Seaweed fiber with photothermal controllable antibacterial function and preparation method thereof
By synthesizing zinc oxide and polydopamine in situ in sodium alginate fibers, photothermal controllable antibacterial algal fibers are prepared, which solves the problem of sodium alginate fibers lacking antibacterial function and antibiotic use, and achieves biocompatibility, degradability and photothermal controllable antibacterial effects.
Patent Information
- Application Number
- CN202411177071.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-08-26
- Publication Date
- 2025-09-02
- Estimated Expiration
- 2044-08-26
AI Technical Summary
The existing sodium alginate fiber materials lack antibacterial function and are difficult to achieve controlled release of antibacterial components. The use of traditional antibiotics leads to bacterial resistance and silver particles are biotoxic.
By synthesizing zinc oxide and polydopamine in situ in sodium alginate solution, algal fibers are prepared using chelation cross-linking technology, and the controlled release of antibacterial function is achieved in combination with photothermal properties.
The prepared seaweed fibers maintain biocompatibility and degradability, have photothermal controllable antibacterial functions, achieve stable release of antibacterial components and significant antibacterial effects, and avoid excessive use of antibiotics.
Smart Images
Figure CN119061529B_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the field of medical composite materials, and in particular relates to a seaweed fiber with photothermal controllable antibacterial function and a preparation method thereof. Background Art
[0002] The development of medical antibacterial functional fibers is mainly due to the need to prevent infection and improve sanitary conditions in the medical field. With the advancement of medical technology and the improvement of patients' requirements for medical care, the shortcomings of traditional fiber materials in antibacterial performance have gradually become apparent. The development of intelligent, controllable, non-toxic, continuously antibacterial, and biocompatible antibacterial fiber materials has always been an urgent problem to be solved in the fields of scientific research and medical applications. Sodium alginate is a natural linear polymer polysaccharide that has great potential in the medical field due to its good biocompatibility and degradability. However, sodium alginate itself does not have antibacterial function, which limits its application in the medical field.
[0003] Doping with antibacterial ingredients is an effective way to give sodium alginate antibacterial properties. Researchers added silver nanoparticles to sodium alginate hydrogels, giving the material good antibacterial properties, but silver particles have potential biotoxicity and can easily cause cell hemolysis. Some researchers have also used tannic acid as an antibacterial agent to blend with sodium alginate and glycerol to develop an antibacterial cotton gauze that has good antibacterial activity against a variety of bacteria, but the composite material cannot control the release rate of antibacterial particles according to the wound condition. Medical dressings with good biocompatibility, sustained antibacterial properties and controlled sustained-release functions have always been urgently needed products in clinical applications.
[0004] Polydopamine is a synthetic melanin inspired by mussels, formed by the slow oxidative polymerization of dopamine hydrochloride in an alkaline solution. Polydopamine contains a large number of functional groups, such as catechols and imines, which can form hydrogen or covalent bonds with polymers containing functional groups such as phenols, amines, and thiols, and can also chelate with metal ions. Therefore, the introduction of polydopamine often improves the mechanical properties of composite materials. Furthermore, due to its excellent photothermal properties, antioxidant capacity, and good biocompatibility, polydopamine has broad application prospects in the medical field.
[0005] Some researchers have physically cross-linked antibiotic-loaded polydopamine and nanocellulose to form a hydrogel. This allows for controlled drug release under near-infrared light or at low pH conditions, but widespread use of antibiotics can lead to bacterial resistance. Zinc oxide has excellent biosafety, chemical stability, and significant antimicrobial activity, and is widely recognized for its antibacterial, anti-inflammatory, and wound healing properties. Zinc oxide as an antimicrobial material can help prevent the overuse of antibiotics. Zinc is essential for maintaining the body's functional mechanisms. When in contact with wounds, zinc oxide ionizes into zinc ions, providing essential elements for wound healing while preventing infection. It is well known that achieving controlled release of antimicrobial components during the dynamic process of wound healing and ensuring the continued effectiveness of the material's antimicrobial function are key features of ideal medical material applications, something that is difficult to achieve with traditional materials. Summary of the Invention
[0006] In order to solve the above-mentioned defects existing in the prior art, the purpose of the present invention is to provide a seaweed fiber with photothermal controllable antibacterial function and a preparation method thereof. The seaweed fiber with photothermal controllable antibacterial function prepared by this method not only maintains the biocompatibility and degradability of sodium alginate, but also, due to the introduction of polydopamine and zinc oxide, gives the material good photothermal controllable antibacterial function while ensuring the excellent antibacterial properties of the composite material.
[0007] The present invention is achieved through the following technical solutions.
[0008] One aspect of the present invention provides a method for preparing seaweed fiber with photothermal controllable antibacterial function, comprising the following steps:
[0009] (a) adding dopamine hydrochloride and tris(hydroxymethylaminomethane) to a sodium alginate solution in a ratio of 10-50% of the mass of dopamine hydrochloride to the mass of sodium alginate and 1-10% of the mass of tris(hydroxymethylaminomethane) to the mass of sodium alginate, stirring and reacting to obtain a sodium alginate / polydopamine solution;
[0010] (b) adding a zinc salt solution and an alkaline solution to the sodium alginate solution in a mass ratio of (100-120): (8-14): (12-16), heating and stirring to react, to obtain a sodium alginate / zinc oxide solution;
[0011] (c) mixing a sodium alginate / polydopamine solution and a sodium alginate / zinc oxide solution in a mass ratio of (100-120):(120-150), injecting the mixed solution into a metal salt aqueous solution coagulation bath through a spinneret using a syringe pump, and chelating and crosslinking the sodium alginate into fibers; and washing the obtained fibers with deionized water and drying them to obtain seaweed fibers.
[0012] Preferably, the mass concentration of the sodium alginate solution is 0.5-5%.
[0013] Preferably, the stirring temperature of dopamine hydrochloride in the sodium alginate solution is 10-30° C. and the stirring time is 4-8 hours.
[0014] Preferably, the zinc salt is one or more of zinc sulfate, zinc nitrate, zinc chloride and zinc acetate.
[0015] Preferably, the alkaline solution is one or more of sodium hydroxide solution, potassium hydroxide solution and calcium hydroxide solution.
[0016] Preferably, the concentration of the zinc salt solution is 0.1-0.25 mol / L; the concentration of the alkaline solution is 0.1-1 mol / L; the stirring temperature is 40-60° C., and the stirring time is 2-4 hours.
[0017] Preferably, the metal salt in the metal salt aqueous solution coagulation bath is one or more of calcium chloride, strontium chloride, zinc chloride and copper chloride.
[0018] Preferably, the mass concentration of the metal salt aqueous solution in the coagulation bath is 1-5%; the temperature for the sodium alginate chelation cross-linking fiber formation is 10-30°C.
[0019] Another aspect of the present invention provides a seaweed fiber with photothermal controllable antibacterial function prepared by the method.
[0020] The present invention adopts the above technical solution, which has the following beneficial effects:
[0021] The composite antimicrobial functional fiber prepared in this invention is composed of zinc oxide synthesized in situ on sodium alginate, polydopamine synthesized in situ, and sodium alginate cross-linked by metal salt chelation. The composite antimicrobial functional fiber not only maintains the biocompatibility and degradability of sodium alginate, but also, thanks to the introduction of polydopamine and zinc oxide, imparts excellent photothermal and controllable antimicrobial properties while maintaining the excellent antimicrobial properties of the composite material.
[0022] 2. The preparation of the sodium alginate solution, the in-situ synthesis of zinc oxide, and the synthesis of polydopamine in the present invention are simple and easy, and the spinning process is environmentally friendly and low-cost. The prepared fiber has good moisture absorption and air permeability and controllable antibacterial properties. The present invention's alginate fiber with photothermal controllable antibacterial properties and its preparation method have broad application prospects in the treatment of tissue growth and postoperative wound repair.
[0023] 3. The seaweed fiber produced in this invention exhibits excellent breathability and moisture absorption properties, and the photothermal effect of polydopamine enables controlled release of antimicrobial components. Textile medical dressings made with this fiber offer significant advantages in clinical applications such as chronic wound care and postoperative wound repair.
[0024] Other features and advantages of the present invention will be described in the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS
[0025] The drawings described herein are used to provide a further understanding of the present invention, constitute a part of this application, and do not constitute an improper limitation of the present invention. In the drawings:
[0026] Figure 1 The present invention shows a process flow chart of a seaweed fiber with photothermal controllable antibacterial function and its preparation method and application;
[0027] Figures 2(a) and (b) respectively show the photothermal effect of the seaweed fiber with photothermal controllable antibacterial function of the present invention; Figure 2(a) is the surface temperature-time curve of the composite film under 100W and 250W near-infrared light; Figure 2(b) is the optical and infrared images of the composite film surface under 250W near-infrared light at different times;
[0028] Figure 3 The antibacterial effect of the seaweed fiber with photothermal controllable antibacterial function in the present invention is shown. DETAILED DESCRIPTION
[0029] The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments. The exemplary embodiments and descriptions of the present invention are used to explain the present invention but are not intended to limit the present invention.
[0030] The present invention provides a method for preparing seaweed fiber with photothermal controllable antibacterial function, comprising the following steps:
[0031] Step 1, prepare sodium alginate solution:
[0032] Sodium alginate is placed in deionized water to obtain a sodium alginate solution with a concentration of 0.5-5%.
[0033] Step 2, prepare polydopamine / sodium alginate solution:
[0034] According to the method, the mass of dopamine hydrochloride is 10-50% of the mass of sodium alginate, and the mass of tris(hydroxymethyl)aminomethane is 1-10% of the mass of sodium alginate, dopamine hydrochloride and tris(hydroxymethyl)aminomethane are added to a sodium alginate solution with a mass concentration of 0.5-5%, and the mixture is stirred for reaction at a temperature of 10-30°C for 4-8 hours. When the color of the solution turns black, it is proved that polydopamine is synthesized in the sodium alginate solution, thereby obtaining a sodium alginate / polydopamine solution.
[0035] In step 2, the addition of tris(hydroxymethyl)aminomethane provides an alkaline environment for the oxidative polymerization of dopamine hydrochloride; dopamine hydrochloride is in situ polymerized in the sodium alginate solution to form polydopamine, and the hydrogen bonding between sodium alginate and polydopamine ensures the uniform dispersion of polydopamine in the solution system.
[0036] Step 3, in situ synthesis of zinc oxide:
[0037] Using sodium alginate as a template, 0.1-0.25 mol / L zinc salt solution and 0.1-1 mol / L alkaline solution are added to the sodium alginate solution in a mass ratio of (100-120): (8-14): (12-16), and the stirring temperature is 40-60°C and the stirring time is 2-4 hours. When the color of the solution turns milky white, it proves that zinc oxide is successfully synthesized to obtain a sodium alginate / zinc oxide solution.
[0038] The zinc salt solution is one or more of zinc sulfate solution, zinc nitrate solution, zinc chloride solution and zinc acetate solution; the alkaline solution is one or more of sodium hydroxide solution, potassium hydroxide solution and calcium hydroxide solution.
[0039] In step 3, the addition of zinc salt solution forms metal ion chelate cross-linking points in the sodium alginate solution system, while the addition of alkaline solution in situ synthesizes zinc oxide at the cross-linking points of the formed zinc ion micro-cross-linked sodium alginate network; zinc oxide can effectively ionize zinc ions in water and occupy the hydrophilic space in the sodium alginate molecular chain network through ion replacement, thereby effectively improving the antibacterial properties of sodium alginate.
[0040] Step 4, preparing seaweed fiber:
[0041] A sodium alginate / polydopamine solution and a sodium alginate / zinc oxide solution are mixed in a mass ratio of (100-120):(120-150), and the mixed solution is injected into a coagulation bath of an aqueous solution of a metal salt (one or more of calcium chloride, strontium chloride, zinc chloride and copper chloride) with a mass concentration of 1-5% through a spinneret using a syringe pump to chelate and crosslink the sodium alginate into fibers. The crosslinking temperature is 10-30°C. The obtained fibers are washed with deionized water and dried to obtain seaweed fibers with photothermal controllable antibacterial functions.
[0042] In step 4, the metal ions replace the sodium ions in the sodium alginate through substitution, forming an "egg box" structure with the metal ions as the core; the zinc oxide is completely encapsulated inside the seaweed fiber, providing a stable antibacterial component for the antibacterial properties of the seaweed fiber.
[0043] The present invention is further described in detail below through specific examples.
[0044] Example 1
[0045] Step 1, prepare sodium alginate solution:
[0046] 0.5 g of sodium alginate was placed in 100 ml of deionized water to obtain a sodium alginate solution with a concentration of 0.5%.
[0047] Step 2, prepare polydopamine / sodium alginate solution:
[0048] According to the mass of dopamine hydrochloride being 10% of the mass of sodium alginate and the mass of tris(hydroxymethyl)aminomethane being 5% of the mass of sodium alginate, dopamine hydrochloride and tris(hydroxymethyl)aminomethane are added to a sodium alginate solution with a mass concentration of 0.5%, the stirring temperature is 10°C, and the stirring time is 8 hours. When the color of the solution turns black, it proves that polydopamine is synthesized in the sodium alginate solution to obtain a sodium alginate / polydopamine solution.
[0049] Step 3, in situ synthesis of zinc oxide:
[0050] Using sodium alginate as a template, 0.15 mol / L zinc sulfate solution and 0.5 mol / L sodium hydroxide solution were added to the sodium alginate solution in a mass ratio of 100:14:15. The stirring temperature was 50°C and the stirring time was 3 hours. When the color of the solution turned milky white, it proved that zinc oxide was successfully synthesized to obtain a sodium alginate / zinc oxide solution.
[0051] Step 4, preparing seaweed fiber:
[0052] Sodium alginate / polydopamine solution and sodium alginate / zinc oxide solution were mixed in a mass ratio of 100:140, and the mixed solution was injected into a coagulation bath with a mass concentration of 3% zinc chloride through a spinneret using a syringe pump to carry out chelation cross-linking of the sodium alginate into fibers at a cross-linking temperature of 20°C. The fibers were washed with deionized water to obtain a seaweed fiber with photothermal controllable antibacterial function.
[0053] Example 2
[0054] Step 1, prepare sodium alginate solution:
[0055] 5 g of sodium alginate was placed in 100 ml of deionized water to obtain a sodium alginate solution with a concentration of 5%.
[0056] Step 2, prepare polydopamine / sodium alginate solution:
[0057] According to the mass of dopamine hydrochloride being 30% of the mass of sodium alginate and the mass of tris(hydroxymethyl)aminomethane being 10% of the mass of sodium alginate, dopamine hydrochloride and tris(hydroxymethyl)aminomethane are added to a sodium alginate solution with a mass concentration of 5%, the stirring temperature is 30°C, and the stirring time is 4 hours. When the color of the solution turns black, it proves that polydopamine is synthesized in the sodium alginate solution to obtain a sodium alginate / polydopamine solution.
[0058] Step 3, in situ synthesis of zinc oxide:
[0059] Using sodium alginate as a template, 0.25 mol / L zinc chloride solution and 1 mol / L potassium hydroxide solution + 1 mol / L calcium hydroxide solution were added to the sodium alginate solution in a mass ratio of 120:10:16. The stirring temperature was 40°C and the stirring time was 4 h. When the color of the solution turned milky white, it proved that zinc oxide was successfully synthesized to obtain a sodium alginate / zinc oxide solution.
[0060] Step 4, preparing seaweed fiber:
[0061] Sodium alginate / polydopamine solution and sodium alginate / zinc oxide solution were mixed in a mass ratio of 120:150, and the mixed solution was injected into a coagulation bath with a mass concentration of 5% calcium chloride and 5% copper chloride through a spinneret using a syringe pump to carry out chelation cross-linking of the sodium alginate into fibers. The cross-linking temperature was 10°C. The obtained fibers were washed with deionized water and dried to obtain seaweed fibers with photothermal controllable antibacterial functions.
[0062] Example 3
[0063] Step 1, prepare sodium alginate solution:
[0064] 1 g of sodium alginate was placed in deionized water to obtain a sodium alginate solution with a concentration of 1%.
[0065] Step 2, prepare polydopamine / sodium alginate solution:
[0066] According to the mass of dopamine hydrochloride being 50% of the mass of sodium alginate, and the mass of tris(hydroxymethyl)aminomethane being 1% of the mass of sodium alginate, dopamine hydrochloride and tris(hydroxymethyl)aminomethane were added to a sodium alginate solution with a mass concentration of 1%. The stirring temperature was 12°C and the stirring time was 4.5 hours. When the color of the solution turned black, it was proved that polydopamine was synthesized in the sodium alginate solution to obtain a sodium alginate / polydopamine solution.
[0067] Step 3, in situ synthesis of zinc oxide:
[0068] Using sodium alginate as a template, 0.1 mol / L zinc acetate solution + 0.1 mol / L zinc nitrate and 0.1 mol / L calcium hydroxide solution were added to the sodium alginate solution in a mass ratio of 110:8:12. The stirring temperature was 60°C and the stirring time was 2 hours. When the color of the solution turned milky white, it proved that zinc oxide was successfully synthesized to obtain a sodium alginate / zinc oxide solution.
[0069] Step 4, preparing seaweed fiber:
[0070] Sodium alginate / polydopamine solution and sodium alginate / zinc oxide solution were mixed in a mass ratio of 110:120, and the mixed solution was injected into a 1% strontium chloride coagulation bath through a spinneret using a syringe pump to carry out chelation cross-linking of sodium alginate into fibers at a cross-linking temperature of 30°C. The obtained fibers were washed with deionized water and dried to obtain seaweed fibers with photothermal controllable antibacterial functions.
[0071] Comparative Example 1
[0072] Zinc oxide particles are added to a sodium alginate solution, and the sodium alginate solution containing zinc oxide is injected into a coagulation bath with a mass concentration of 1% copper chloride through a spinneret using a syringe pump to chelate and crosslink the sodium alginate into fibers at a crosslinking temperature of 10°C. The fibers are then washed with deionized water to obtain an antibacterial seaweed fiber.
[0073] The antibacterial fiber materials obtained in Examples 1-3 and the comparative example were sterilized by irradiation and then subjected to relevant performance tests. The specific test contents and material properties are shown in Table 1 below.
[0074] Table 1 Comparison of the performance of antibacterial fiber materials of Examples 1-3 and Comparative Examples
[0075]
[0076]
[0077] Figure 1 As can be seen from Figure 2 (a) and (b), the seaweed fiber of the present invention has good photothermal response and thermal stability, with a maximum temperature of approximately 70°C. Figure 3It can be seen that the photothermally controlled antibacterial seaweed fiber of the present invention has excellent inhibitory effects on Escherichia coli, Staphylococcus aureus, and Pseudomonas aeruginosa, and its antibacterial effect is even more significant under the photothermal assisted antibacterial effect of polydopamine. Combining the above examples and Table 1, it can be seen that the photothermally controlled antibacterial seaweed fiber prepared by the present invention not only maintains the biocompatibility, degradability, and moisture absorption and water retention of the alginate material and polydopamine, but also imparts the material with excellent photothermally controlled antibacterial function, good moisture absorption and breathability, and long-lasting antibacterial properties. Its wet tensile strength is not less than 2.5 kPa, its dry tensile strength is not less than 20 kPa, its water absorption rate is not less than 200%, and its Escherichia coli inhibition effect in the composite antibacterial material is not less than 2 mm, Staphylococcus aureus effect is not less than 3 mm, and Pseudomonas aeruginosa effect is not less than 1 mm. The zinc ion release time can reach 7 days; it also has photothermally controlled antibacterial properties. The photothermally controlled antibacterial seaweed fiber material prepared by the present invention is a polymer composite material with excellent processing performance.
[0078] The present invention is not limited to the above-mentioned embodiments. On the basis of the technical solutions disclosed in the present invention, those skilled in the art can make some substitutions and modifications to some of the technical features therein according to the disclosed technical content without creative labor, and these substitutions and modifications are all within the protection scope of the present invention.
Claims
1. A method for preparing seaweed fiber with photothermal controllable antibacterial function, characterized in that: The steps include: (a) adding dopamine hydrochloride and tris(hydroxymethylaminomethane) to a sodium alginate solution in a ratio of 10-50% of the mass of dopamine hydrochloride to the mass of sodium alginate and 1-10% of the mass of tris(hydroxymethylaminomethane) to the mass of sodium alginate, stirring and reacting to obtain a sodium alginate / polydopamine solution; (b) adding a zinc salt solution and an alkaline solution to the sodium alginate solution in a mass ratio of (100-120): (8-14): (12-16), heating and stirring to react, to obtain a sodium alginate / zinc oxide solution; (c) mixing a sodium alginate / polydopamine solution and a sodium alginate / zinc oxide solution in a mass ratio of (100-120):(120-150), injecting the mixed solution into a metal salt aqueous solution coagulation bath through a spinneret using a syringe pump to chelate and crosslink the sodium alginate into fibers; The obtained fibers are washed with deionized water and dried to obtain seaweed fibers.
2. The method for preparing seaweed fiber with photothermal controllable antibacterial function according to claim 1, characterized in that: The mass concentration of the sodium alginate solution is 0.5-5%.
3. The method for preparing seaweed fiber with photothermal controllable antibacterial function according to claim 1, characterized in that: The stirring temperature of dopamine hydrochloride in the sodium alginate solution is 10-30° C. and the stirring time is 4-8 hours.
4. The method for preparing seaweed fiber with photothermal controllable antibacterial function according to claim 1, characterized in that: The zinc salt is one or more of zinc sulfate, zinc nitrate, zinc chloride and zinc acetate.
5. The method for preparing seaweed fiber with photothermal controllable antibacterial function according to claim 1, characterized in that: The alkaline solution is one or more of sodium hydroxide solution, potassium hydroxide solution and calcium hydroxide solution.
6. The method for preparing seaweed fiber with photothermal controllable antibacterial function according to claim 1, characterized in that: The concentration of the zinc salt solution is 0.1-0.25 mol / L; the concentration of the alkaline solution is 0.1-1 mol / L; the stirring temperature is 40-60° C., and the stirring time is 2-4 hours.
7. The method for preparing seaweed fiber with photothermal controllable antibacterial function according to claim 1, characterized in that: The metal salt in the metal salt aqueous solution coagulation bath is one or more of calcium chloride, strontium chloride, zinc chloride and copper chloride.
8. The method for preparing seaweed fiber with photothermal controllable antibacterial function according to claim 1, characterized in that: The mass concentration of the metal salt aqueous solution in the coagulation bath is 1-5%; the temperature for the sodium alginate chelating and cross-linking fiber formation is 10-30°C.
9. A seaweed fiber with photothermal controllable antibacterial function prepared by the method according to any one of claims 1 to 8.
10. The seaweed fiber with photothermal controllable antibacterial function according to claim 9 is used as an antibacterial medical dressing in the clinical treatment of chronic wound care and postoperative wound repair.