Then, immerse the polyester fiber fabric with the anticoagulant coating in the zinc sulfate solution and incubate for 24 hours. After obtaining the antibacterial and anticoagulant coating, ultrasonically clean and dry it with deionized water for later use.

[0074] Performance testing

[0075] (1) Morphological observation: Figure 1 , 2 Images 3 and 4 are scanning electron microscope (SEM) images of polyester fiber fabric, polyester fiber fabric in Example 1 after deposition of a polyaminomalonium coating, and polyester fiber fabric in Example 2 after deposition of an anticoagulant coating, respectively.

[0076] (2) Hemolysis rate test: Take 8 mL of fresh human whole blood containing 10.9 mM sodium citrate solution and dilute it with 10 mL of physiological saline. Immerse PET-AMN (Example 1), PET-AMN-Hep (Example 2), and PET-AMN-Hep-Zn (Example 3) specimens (10 mm × 10 mm) in 0.5 mL of diluted blood and incubate at 37 °C for 1 h. Remove the specimens, add 9 mL of physiological saline, centrifuge the diluted blood at 3000 rpm for 5 min, and measure the absorbance of the supernatant at 545 nm using a UV spectrophotometer, and record it as M1. Add 9 mL of deionized water to 0.5 mL of diluted blood, centrifuge the composite solution at 3000 rpm for 5 min, and use the supernatant as a positive reference to measure the absorbance at 545 nm, and record it as M2. Then, 9 mL of physiological saline was added to 0.5 mL of diluted blood. The composite solution was centrifuged at 3000 rpm for 5 min. Using the supernatant as a negative reference, the absorbance was measured at 545 nm and recorded as X3. The hemolysis rate can be calculated as follows:

[0077]

[0078] (3) APTT test: Fresh human whole blood was centrifuged at 3000 rpm for 10 min with 10.9 mM sodium citrate solution to obtain platelet-free plasma (PPP). PET-AMN (Example 1), PET-AMN-Hep (Example 2), and PET-AMN-Hep-Zn (Example 3) samples (10 mm × 10 mm) were incubated with 500 μL of PPP at 37 °C for 1 h. Then, the APTT of PPP was measured using an APTT kit after sample collection.

[0079] Figure 4 The graphs show the hemolysis rate and APTT test results of the polyester fiber fabrics obtained in Examples 1, 2, and 3; Figure 4 As shown in (a), all heparin-containing coatings can reduce the hemolysis rate to below 0.5%. According to ISO 10993-4, if the hemolysis index is <2%, the material is classified as non-hemolytic. Therefore, all heparin-containing coatings are non-hemolytic. The APTT value was measured to evaluate the anticoagulant effect of PET surfaces with different coatings, such as... Figure 4 As shown in (b), the composite coating containing heparin can prolong the APTT value by more than 15s.

[0080] (4) Antibacterial zone test: Polyester fiber fabrics (PET), PET-AMN-Hep (Example 2), and PET-AMN-Hep-Zn (Example 3) were cut and prepared for use. The polyester fiber fabrics were respectively attached to the antibacterial zone coated with Escherichia coli (E. coli) (10). 7 CFU / mL) and coated with Staphylococcus aureus (S. aureus) (107 In a petri dish containing (CFU / mL) three replicates per group, the samples were incubated at 37°C and 95% humidity for 24 hours. After the experiment, the samples were removed, and the diameter of the inhibition zone was measured using calipers and photographed. Figure 5 As shown, the PET-AMN-Hep-Zn (Example 3) coating material prepared by the present invention has excellent antibacterial effect.

[0081] Unless otherwise specified, the raw materials and equipment used in this invention are all commonly used in the field; unless otherwise specified, the methods used in this invention are all conventional methods in the field.

[0082] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any simple modifications, alterations, and equivalent transformations made to the above embodiments based on the technical essence of the present invention shall still fall within the protection scope of the present invention.

Claims

1. A method for preparing an anticoagulant coating on the surface of a polyester fiber fabric, characterized in that... Includes the following steps: S1: Modify heparin to introduce aldehyde groups to obtain heparin with aldehyde groups; S2: Dissolve aminomalonitrile p-toluenesulfonate and heparin with aldehyde group together in tris(hydroxymethyl)aminomethane hydrochloride buffer solution with pH=8.0-8.8, and adjust the pH of the system to 8-9 with alkali to obtain anticoagulant coating solution. The concentration of aminomalonitrile p-toluenesulfonate in the anticoagulant coating solution is 10-50 mg / mL, and the concentration of heparin with an aldehyde group is 0.5-2 mg / mL. S3: Immerse the polyester fiber fabric in the anticoagulant coating solution, shake and incubate, then remove it, wash away any residual unpolymerized precipitate or its derivatives on the surface of the polyester fiber fabric, and dry it to obtain a polyester fiber fabric with a uniformly deposited anticoagulant coating on the surface. S4: The polyester fiber fabric with a uniformly deposited anticoagulant coating obtained in S3 is immersed in an antibacterial modification solution containing zinc sulfate, and subjected to a secondary oscillation reaction. After ultrasonic cleaning and drying, a secondary modified anticoagulant coating is obtained; the number of amino groups in the aminomalonitrile p-toluenesulfonate is excessive compared to the number of aldehyde groups in the aldehyde-containing heparin.

2. The preparation method according to claim 1, characterized in that: In S1, the method for modifying the aldehyde group of heparin is as follows: dissolve 10-20 mg / mL of heparin in water, adjust the pH to 1.5-3, add 0.4-0.8 mg / mL of sodium nitrite to cleave the heparin at 1-10 °C for 2-4 h; adjust the pH to 6.0-7.0 with alkali to terminate the reaction; dialyze in NH4HCO3 solution to obtain a heparin solution with aldehyde group, freeze-dry it for later use.

3. The preparation method according to claim 1, characterized in that: In S3, the temperature for the oscillation incubation is 20-30℃, and the time is 8-12 h.

4. The preparation method according to claim 1, characterized in that: The temperature of the secondary oscillation reaction is 20-30℃, and the time is 12-24 h.

5. The preparation method according to claim 1, characterized in that: The total concentration of zinc sulfate in the antibacterial modified solution is 60-80 μM.

6. The preparation method according to claim 5, characterized in that: In S3, the cleaning is ultrasonic cleaning: using deionized water for ultrasonic cleaning for at least 15 minutes, with an ultrasonic frequency of 20-35kHz and a power of 100-150W.

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