Collagen fiber with antibacterial property and preparation method and application thereof

By loading silver ions into collagen fibers using multiphase channel microfluidic spinning technology, the problems of insufficient mechanical and antibacterial properties of collagen fibers have been solved, enabling the application of high-strength, antibacterial medical sutures.

CN117604670BActive Publication Date: 2025-12-12WUHAN TEXTILE UNIV
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Patent Information

Application Number
CN202311572593.4
Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Filing Date
2023-11-23
Publication Date
2025-12-12
Estimated Expiration
2043-11-23

AI Technical Summary

Technical Problem

Existing collagen fiber molding methods make it difficult to apply stretching force during the molding process, resulting in insufficient mechanical properties. In addition, the surface of collagen fibers is highly hydrophilic, and they swell and lose strength when exposed to water, which cannot meet the requirements for use in medical sutures. Furthermore, traditional sutures suffer significant loss of antibacterial properties during sterilization, posing a risk of infection.

Method used

The multiphase channel microfluidic spinning technology is adopted. The spinning solution is injected through the inner channel, the silver nitrate solution is injected into the first outer channel, and the ethanol is injected into the second outer channel. The tannic acid forms hydrogen bonds with collagen to load silver ions, which enhances the mechanical properties of the fiber and endows it with antibacterial properties.

Benefits of technology

It improves the breaking strength and antibacterial properties of collagen fibers, meets the standards for medical surgical sutures, reduces the risk of infection, and has better biodegradability.

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Abstract

The present application relates to the technical field of medical instrument preparation, and particularly relates to collagen fibers with antibacterial properties and a preparation method and application thereof. The present application provides a preparation method of collagen fibers with antibacterial properties, comprising the following steps: (1) mixing a tannic acid solution with a collagen stock solution, swelling and dissolving to obtain a spinning stock solution; (2) extruding the spinning stock solution to obtain nascent fibers, and after the nascent fibers are coagulated, collagen fibers with antibacterial properties are obtained. A certain amount of tannic acid is added to the collagen, and the silver ions are loaded on the surface of the collagen fibers through the multiphase channel microfluidic spinning technology, so that the collagen fibers with improved mechanical properties are obtained, and the collagen fibers are endowed with antibacterial properties, and the obtained fibers meet the relevant standards of medical surgical sutures.
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Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of medical device preparation, in particular to a collagen fiber with antibacterial performance and a preparation method and application thereof. BACKGROUND

[0002] Modern medical sutures are medical textile materials prepared by fiber monofilament and multifilament, and are essential medical devices in surgery, which have important functions such as suturing of larger wounds and promoting tissue closure. With the continuous progress of design and production technology, the suturing line material has experienced four generations of development: the first generation is silk thread, the second generation is catgut, the third generation is artificial chemical synthetic absorbable suture (PGA, PGLA, PLA), and the fourth generation is absorbable collagen suture.

[0003] At present, the collagen definition universally accepted by the international community is "collagen is a structural protein of extracellular matrix, containing one or more triple helix domains", and the basic building unit is collagen molecule, which is about 300 nm long and 1.5 nm in diameter. Collagen can spontaneously assemble into ordered collagen fibers and fiber bundles in vivo, and then form a macroscopic network structure, providing a structural framework and mechanical support for numerous biological tissues.

[0004] The common manufacturing methods of collagen-based fiber materials mainly include wet spinning, dry-wet spinning and electrospinning. However, the traditional collagen fiber forming method is difficult to apply a certain stretching force to the initial fiber during the forming process to obtain a certain orientation, so that the mechanical properties of the regenerated collagen fiber cannot meet the use requirements. In addition, the surface of collagen molecule has a large number of hydrophilic groups, which leads to swelling of the regenerated collagen fiber when it comes into contact with water, and almost no strength in wet state, so it cannot meet the use requirements of medical sutures.

[0005] Infection related to medical devices is a major public health challenge that can have serious consequences for patients. Inflammation is the most likely biological response in vivo after the implantation of biomaterials, and changes or adjustments in the conformation, size, number, surface molecules and chemical properties of the material will have different effects on the intensity of the inflammatory response. During the use of medical sutures, the line body may come into contact with microorganisms in the environment, forming a bacterial biofilm, which can cause surgical site infection, trigger inflammatory and foreign body reactions. Long-term inflammation can cause tissue damage, forming a thick fibrous capsule around the suture, separating the material from the tissue and failing to function, and there is a risk of inducing wound infection, which will eventually lead to suture failure, which will also become an obstacle to tissue repair and regeneration.

[0006] At present, the antibacterial functionalization of medical sutures is considered as an effective alternative. In recent years, the development of antibacterial sutures with the functions of reducing inflammatory response and rapid tissue absorption has made significant progress. However, no matter absorbable or non-absorbable sutures, the tensile strength thereof is widely lost during the disinfection and sterilization process. The research and development of new multifunctional and high-performance medical sutures with the abilities of antibacterial, drug-loaded sustained release and anti-inflammatory is an urgent bottleneck to be broken through in the field of medical devices.

[0007] In summary, it is necessary to develop a new collagen fiber forming method to improve the mechanical properties of collagen fibers and endow them with antibacterial properties. SUMMARY

[0008] The purpose of the present application is to provide a collagen fiber with antibacterial properties and a preparation method and application thereof.

[0009] In order to achieve the above-mentioned purpose of the application, the present application provides the following technical solutions:

[0010] The present application provides a preparation method of a collagen fiber with antibacterial properties, comprising the following steps:

[0011] (1) mixing a tannic acid solution with a collagen stock solution, swelling and dissolving to obtain a spinning stock solution;

[0012] (2) extruding the spinning stock solution to form a primary fiber, and after the primary fiber is coagulated, a collagen fiber with antibacterial properties is obtained;

[0013] The extrusion forming is provided with an inward channel, a first outer phase channel and a second outer phase channel; the inward channel is injected with the spinning stock solution; the first outer phase channel is injected with a silver nitrate solution; and the second outer phase channel is injected with ethanol.

[0014] Preferably, in step (1), the concentration of tannic acid in the tannic acid solution is 0.1-0.7 mg / mL; the tannic acid solution uses an acetic acid solution as a solvent; and the concentration of the acetic acid solution is 0.3-0.7 mol / L.

[0015] Preferably, in step (1), the concentration of collagen in the collagen stock solution is 6-10 mg / mL; and the collagen is type I collagen.

[0016] Preferably, in step (1), the swelling temperature is 4-6℃, and the time is 15-25 min; the dissolving speed is 150-250 rpm, the time is 6-8 h, and the temperature is 4-6℃.

[0017] Preferably, in step (1), after the dissolving, centrifugal defoaming is further performed, the centrifugal defoaming speed is 8000-10000 rpm, the time is 30-50 min, and the temperature is 4-6℃.

[0018] Preferably, the extrusion speed of the inner channel in step (2) is 0.3-0.7 mL / min; the extrusion speed of the first outer phase channel is 0.05-0.20 mL / min; and the extrusion speed of the second outer phase channel is 0.05-0.25 mL / min.

[0019] Preferably, the concentration of the silver nitrate solution in step (2) is 0.5-2.5 mg / mL; and the ethanol is anhydrous ethanol.

[0020] Preferably, the coagulation in step (2) is carried out in a coagulation bath, the coagulation bath comprising acetone and ammonia water; the volume ratio of the acetone and ammonia water is 15-25:1; the temperature of the coagulation bath is set to 20-30℃; and the nascent fiber stays in the coagulation bath for 2-4 min.

[0021] The application further provides the collagen fiber with antibacterial performance prepared by the preparation method.

[0022] The application further provides application of the collagen fiber with antibacterial performance in preparation of medical suture.

[0023] Compared with the prior art, the application has the following beneficial effects:

[0024] The application realizes loading of silver ions on the surface of the collagen fiber through the multiphase channel microfluidic spinning technology by adding a certain amount of tannic acid in the collagen, so that the collagen fiber with improved mechanical properties is obtained, and the collagen fiber is endowed with antibacterial performance, and the obtained fiber meets the relevant standards of medical surgical suture.

[0025] On one hand, the tannic acid can produce hydrogen bond action with the collagen protein, so as to enhance the mechanical properties of the collagen fiber. On the other hand, the tannic acid has strong reducing property, and can load the silver ions on the collagen fiber. In addition, the tannic acid also has certain antibacterial effect.

[0026] The spinning dope of the application does not need to add synthetic polymers, so the biodegradability is better. In addition, by controlling the process parameters, the method of the application can further improve the breaking strength of the collagen fiber. BRIEF DESCRIPTION OF DRAWINGS

[0027] In order to more clearly illustrate the technical solutions in the embodiments of the application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or prior art description. Obviously, the drawings in the following description only the embodiments of the application, and for those skilled in the art, without creative labor, can also obtain other drawings according to the provided drawings.

[0028] Figure 1 Structure diagram of multi-phase channel microfluidic spinning device;

[0029] It comprises injection pump 1, injection pump 2, injection pump 3, microfluidic chip and spinneret 4; the microfluidic chip comprises inner phase channel (connected with injection pump 1), first outer phase channel (connected with injection pump 2) and second outer phase channel (connected with injection pump 3), and a coagulation bath is arranged below the spinneret 4.

[0030] Figure 2 Structure diagram of inner phase channel, first outer phase channel and second outer phase channel in microfluidic chip. DETAILED DESCRIPTION

[0031] The application provides a preparation method of collagen fibers with antibacterial performance.

[0032] (1) mixing a tannic acid solution with a collagen stock solution, swelling and dissolving to obtain a spinning stock solution;

[0033] (2) extruding the spinning stock solution to obtain nascent fibers, and coagulating the nascent fibers to obtain collagen fibers with antibacterial performance;

[0034] During the extrusion molding, three channels are needed, including an inward channel, a first outer phase channel and a second outer phase channel; the inward channel is used to inject the spinning stock solution; the first outer phase channel is used to inject a silver nitrate solution; and the second outer phase channel is used to inject ethanol.

[0035] In the application, step (2) is an extrusion molding process using a multi-phase channel microfluidic spinning device.

[0036] In the application, the concentration of tannic acid in the tannic acid solution in step (1) is 0.1-0.7 mg / mL; preferably 0.2-0.6 mg / mL; further preferably 0.3-0.5 mg / mL; and more preferably 0.4 mg / mL.

[0037] In the application, the tannic acid solution in step (1) uses an acetic acid solution as a solvent.

[0038] In the application, the concentration of the acetic acid solution is 0.3-0.7 mol / L; preferably 0.4-0.6 mol / L; and further preferably 0.5 mol / L.

[0039] In the application, the concentration of collagen in the collagen stock solution in step (1) is 6-10 mg / mL; preferably 7-9 mg / mL; and further preferably 8 mg / mL.

[0040] In the application, the collagen is type I collagen.

[0041] In the present application, the collagen is derived from bovine Achilles tendon, pigskin or cowhide; preferably pigskin.

[0042] In the present application, the collagen is purchased from Tianjin Saineng Biological Engineering Technology Co., Ltd.

[0043] In the present application, the swelling temperature in step (1) is 4-6℃; preferably 5℃.

[0044] In the present application, the swelling time in step (1) is 15-25min; preferably 17-23min; further preferably 19-21min; more preferably 20min.

[0045] In the present application, the stirring and dissolving speed in step (1) is 150-250rpm; preferably 170-230rpm; further preferably 190-210rpm; more preferably 200rpm.

[0046] In the present application, the stirring and dissolving time in step (1) is 6-8h; preferably 7h.

[0047] In the present application, the stirring and dissolving temperature in step (1) is 4-6℃; preferably 5℃.

[0048] In the present application, the centrifugal defoaming speed in step (1) is 8000-10000rpm; preferably 8200-9800rpm; further preferably 8400-9600rpm; more preferably 8500rpm.

[0049] In the present application, the centrifugal defoaming time after dissolving in step (1) is 30-50min; preferably 34-46min; further preferably 38-42min; more preferably 40min.

[0050] In the present application, the centrifugal defoaming temperature in step (1) is 4-6℃; preferably 5℃.

[0051] In the present application, the extrusion speed of the inward channel in step (2) is 0.3-0.7mL / min; preferably 0.4-0.6mL / min; further preferably 0.5mL / min.

[0052] In the present application, the extrusion speed of the first outward phase channel in step (2) is 0.05-0.20mL / min; preferably 0.10-0.15mL / min; further preferably 0.13mL / min.

[0053] In the present application, the extrusion speed of the second outer phase channel in step (2) is 0.05-0.25 mL / min; preferably 0.10-0.20 mL / min; further preferably 0.15 mL / min.

[0054] In the present application, the concentration of the silver nitrate solution in step (2) is 0.5-2.5 mg / mL; preferably 1.0-1.5 mg / mL; further preferably 1.3 mg / mL.

[0055] In the present application, the ethanol in step (2) is anhydrous ethanol.

[0056] In the present application, the coagulation in step (2) is carried out in a coagulation bath, and the coagulation includes acetone and ammonia water.

[0057] In the present application, the volume ratio of the acetone and ammonia water is 15-25:1; preferably 17-23:1; further preferably 19-21:1; more preferably 20:1.

[0058] In the present application, the temperature of the coagulation bath is set to 20-30℃; preferably 22-28℃; further preferably 24-26℃; more preferably 25℃.

[0059] In the present application, the time for the nascent fiber to stay in the coagulation bath is 2-4 min; preferably 3 min.

[0060] The present application also provides the collagen fiber with antibacterial performance prepared by the preparation method.

[0061] The present application also provides the use of the collagen fiber with antibacterial performance in the preparation of medical suture.

[0062] The distance from the surface of the coagulation bath to the bottom of the coagulation bath of the microfluidic spinning device used in the present application is 50 mm.

[0063] The operation principle of the microfluidic spinning device used in the present application is as follows: the inner phase channel is connected to the spinning dope, the extrusion of the fluid through the first and second outer phase channels (referred to as fluid dynamic focusing effect) forms a spinning fine stream, and then the collagen fiber is obtained after passing through the coagulation bath. The principle is the same as that of the microfluidic wet spinning machine produced by Nanjing Jetnas New Material Co., Ltd.

[0064] The technical solutions provided by the present application will be described in detail below in combination with examples, but they should not be understood as limiting the scope of protection of the present application.

[0065] Example 1

[0066] A preparation method of a collagen fiber with antibacterial performance, the steps are as follows:

[0067] (1) Tannic acid was added into 0.5 mol / L acetic acid solution and stirred magnetically for 20 min to obtain a tannic acid solution with a final concentration of 0.1 mg / mL.

[0068] (2) Collagen raw material (type I collagen with a concentration of 8 mg / mL) was added into the tannic acid solution obtained in step (1) and swelled at 4°C for 20 min. Mechanical stirring was used to fully stir the solution at 150 rpm for 8 h until the collagen raw material was completely dissolved. The whole solution process was maintained at 4°C. Then, the solution was centrifuged at 9000 r / min at 4°C for 40 min to remove bubbles and obtain a spinning dope.

[0069] (3) The spinning dope obtained in step (2) was transferred to a multi-phase channel microfluidic spinning device for extrusion molding (the storage time of the spinning dope in the microfluidic spinning device was less than 6 h to prevent local coagulation and affect the fiber properties). The extrusion speed of the inner phase channel (injected with the spinning dope) was 0.5 mL / min; the extrusion speed of the first outer phase channel (injected with 0.5 mg / mL silver nitrate aqueous solution) was 0.1 mL / min; the extrusion speed of the second outer phase channel (injected with anhydrous ethanol) was 0.15 mL / min; the spinning stream extruded from the spinneret 4 entered a coagulation bath at 25°C and stayed for 3 min for coagulation. After air-drying, collagen fibers with antibacterial properties were obtained; the coagulation bath included acetone and ammonia water at a volume ratio of 20:1.

[0070] Example 2

[0071] A method for preparing collagen fibers with antibacterial properties, the steps of which are as follows:

[0072] (1) Tannic acid was added into 0.5 mol / L acetic acid solution and stirred magnetically for 20 min to obtain a tannic acid solution with a final concentration of 0.3 mg / mL.

[0073] (2) Collagen raw material (type I collagen with a concentration of 8 mg / mL) was added into the tannic acid solution obtained in step (1) and swelled at 4°C for 20 min. Mechanical stirring was used to fully stir the solution at 150 rpm for 8 h until the collagen raw material was completely dissolved. The whole solution process was maintained at 4°C. Then, the solution was centrifuged at 9000 r / min at 4°C for 40 min to remove bubbles and obtain a spinning dope.

[0074] (3) The spinning dope obtained in step (2) is transferred to a multi-phase channel microfluidic spinning device for extrusion molding (the storage time of the spinning dope in the microfluidic spinning device is less than 6 h to prevent local coagulation and affect the fiber properties). The extrusion speed of the inner phase channel (injecting the spinning dope) is 0.5 mL / min; the extrusion speed of the first outer phase channel (injecting 0.5 mg / mL silver nitrate aqueous solution) is 0.1 mL / min; the extrusion speed of the second outer phase channel (injecting anhydrous ethanol) is 0.15 mL / min; the spinning stream extruded from the spinneret 4 enters a coagulation bath at 25°C for 3 min for coagulation, and after air-drying, collagen fibers with antibacterial properties are obtained; the coagulation bath comprises acetone and ammonia water in a volume ratio of 20:1.

[0075] Example 3

[0076] A method for preparing collagen fibers with antibacterial properties, the steps are as follows:

[0077] (1) Tannic acid is added to a 0.5 mol / L acetic acid solution, and magnetic stirring is performed for 20 min to obtain a tannic acid solution with a final concentration of 0.5 mg / mL.

[0078] (2) Collagen raw material (type I collagen, concentration 8 mg / mL) is added to the tannic acid solution obtained in step (1), swells at 4°C for 20 min, and is fully stirred using mechanical stirring for 8 h until the collagen raw material is completely dissolved. The entire dissolution process is maintained at 4°C, and then centrifugal defoaming is performed at 9000 r / min for 40 min at 4°C to obtain a spinning dope.

[0079] (3) The spinning dope obtained in step (2) is transferred to a multi-phase channel microfluidic spinning device for extrusion molding (the storage time of the spinning dope in the microfluidic spinning device is less than 6 h to prevent local coagulation and affect the fiber properties). The extrusion speed of the inner phase channel (injecting the spinning dope) is 0.5 mL / min; the extrusion speed of the first outer phase channel (injecting 0.5 mg / mL silver nitrate aqueous solution) is 0.1 mL / min; the extrusion speed of the second outer phase channel (injecting anhydrous ethanol) is 0.15 mL / min; the spinning stream extruded from the spinneret 4 enters a coagulation bath at 25°C for 3 min for coagulation, and after air-drying, collagen fibers with antibacterial properties are obtained; the coagulation bath comprises acetone and ammonia water in a volume ratio of 20:1.

[0080] Example 4

[0081] A method for preparing collagen fibers with antibacterial properties, the steps are as follows:

[0082] (1) Tannic acid is added to a 0.5 mol / L acetic acid solution, and magnetic stirring is performed for 20 min to obtain a tannic acid solution with a final concentration of 0.5 mg / mL.

[0083] (2) Collagen raw material (Type I collagen, concentration 8 mg / mL) was added to the tannic acid solution obtained in step (1), and swelled at 4°C for 20 min. Mechanical stirring was used to fully stir for 8 h until the collagen raw material was completely dissolved. The whole dissolving process was maintained at 4°C. Then, centrifugal defoaming was performed at 9000 r / min for 40 min at 4°C to obtain a spinning dope.

[0084] (3) The spinning dope obtained in step (2) was transferred to a multi-phase channel microfluidic spinning device for extrusion molding (the storage time of the spinning dope in the microfluidic spinning device was less than 6 h to prevent local coagulation and affect the fiber properties). The extrusion speed of the inner phase channel (injecting the spinning dope) was 0.5 mL / min; the extrusion speed of the first outer phase channel (injecting 1.5 mg / mL silver nitrate aqueous solution) was 0.1 mL / min; the extrusion speed of the second outer phase channel (injecting anhydrous ethanol) was 0.15 mL / min; the spinning stream extruded from spinneret 4 entered a coagulation bath at 25°C for 3 min for coagulation. After air-drying, collagen fibers with antibacterial properties were obtained; the coagulation bath included acetone and ammonia water at a volume ratio of 20:1.

[0085] Example 5

[0086] A method for preparing collagen fibers with antibacterial properties, the steps being as follows:

[0087] (1) Tannic acid was added to a 0.5 mol / L acetic acid solution, and magnetic stirring was performed for 20 min to obtain a tannic acid solution with a final concentration of 0.5 mg / mL.

[0088] (2) Collagen raw material (Type I collagen, concentration 8 mg / mL) was added to the tannic acid solution obtained in step (1), and swelled at 4°C for 20 min. Mechanical stirring was used to fully stir for 8 h until the collagen raw material was completely dissolved. The whole dissolving process was maintained at 4°C. Then, centrifugal defoaming was performed at 9000 r / min for 40 min at 4°C to obtain a spinning dope.

[0089] (3) The spinning dope obtained in step (2) was transferred to a multi-phase channel microfluidic spinning device for extrusion molding (the storage time of the spinning dope in the microfluidic spinning device was less than 6 h to prevent local coagulation and affect the fiber properties). The extrusion speed of the inner phase channel (injecting the spinning dope) was 0.5 mL / min; the extrusion speed of the first outer phase channel (injecting 1.5 mg / mL silver nitrate aqueous solution) was 0.1 mL / min; the extrusion speed of the second outer phase channel (injecting anhydrous ethanol) was 0.15 mL / min; the spinning stream extruded from spinneret 4 entered a coagulation bath at 25°C for 3 min for coagulation. After air-drying, collagen fibers with antibacterial properties were obtained; the coagulation bath included acetone and ammonia water at a volume ratio of 20:1.

[0090] Example 6

[0091] A method for preparing collagen fibers with antibacterial properties, comprising the following steps:

[0092] (1) Add tannic acid to 0.5 mol / L acetic acid solution, and magnetically stir for 20 min to obtain a tannic acid solution with a final concentration of 0.5 mg / mL.

[0093] (2) Add collagen raw material (type I collagen, concentration 8 mg / mL) to the tannic acid solution obtained in step (1), and swell at 4°C for 20 min. Use mechanical stirring to fully stir for 8 h until the collagen raw material is completely dissolved. Maintain the temperature at 4°C during the entire dissolution process. Then centrifuge at 9000 r / min at 4°C for 40 min to remove bubbles, and obtain a spinning dope.

[0094] (3) Transfer the spinning dope obtained in step (2) to a multi-phase channel microfluidic spinning device for extrusion molding (the storage time of the spinning dope in the microfluidic spinning device is less than 6 h to prevent local coagulation and affect the fiber properties). The extrusion speed of the inner phase channel (injecting the spinning dope) is 0.5 mL / min; the extrusion speed of the first outer phase channel (injecting 2.5 mg / mL silver nitrate aqueous solution) is 0.1 mL / min; the extrusion speed of the second outer phase channel (injecting anhydrous ethanol) is 0.15 mL / min; the spinning stream extruded from the spinneret 4 enters a coagulation bath at 25°C and stays for 3 min for coagulation. After air-drying, collagen fibers with antibacterial properties are obtained; the coagulation bath comprises acetone and ammonia water in a volume ratio of 20:1.

[0095] Example 7

[0096] A method for preparing collagen fibers with antibacterial properties, comprising the following steps:

[0097] (1) Add tannic acid to 0.5 mol / L acetic acid solution, and magnetically stir for 20 min to obtain a tannic acid solution with a final concentration of 0.5 mg / mL.

[0098] (2) Add collagen raw material (type I collagen, concentration 8 mg / mL) to the tannic acid solution obtained in step (1), and swell at 4°C for 20 min. Use mechanical stirring to fully stir for 8 h until the collagen raw material is completely dissolved. Maintain the temperature at 4°C during the entire dissolution process. Then centrifuge at 9000 r / min at 4°C for 40 min to remove bubbles, and obtain a spinning dope.

[0099] (3) The spinning dope obtained in step (2) is transferred to a multi-phase channel microfluidic spinning device for extrusion molding (the storage time of the spinning dope in the microfluidic spinning device is less than 6 h to prevent local coagulation and affect the fiber properties). The extrusion speed of the inner phase channel (injecting the spinning dope) is 0.5 mL / min; the extrusion speed of the first outer phase channel (injecting 0.5 mg / mL silver nitrate aqueous solution) is 0.1 mL / min; the extrusion speed of the second outer phase channel (injecting anhydrous ethanol) is 0.15 mL / min; the spinning stream extruded from the spinneret 4 enters a coagulation bath at 25°C for 3 min for coagulation, and after air-drying, collagen fibers with antibacterial properties are obtained; the coagulation bath comprises acetone and ammonia water in a volume ratio of 20:1.

[0100] Example 8

[0101] A method for preparing collagen fibers with antibacterial properties, the steps are as follows:

[0102] (1) Tannic acid is added to a 0.5 mol / L acetic acid solution, and magnetic stirring is performed for 20 min to obtain a tannic acid solution with a final concentration of 0.7 mg / mL.

[0103] (2) Collagen raw material (type I collagen, concentration 8 mg / mL) is added to the tannic acid solution obtained in step (1), swelled at 4°C for 20 min, and fully stirred using mechanical stirring for 8 h until the collagen raw material is completely dissolved. The whole dissolution process is maintained at 4°C, and then centrifugal defoaming is performed at 9000 r / min for 40 min at 4°C to obtain a spinning dope.

[0104] (3) The spinning dope obtained in step (2) is transferred to a multi-phase channel microfluidic spinning device for extrusion molding (the storage time of the spinning dope in the microfluidic spinning device is less than 6 h to prevent local coagulation and affect the fiber properties). The extrusion speed of the inner phase channel (injecting the spinning dope) is 0.5 mL / min; the extrusion speed of the first outer phase channel (injecting 0.5 mg / mL silver nitrate aqueous solution) is 0.1 mL / min; the extrusion speed of the second outer phase channel (injecting anhydrous ethanol) is 0.15 mL / min; the spinning stream extruded from the spinneret 4 enters a coagulation bath at 25°C for 3 min for coagulation, and after air-drying, collagen fibers with antibacterial properties are obtained; the coagulation bath comprises acetone and ammonia water in a volume ratio of 20:1.

[0105] Experimental Example 1

[0106] The physical properties and antibacterial properties of the fibers obtained in Examples 1-8 are determined, as shown in Table 1.

[0107] The physical performance determination method is as follows (reference: GB / T 14337-2022): the fiber measurement length is 10 mm, the tensile rate is 10 mm / min, and the measurement average value of 10 samples in each group is taken.

[0108] Instrument: electronic single fiber strength tester (Laizhou Electronic Instrument Co., Ltd.).

[0109] The antibacterial performance is determined by the national standard GB / T 20944.3-2008.

[0110] Table 1 determination result

[0111]

[0112]

[0113] From the content recorded in Table 1, it can be seen that the fiber prepared by the method of the application meets the requirements of the medical industry standard YY1116-2020 absorbable surgical suture.

[0114] From the data of the examples, it can be seen that the setting of the tannin solution concentration and the silver nitrate solution concentration is very important, and if it is not set properly, it will obviously affect the elongation at break of the fiber, but has little effect on the breaking strength and antibacterial property.

[0115] In the prior art, the properties of the fiber are mainly judged according to the breaking strength, and the breaking strength of pure fiber is generally 1.8-2.3 cN / dtex, while the breaking strength of the collagen fiber prepared in Example 5 of the application can reach 4.15 cN / dtex, which is obviously better than that of pure fiber.

[0116] The above is only the preferred embodiment of the application, and it should be pointed out that for ordinary skilled persons in the technical field, some improvements and refinements can be made without departing from the principles of the application, and these improvements and refinements should also be regarded as the protection scope of the application.

Claims

1. A method for producing collagen fibers having antibacterial properties, characterized by, The preparation method comprises the following steps: (1) mixing a tannic acid solution with a collagen stock solution to swell and dissolve, to obtain a spinning stock solution; (2) extruding the spinning stock solution to obtain nascent fibers, and the nascent fibers are coagulated to obtain collagen fibers with antibacterial properties; The extrusion molding is provided with an inward channel, a first outer phase channel and a second outer phase channel; The inward channel is injected with the spinning stock solution; The first outer phase channel is injected with a silver nitrate solution; and the second outer phase channel is injected with ethanol; In step (1), the concentration of tannic acid in the tannic acid solution is 0.3-0.7 mg / mL; the tannic acid solution uses an acetic acid solution as a solvent; and the concentration of the acetic acid solution is 0.3-0.7 mol / L; In step (1), the concentration of collagen in the collagen stock solution is 6-10 mg / mL; and the collagen is type I collagen; In step (2), the concentration of the silver nitrate solution is 0.5-2.5 mg / mL; and the ethanol is anhydrous ethanol.

2. The production method according to claim 1, characterized by, In step (1), the swelling temperature is 4-6℃, and the time is 15-25 min; the dissolution speed is 150-250 rpm, the time is 6-8 h, and the temperature is 4-6℃.

3. The preparation method according to claim 1, characterized in that, In step (1), after dissolution, centrifugal defoaming is further performed, the centrifugal defoaming speed is 8000-10000 rpm, the time is 30-50 min, and the temperature is 4-6℃.

4. The method of claim 1, wherein, In step (2), the extrusion speed of the inward channel is 0.3-0.7 mL / min; the extrusion speed of the first outer phase channel is 0.05-0.20 mL / min; and the extrusion speed of the second outer phase channel is 0.05-0.25 mL / min.

5. The preparation method according to claim 1, characterized in that, In step (2), the coagulation is performed in a coagulation bath, the coagulation bath comprises acetone and ammonia water; the volume ratio of the acetone to the ammonia water is 15-25:1; the temperature of the coagulation bath is set to 20-30℃; and the nascent fibers stay in the coagulation bath for 2-4 min.

6. The collagen fibers with antibacterial properties prepared by the preparation method in any one of claims 1-5.

7. The use of the collagen fibers with antibacterial properties in claim 6 in the preparation of medical sutures.

Citation Information

Patent Citations

  • Oriented conductive collagen hydrogel, biomimetic conductive nerve scaffold material and preparation method of oriented conductive collagen hydrogel and biomimetic conductive nerve scaffold material

    CN110124113A

  • Preparation method of plant antibacterial, antiviral, skin-care and health-care cellulose fibers

    CN112210846A