Photocuring hydrogel anticoagulant coating and preparation method thereof

Abstract

The invention discloses a photocuring hydrogel anticoagulant coating and a preparation method thereof, and belongs to the technical field of biomedicine. The preparation method comprises the following steps: firstly, preparing methacrylated polyvinyl alcohol, methacrylated heparin, a photoinitiator and water into a uniform coating dipping solution, dipping a substrate with a clean surface into the coating dipping solution for 5-100 minutes, taking out the substrate, airing, repeatedly dipping for 2-10 times, and curing the obtained substrate under ultraviolet excitation light to obtain the coating. The preparation process of the photocuring hydrogel anticoagulant coating is simple and easy to operate, the reaction condition is mild, and the prepared photocuring hydrogel anticoagulant coating has very good biocompatibility, can be firmly combined with a substrate material, has very excellent anticoagulant performance and has very good application prospects.

Description

Technical Field

[0001] The present invention belongs to the field of biomedical technology, and in particular relates to a photocurable hydrogel anti-coagulation coating and a preparation method thereof. Background Art

[0002] With the recent development of cardiovascular interventional devices, improving the blood compatibility of their surfaces and preventing thrombosis have become key issues in promoting their clinical application. Heparin is a commonly used anticoagulant. In recent years, existing technologies have primarily focused on covalently bonding heparin to the inner wall of vascular interventional devices to prevent clotting. However, covalent bonding often requires additional plasma equipment or complex synthesis steps, resulting in high production costs and poor biocompatibility.

[0003] Hydrogels have a large number of hydrophilic groups and a unique three-dimensional network structure, which can absorb and retain large amounts of water, similar to the extracellular matrix. After absorbing water, the friction and mechanical effects on the surrounding tissues are reduced, and the biological properties of the material are also significantly improved. At the same time, some hydrogel materials have good biocompatibility and anti-fouling properties. These properties make hydrogels have the potential to become anti-coagulation coatings. Methacryloylated polyvinyl alcohol is a photocurable hydrogel material with good biocompatibility. It can quickly form a hydrophilic coating with methacrylated heparin through photoinitiation. The preparation process is simple and the reaction conditions are mild. However, to date, there have been no reports on the preparation of photocurable hydrogel anti-coagulation coatings using methacrylated polyvinyl alcohol and methacrylated heparin. Summary of the Invention

[0004] In view of this, an object of the present invention is to provide a photocurable hydrogel anticoagulant coating and a preparation method thereof.

[0005] The object of the present invention is to achieve the following goals:

[0006] In a first aspect, the present invention provides a method for preparing a photocurable hydrogel anti-coagulation coating, comprising the following steps:

[0007] (1) preparing a uniform coating impregnation solution by methacryloylating polyvinyl alcohol, methacryloylating heparin, a photoinitiator and water, and storing the solution in the dark;

[0008] (2) immersing the substrate with a cleaned surface into the coating impregnation solution obtained in step (1) for 5 to 100 minutes, removing the substrate, drying it, and repeating the immersion process 2 to 10 times;

[0009] (3) The substrate of step (2) is placed under an excitation light for curing.

[0010] Based on the above technical solution, further, the concentration of methacrylated polyvinyl alcohol in the coating impregnation solution in step (1) is 1 to 10 wt%, preferably 3 to 8 wt%.

[0011] Based on the above technical solution, further, the concentration of methacryloyl heparin in the coating impregnation solution in step (1) is 0.5-10 wt%, preferably 1-5 wt%.

[0012] Based on the above technical solution, further, the photoinitiator in step (1) includes Irgacure 2959 and LAP, with a concentration of 0.1 to 2 wt%, preferably 0.2 to 1 wt%.

[0013] Based on the above technical solution, further, the substrate described in step (2) includes a stainless steel substrate and a polyurethane substrate.

[0014] Based on the above technical solution, further, the single immersion time in step (2) is 10 to 60 minutes.

[0015] Based on the above technical solution, further, the excitation light in step (3) is ultraviolet light, and the curing time is 0.1 to 30 minutes.

[0016] In a second aspect, the present invention provides a photocurable hydrogel anticoagulant coating obtained by the above preparation method.

[0017] In a third aspect, the present invention provides the use of the above-mentioned photocurable hydrogel anticoagulant coating in the preparation of artificial blood vessels.

[0018] Compared with the prior art, the present invention has the following beneficial effects:

[0019] The preparation process of the photocurable hydrogel anticoagulant coating of the present invention is simple and easy to operate, and the reaction conditions are mild. The prepared photocurable hydrogel anticoagulant coating has excellent biocompatibility and can be firmly bonded to the substrate material. The number of platelets adhered to the stainless steel coated with the photocurable hydrogel anticoagulant coating is significantly less than that of the stainless steel not coated with the photocurable hydrogel anticoagulant coating, indicating that the photocurable hydrogel anticoagulant coating of the present invention has very excellent anticoagulant properties and has very good application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] In order to more clearly illustrate the embodiments of the present invention, the drawings related to the embodiments are briefly introduced below.

[0021] Figure 1 Figures showing platelet adhesion on the surface of the stainless steel substrate before (A) and after (B) coating in Example 1. DETAILED DESCRIPTION

[0022] The present invention is described in detail below with reference to the embodiments, but the embodiments of the present invention are not limited thereto. Obviously, the embodiments described below are only some embodiments of the present invention. For those skilled in the art, other similar embodiments obtained without creative work all fall within the scope of protection of the present invention.

[0023] Unless otherwise specified, the experimental methods described in the following examples are conventional methods; the reagents and materials described are all commercially available unless otherwise specified.

[0024] Example 1

[0025] This embodiment provides a method for preparing a photocurable hydrogel anti-coagulation coating, comprising the following steps:

[0026] Methacrylated polyvinyl alcohol (prepared by the esterification reaction of vinyl alcohol and methacrylic anhydride), methacrylated heparin, photoinitiator Irgacure 2959, and deionized water were uniformly mixed to form a uniform coating impregnation solution, which was stored in the dark. The concentration of the methacrylated polyvinyl alcohol was 5%, the concentration of the methacrylated heparin was 1%, and the concentration of the photoinitiator Irgacure 2959 was 0.25%. A polished stainless steel substrate was immersed in the coating impregnation solution, removed after 10 minutes, and air-dried. The above steps were repeated three times. After the final removal, the liquid was drained and then cured by UV irradiation for 1 minute to obtain an anticoagulant coating.

[0027] Platelet adhesion experiments were conducted on stainless steel without and with impregnation coatings, i.e., platelet-rich plasma was dripped onto the sample surface and incubated at 37°C for 10 minutes. Non-adherent platelets were washed away with saline and observed using a scanning electron microscope after the experiment. The results are as follows: Figure 1 As shown, it can be seen that the number of platelets adhered to the stainless steel with the photocured hydrogel anticoagulant coating is significantly less than that of the stainless steel without the photocured hydrogel anticoagulant coating, indicating that the photocured hydrogel anticoagulant coating prepared in this example has a very excellent anticoagulant effect.

[0028] Example 2

[0029] This embodiment provides a method for preparing a photocurable hydrogel anti-coagulation coating, comprising the following steps:

[0030] Methacrylated polyvinyl alcohol, methacrylated heparin, photoinitiator LAP and deionized water are uniformly mixed to form a uniform coating impregnation solution, which is stored in the dark. The concentration of methacrylated polyvinyl alcohol is 5%, the concentration of methacrylated heparin is 5%, and the concentration of photoinitiator LAP is 1%; the polyurethane substrate is immersed in the coating impregnation solution, taken out after 10 minutes and dried; the above steps are repeated 3 times. After the last time of taking out, the liquid is drained and then cured by UV irradiation for 1 minute to obtain an anticoagulant coating.

[0031] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a photocurable hydrogel anticoagulant coating, characterized in that: The following steps are involved: (1) preparing a uniform coating impregnation solution by methacryloylating polyvinyl alcohol, methacryloylating heparin, a photoinitiator and water, and storing the solution in the dark; (2) immersing the substrate with a cleaned surface into the coating impregnation solution obtained in step (1) for 5 to 100 minutes, removing the substrate, drying it, and repeating the immersion process 2 to 10 times; (3) The substrate of step (2) is placed under an excitation light for curing.

2. The preparation method according to claim 1, characterized in that The concentration of methacrylated polyvinyl alcohol in the coating impregnation solution in step (1) is 1 to 10 wt %, preferably 3 to 8 wt %.

3. The preparation method according to claim 1, characterized in that The concentration of methacryloyl heparin in the coating impregnation solution in step (1) is 0.5-10 wt %, preferably 1-5 wt %.

4. The preparation method according to claim 1, characterized in that The photoinitiator in step (1) includes Irgacure 2959 and LAP, with a concentration of 0.1 to 2 wt%, preferably 0.2 to 1 wt%.

5. The preparation method according to claim 1, characterized in that The substrate described in step (2) includes a stainless steel substrate and a polyurethane substrate.

6. The preparation method according to claim 1, characterized in that The single immersion time in step (2) is 10 to 60 minutes.

7. The preparation method according to claim 1, characterized in that The excitation light in step (3) is ultraviolet light, and the curing time is 0.1 to 30 minutes.

8. The photocurable hydrogel anti-coagulation coating obtained by the preparation method according to any one of claims 1 to 7.

9. Use of the photocurable hydrogel anticoagulant coating according to claim 8 in the preparation of artificial blood vessels.

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