A nanofiber capable of rapid UV curing, and its preparation method and application

Abstract

This invention discloses a fast-curing ultraviolet (UV) nanofiber, its preparation method, and application. The nanofiber is prepared by first introducing a high density of amino groups into a carboxylated nanocellulose fiber matrix, and then grafting methacrylic anhydride via a nucleophilic addition-elimination reaction to introduce carbon-carbon double bonds. This fast-curing UV nanofiber exhibits both rapid UV curing and rapid hemostasis, and can be used to rapidly stop bleeding in aortic and cardiac trauma or wounds.

Description

Technical Field

[0001] The present invention belongs to the technical field of biomass fiber modification, and in particular relates to a nanofiber capable of rapid ultraviolet light curing, a preparation method thereof, and an application thereof. Background Art

[0002] UV curing technology uses high-intensity UV light as a radiation source. It irradiates a liquid containing a photoinitiator. The photoinitiator absorbs the UV light quanta, triggering a chemical reaction that instantly converts the liquid into a solid. UV curing technology offers advantages such as low energy consumption, ecological balance, high economic efficiency, excellent product performance, and easy equipment operation. Consequently, it has gained widespread industrial application in many fields. Research and development of photoinitiators / systems for diverse application areas is a future trend. Among them, UV curable materials hold broad application prospects in the field of hemostasis. Uncontrolled bleeding after trauma or during surgery is a major cause of further deterioration in patients' conditions, such as in the repair of aortic ruptures, hemostasis of penetrating cardiac wounds, and wound hemostasis. Currently, surgical suturing is the only clinical solution to these problems. However, this method is limited in time and space. With advances in materials science, a variety of chemical agents have been developed for rapid wound sealing, including fibrin glue, gelatin, collagen, zeolites, peptides, polymers, and hydrogels. However, due to their long hemostasis time, poor adhesion to wet tissue surfaces, and weak bonding mechanics, they are not suitable for hemostasis and closure of aortic and cardiac trauma and wounds. Summary of the Invention

[0003] The purpose of the present invention is to provide a nanofiber that can be quickly cured by ultraviolet light, and its preparation method and application. The material has rapid ultraviolet curing performance and rapid hemostasis performance, and is used for rapid hemostasis of aortic and cardiac trauma or wounds.

[0004] The above-mentioned purpose of the present invention is achieved through the following technical solutions:

[0005] A method for preparing nanofibers capable of rapid UV curing comprises the following steps:

[0006] S1: Preparation of amino group-rich nanocellulose fibers: Using carboxylated nanocellulose fibers as a matrix, small amine compounds rich in amino groups are grafted onto their surfaces through an amidation reaction to prepare amino group-rich nanocellulose fibers;

[0007] S2: Preparation of nanofibers that can be rapidly cured by ultraviolet light: Using the amino group-rich nanocellulose fibers obtained in step S1 as a matrix, methacrylic anhydride is grafted via a nucleophilic addition-elimination reaction to introduce carbon-carbon double bonds to prepare nanofibers that can be rapidly cured by ultraviolet light.

[0008] Preferably, the small molecule amine compound is ethylenediamine, diethylenetriamine, pyrimidine-4,5,6-triamine, triethylenetetramine or tetraethylenepentamine.

[0009] Furthermore, the preparation of the nanocellulose fibers rich in amino groups in step S1 mainly involves the following operations: adding deionized water to the carboxylated nanocellulose fibers, uniformly dispersing them by ultrasound, and then adding 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide in sequence, and then adding a small molecule amine compound. After mixing evenly, stirring at room temperature to react, after the reaction is completed, centrifuging the product, pouring out the supernatant, and repeatedly washing the precipitate with deionized water until the washing liquid is neutral. The resulting product is a nanocellulose fiber rich in amino groups; the mass ratio of the carboxylated nanocellulose fibers to the small molecule amine compound is 1:2~4.

[0010] Furthermore, the preparation of the nanofibers that can be rapidly cured by ultraviolet light in step S2 mainly involves the following steps: uniformly dispersing the amino group-rich nanocellulose fibers obtained in step S1 in deionized water at 45-55°C to obtain a dispersion, controlling the stirring speed at 100-300 rpm, and adding methacrylic anhydride to the dispersion at a drop rate of 6-8 s / drop, and reacting for 2-4 hours; after the reaction, dialyzing the product in a constant temperature water tank at 35-45°C for 2-4 days, and freeze-drying the dialyzed product. The resulting product is a nanofiber that can be rapidly cured by ultraviolet light, and the mass ratio of the amino group-rich nanocellulose fibers to methacrylic anhydride is 1:1.

[0011] The nanofibers that can be rapidly cured by the preparation method of the present invention can be used for rapid hemostasis of aortic or cardiac trauma or wounds, and can be cured and formed by irradiating them with 360 nm ultraviolet light for 8 to 15 seconds.

[0012] The present invention has the following beneficial effects:

[0013] (1) The nanofibers prepared by the present invention can be rapidly cured by ultraviolet light. The material has the characteristics of rapid ultraviolet curing, fast hemostasis time, good adhesion to wet tissue surface, strong bonding mechanics, etc., and is suitable for hemostasis and sealing of aortic and cardiac trauma and wounds. It overcomes the problems of traditional hemostasis methods in time and space limitations, long hemostasis time, and unfriendliness to wet tissues.

[0014] (2) The present invention uses small molecule amines to chemically modify the nanocellulose fibers, giving the nanocellulose fibers a high amino density (greater than 12 mmol / g). The nanocellulose fibers with high amino density can provide sufficient sites to introduce more methacrylic groups. The construction of more methacrylic groups greatly reduces the UV curing time of the UV-cured methacrylylated nanofibers, and the curing time can be reduced to 8~15 s.

[0015] (3) The matrix of the present invention is nanofiber, which has good biocompatibility, giving it an inherent advantage in the fields of bioengineering, tissue engineering, etc. At the same time, the abundant negatively charged carboxyl groups on the nanofiber segments that have not been amidated can promote the rapid hydration and swelling of the material. At the same time, the carboxylic acid groups form temporary crosslinks with the tissue surface through intermolecular bonds, hydrogen bonds and electronic interactions, resulting in instantaneous adhesion, so that the material of the present invention also has excellent wet tissue adhesion, further making it widely used. DETAILED DESCRIPTION

[0016] Example 1

[0017] S1. Preparation of amino group-rich nanocellulose fibers: 100 mL of deionized water was added to 1.0 g of carboxylated nanocellulose fibers and the fibers were evenly dispersed by ultrasonication. 1.0 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 1.0 g of N-hydroxysuccinimide were then added in sequence, followed by 2.0 g of ethylenediamine. After mixing well, the mixture was stirred at room temperature for reaction. After the reaction was completed, the product was centrifuged, the supernatant was poured out, and the precipitate was repeatedly washed with deionized water until the washing solution was neutral. The resulting product was amino group-rich nanocellulose fibers.

[0018] S2. Preparation of rapidly UV-curable nanofibers: 1.0 g of amino-rich nanocellulose fibers was uniformly dispersed in 100 mL of deionized water at 45°C to obtain a dispersion. 1.0 g of methacrylic anhydride was added dropwise to the dispersion at a rate of 6 s / drop with stirring at 100 rpm. The mixture was allowed to react for 2 h. After the reaction, the product was dialyzed in a constant-temperature water tank at 35°C for 2 days. The dialyzed product was freeze-dried to obtain rapidly UV-curable nanofibers.

[0019] The rapidly UV-curable nanofibers prepared in Example 1 were used to stop bleeding in pigs with penetrating heart injuries. After general anesthesia, the left ventricle of the pig's heart was punctured using a needle with an inner diameter of 6 mm. In the experimental group, the defect and surrounding tissue were quickly covered with the nanofibers prepared in Example 1 and irradiated with 360 nm ultraviolet light. The hemostasis time was recorded as 15 seconds.

[0020] Example 2

[0021] S1. Preparation of amino group-rich nanocellulose fibers: 100 mL of deionized water was added to 2.0 g of carboxylated nanocellulose fibers and the fibers were evenly dispersed by sonication. Then, 4.0 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 2.0 g of N-hydroxysuccinimide were added in sequence, followed by 6.0 g of diethylenetriamine. After mixing well, the mixture was stirred at room temperature for reaction. After the reaction was completed, the product was centrifuged, the supernatant was poured out, and the precipitate was repeatedly washed with deionized water until the washing solution was neutral. The resulting product was amino group-rich nanocellulose fibers.

[0022] S2. Preparation of rapidly UV-curable nanofibers: 5.0 g of amino-rich nanocellulose fibers were uniformly dispersed in 500 mL of deionized water at 50°C to obtain a dispersion. 5.0 g of methacrylic anhydride was added dropwise to the dispersion at a rate of 7 s / drop with stirring at 200 rpm. The reaction was allowed to proceed for 3 h. After the reaction, the product was dialyzed in a constant-temperature water tank at 40°C for 3 days. The dialyzed product was freeze-dried to obtain rapidly UV-curable nanofibers.

[0023] The rapidly UV-curable nanofibers prepared in Example 2 were used to stop bleeding in pig carotid arteries. After general anesthesia, the pigs' carotid arteries were punctured using a 4 mm inner diameter needle. In the experimental group, the defect and surrounding tissue were quickly covered with the nanofibers prepared in Example 2 and irradiated with 360 nm UV light. The hemostasis time was recorded as 13 seconds.

[0024] Example 3

[0025] S1. Preparation of amino group-rich nanocellulose fibers: 500 mL of deionized water was added to 5.0 g of carboxylated nanocellulose fibers and the fibers were evenly dispersed by ultrasonication. 5.0 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 5.0 g of N-hydroxysuccinimide were then added in sequence, followed by 20.0 g of triethylenetetramine. After mixing well, the mixture was stirred at room temperature for reaction. After the reaction was completed, the product was centrifuged, the supernatant was poured out, and the precipitate was repeatedly washed with deionized water until the washing solution was neutral. The resulting product was amino group-rich nanocellulose fibers.

[0026] S2. Preparation of rapidly UV-curable nanofibers: 10.0 g of amino-rich nanocellulose fibers was uniformly dispersed in 1000 mL of deionized water at 55°C to obtain a dispersion. 10.0 g of methacrylic anhydride was added dropwise to the dispersion at a rate of 8 s / drop with stirring at 300 rpm. The reaction was allowed to proceed for 4 h. After the reaction, the product was dialyzed in a constant-temperature water tank at 45°C for 4 days. The dialyzed product was freeze-dried to obtain rapidly UV-curable nanofibers.

[0027] The rapidly UV-curable nanofibers prepared in Example 3 were used to stop bleeding in pig skin wounds. After general anesthesia, the pigs were punctured with an 8 mm inner diameter needle. In the experimental group, the defect and surrounding tissue were quickly covered with the nanofibers prepared in Example 3 and irradiated with 360 nm UV light. The hemostasis time was recorded as 8 seconds.

Claims

1. A method for preparing nanofibers that can be rapidly cured by ultraviolet light, characterized in that: The following steps are involved: S1: Preparation of amino group-rich nanocellulose fibers: Carboxylated nanocellulose fibers are used as a matrix, and a small molecule amine compound rich in amino groups is grafted onto the surface of the matrix via an amidation reaction to prepare the amino group-rich nanocellulose fibers; the mass ratio of the carboxylated nanocellulose fibers to the small molecule amine compound is 1:2-4; S2: Preparation of nanofibers that can be rapidly cured by ultraviolet light: Using the nanocellulose fibers rich in amino groups obtained in step S1 as a matrix, methacrylic anhydride is grafted onto the fibers through a nucleophilic addition-elimination reaction to introduce carbon-carbon double bonds, thereby preparing nanofibers that can be rapidly cured by ultraviolet light; the mass ratio of the nanocellulose fibers rich in amino groups to methacrylic anhydride is 1:

1.

2. The preparation method according to claim 1, characterized in that The small molecule amine compound is ethylenediamine, diethylenetriamine, pyrimidine-4,5,6-triamine, triethylenetetramine or tetraethylenepentamine.

3. The preparation method according to claim 1, characterized in that The main operations for preparing the nanocellulose fibers rich in amino groups in step S1 are: adding deionized water to the carboxylated nanocellulose fibers, ultrasonically dispersing them uniformly, then adding 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide in sequence, and then adding a small molecule amine compound. After mixing evenly, stirring at room temperature for reaction. After the reaction is completed, centrifuging the product, pouring out the supernatant, and repeatedly washing the precipitate with deionized water until the washing liquid is neutral. The resulting product is nanocellulose fibers rich in amino groups; the mass ratio of the carboxylated nanocellulose fibers to the small molecule amine compound is 1:2~4.

4. The preparation method according to claim 1, characterized in that The main operation of preparing the nanofibers that can be rapidly cured by ultraviolet light in step S2 is as follows: the nanocellulose fibers rich in amino groups obtained in step S1 are uniformly dispersed in deionized water at 45-55°C to obtain a dispersion, methacrylic anhydride is added dropwise to the dispersion at a dropping rate of 6-8s / drop under a stirring speed controlled at 100-300 rpm, and the reaction is carried out for 2-4 hours; after the reaction is completed, the product is placed in a constant temperature water tank at 35-45°C for 2-4 days, and the dialyzed product is freeze-dried to obtain a product that can be rapidly cured by ultraviolet light, wherein the mass ratio of the nanocellulose fibers rich in amino groups to methacrylic anhydride is 1:

1.

5. Nanofibers capable of rapid UV curing prepared by the preparation method according to any one of claims 1 to 4.

6. Use of the fast UV-curable nanofibers prepared by the preparation method according to any one of claims 1 to 4 in preparing fast hemostatic materials for aortic or cardiac trauma or wounds.