Dopamine / sodium alginate oxide composite photothermal hydrogel fiber and preparation method thereof

Abstract

The application discloses a dopamine / sodium alginate oxide composite photothermal hydrogel fiber and a preparation method thereof, and belongs to the field of functional fibers. The application takes a sodium alginate solution as a base, partially oxidizes the sodium alginate, combines dopamine with the oxidized sodium alginate, forms a Schiff base, and improves the stability and utilization rate of the dopamine; and the dopamine / sodium alginate oxide composite photothermal hydrogel fiber is prepared through wet spinning. The utilization rate of the dopamine in the dopamine / sodium alginate oxide composite photothermal hydrogel fiber prepared by the application is high.

Description

Technical Field

[0001] This invention relates to a dopamine / sodium oxidized alginate composite photothermal hydrogel fiber and its preparation method, belonging to the field of functional fibers. Background Technology

[0002] Hydrogel fibers differ significantly from traditional polymer fibers in several aspects. Hydrogel fibers are fibers with high water content, their core characteristic being the ability to maintain their structure in water while simultaneously adsorbing and releasing large amounts of water. Hydrogel fibers combine the performance characteristics of hydrogels with the structural advantages of fiber materials, making them excellent drug delivery platforms. Their high specific surface area gives them superior hygroscopicity, moisture retention, and breathability, and their size can be controlled to mimic the microfiber structures of human tissues, such as nerve cells, muscle fibers, tendons, and ligaments.

[0003] Currently, hydrogel fibers have wide applications in photothermal therapy. Photothermal therapy (PTT) is an emerging tumor treatment strategy that utilizes the photothermal effect of photothermal conversion materials (PTAs) to harvest energy from specific wavelengths of light and convert it into heat, raising the temperature of the surrounding environment, inhibiting tumor metastasis, and inducing cancer cell death. PTT can also be used for photothermal physiotherapy, achieving rapid local warming through natural light. In current research, good photothermal conversion effects are mostly achieved through dopamine.

[0004] Dopamine possesses excellent antioxidant, anti-inflammatory, antibacterial, and antiviral pharmacological activities. Under specific conditions, it can undergo oxidative rearrangement and self-polymerize to form polydopamine. Its good biodegradability, photostability, and high photothermal conversion efficiency enable dopamine to participate in fiber modification, leading to its wide application in the field of biomedical materials; for example:

[0005] CN116637090A discloses an electrospun carrier for oral mucosal drug delivery, which is a fiber membrane prepared by electrospinning after blending polyvinyl alcohol as the spinning material with dopamine-modified gelatin.

[0006] CN116943553A discloses a photothermal hydrogel for treating high-salt organic wastewater. It is based on the preparation of nanofibers by electrospinning technology, the construction of nanofiber hydrogel substrate by chemical cross-linking, the in-situ growth of polydopamine on nanofiber hydrogel substrate to form photothermal hydrogel, and finally the loading of iron-based catalyst onto photothermal hydrogel by hydrothermal reaction to obtain photothermal hydrogel that simultaneously desalinates and degrades organic pollutants.

[0007] However, due to its strong hydrophilicity, dopamine is prone to leakage during wet spinning, resulting in low utilization in hydrogel fibers. Therefore, electrospinning is often chosen in actual production to prepare hydrogel fibers containing dopamine. However, the solvents used in electrospinning are mostly toxic organic solvents, posing significant hazards. The production process requires a long curing time for the solution and involves high voltage, placing higher demands on equipment. This makes electrospinning complex and costly in industrial applications.

[0008] From a practical application perspective, it is essential to prepare a dopamine / sodium alginate composite photothermal gel fiber with high dopamine utilization rate, which can be prepared by wet spinning. Summary of the Invention

[0009] [Technical Issues]

[0010] Dopamine has excellent hydrophilicity and is easily leached out during wet spinning, resulting in extremely low utilization.

[0011] [Technical Solution]

[0012] To address the aforementioned issues, this invention uses sodium alginate solution as a base, partially oxidizing sodium alginate to combine dopamine and oxidized sodium alginate, forming a Schiff base to improve the stability and utilization rate of dopamine. Dopamine / oxidized sodium alginate composite photothermal gel fiber is then prepared via wet spinning. The dopamine / oxidized sodium alginate composite photothermal gel fiber prepared by this invention exhibits high dopamine utilization.

[0013] The first objective of this invention is to provide a method for preparing dopamine / sodium alginate composite photothermal hydrogel fibers, comprising the following steps:

[0014] (1) Mix sodium oxidized alginate, dopamine and sodium alginate aqueous solution to react and form Schiff base to obtain spinning solution;

[0015] (2) The spinning solution was wet-spun to prepare dopamine / sodium oxidized alginate photothermal gel fiber.

[0016] In one embodiment of the present invention, the dopamine in step (1) is dopamine hydrochloride.

[0017] In one embodiment of the present invention, the oxidation degree of sodium alginate in step (1) is 10% to 40%, preferably 32%.

[0018] As one embodiment of the present invention, the method for preparing sodium oxidized alginate in step (1) is as follows:

[0019] Sodium periodate solution was added to sodium alginate ethanol solution to carry out an oxidation reaction; after a period of time, ethylene glycol was added to terminate the reaction, followed by dialysis and freeze-drying to obtain oxidized sodium alginate.

[0020] The sodium periodate solution is an aqueous solution of sodium periodate, and the mass ratio of sodium periodate to water is 10-20:100, preferably 16:100.

[0021] Sodium alginate ethanol solution is a mixed solution of sodium alginate and anhydrous ethanol; the ratio of sodium alginate to anhydrous ethanol is 10-50g:100mL.

[0022] The mass ratio of sodium alginate to sodium periodate is 5:4;

[0023] Sodium periodate solution is added slowly by injection at a rate of 0.6–1 mL / min.

[0024] The oxidation reaction was carried out under light-protected conditions, at 25–30°C and 300–800 rpm, with stirring for 2–6 hours.

[0025] Dialysis refers to using an MWCO 3500Da dialysis bag for 1 to 5 days, with the deionized water being replaced periodically.

[0026] Freeze-drying involves freezing at -40℃ for 12-24 hours.

[0027] In one embodiment of the present invention, the mass ratio of sodium oxidized alginate to dopamine in step (1) is 1:1.

[0028] In one embodiment of the present invention, the mass concentration of oxidized sodium alginate in the sodium alginate aqueous solution in step (1) is 1% to 5%, preferably 3%.

[0029] In one embodiment of the present invention, the mass concentration of sodium alginate aqueous solution in step (1) is 1% to 3%.

[0030] In one embodiment of the present invention, the reaction in step (1) is carried out at 40-80°C for 2-10 hours.

[0031] In one embodiment of the present invention, the coagulation bath for wet spinning in step (2) is an aqueous solution of calcium chloride with a mass concentration of 1% to 5%, preferably 3%.

[0032] In one embodiment of the present invention, the wet spinning in step (2) is carried out by spinning through a flexible drawing spinning platform.

[0033] In one embodiment of the present invention, the extrusion speed of the spinning solution in the wet spinning process in step (2) is 0.5-5 mL / min, the fluid circulation speed is 0.42-2.73 m / s, and the inner diameter of the injection needle is 0.19-0.5 mm.

[0034] The second objective of this invention is to prepare dopamine / sodium oxidized alginate composite photothermal hydrogel fiber using the method described herein.

[0035] As one embodiment of the present invention, the diameter of the dopamine / sodium oxidized alginate composite photothermal hydrogel fiber is 30μm-50μm.

[0036] As one embodiment of the present invention, the dopamine / sodium oxidized alginate composite photothermal gel fiber can be heated to 80°C after 5 minutes of light irradiation.

[0037] The third objective of this invention is the application of the dopamine / sodium alginate composite photothermal hydrogel fiber described herein in textile materials.

[0038] As one embodiment of the present invention, textile materials include materials prepared by textile processing technologies such as knitting, weaving, braiding, and nonwovens.

[0039] The fourth objective of this invention is the application of the dopamine / sodium oxidized alginate composite photothermal hydrogel fiber described herein in the biomedical field.

[0040] As one embodiment of the present invention, the biomedical field includes photothermal therapy (PTT); PTT utilizes a photothermal agent to absorb light of a specific wavelength and then converts the absorbed light into heat, the generated heat energy of which can be used to destroy cancer cells.

[0041] The fifth objective of this invention is a photothermal therapy patch that utilizes the dopamine / sodium oxidized alginate composite photothermal hydrogel fiber described in this invention.

[0042] The sixth objective of this invention is to provide a method for improving the utilization of dopamine in wet-spun hydrogel fibers, which employs the dopamine / sodium alginate composite photothermal hydrogel fiber described in this invention.

[0043] The seventh objective of this invention is to provide a method for improving the photothermal effect of hydrogel fibers under both sunlight and infrared light, which employs the dopamine / sodium alginate composite photothermal hydrogel fiber described in this invention.

[0044] [Beneficial Effects]

[0045] (1) The process of preparing dopamine / sodium oxidized alginate composite photothermal hydrogel fiber by the present invention is green and environmentally friendly, does not use toxic and harmful reagents, and is more suitable for the biomedical field.

[0046] (2) The preparation method of sodium oxidized alginate and dopamine / sodium oxidized alginate composite photothermal gel fiber in this invention is simple to operate, and the instruments required in the preparation process are suitable for mass production of photothermal gel fiber in factories; the spinning speed is fast; the production cost is low, and it is suitable for production scale-up.

[0047] (3) The dopamine / sodium oxidized alginate composite photothermal gel fiber prepared by the present invention has excellent photothermal effect, good biocompatibility and controllable biodegradability and other excellent properties, which have important scientific research value and practical significance in the field of photothermal therapy. Attached Figure Description

[0048] Figure 1 The infrared spectrum of sodium oxidized alginate prepared in Example 1.

[0049] Figure 2 Electron micrograph of dopamine / sodium oxidized alginate composite photothermal hydrogel fiber prepared in Example 1.

[0050] Figure 3 The infrared photothermal heating trend of the dopamine / sodium oxidized alginate photothermal gel nonwoven fabric prepared in Example 2.

[0051] Figure 4 The solar photothermal heating trend of the dopamine / sodium oxidized alginate photothermal gel nonwoven fabric prepared in Example 2 is shown in the figure.

[0052] Figure 5 Antioxidant activity analysis of the dopamine / sodium oxidized alginate composite photothermal hydrogel fiber nonwoven fabric prepared in Example 3.

[0053] Figure 6 The image shows the photothermal effect of the dopamine / sodium oxidized alginate composite photothermal gel fiber nonwoven fabric prepared in Example 3. Detailed Implementation

[0054] The preferred embodiments of the present invention are described below. It should be understood that the embodiments are for better explanation of the present invention and are not intended to limit the present invention.

[0055] Test method:

[0056] 1. DPPH test:

[0057] Add 1 mL of DPPH to ethanol in a light-protected environment; then weigh 5 mg of the sample into a 2 mL centrifuge tube. Add 1 mL of 0.04 mg / mL DPPH ethanol solution to the centrifuge tube and incubate at room temperature in the dark for 1 h. Measure the absorbance of the solution at 517 nm using a microplate reader.

[0058] 2. Photothermal test:

[0059] The test sample was cut into 1cm pieces. 2 With a fixed size, a solar simulator and thermal infrared light sources were used to provide light sources, respectively. A thermal infrared imager recorded the temperature changes and heat transfer of the sample surface. Under room temperature conditions, the sample surface temperature was recorded after heating for 5–10 minutes and then cooling for 5–10 minutes.

[0060] 3. Biocompatibility testing:

[0061] Weigh 2 mg of sample into a centrifuge tube, then add 800 μL of PBS to a 200 μM red blood cell suspension, and incubate at 37 °C for 1 h. After incubation at 37 °C for 1 hour, centrifuge at 5000 rpm for 5 min, collect the supernatant, and measure the absorbance of the supernatant at 540 nm using a microplate reader.

[0062] 4. Determination of oxidation degree:

[0063] The degree of oxidation of oxidized alginate was calculated using hydroxylamine hydrochloride-methyl orange.

[0064] Prepare a 0.25 mol / L hydroxylamine hydrochloride-methyl orange solution, and add 0.1 g of oxidized alginate to 25 mL of the hydroxylamine hydrochloride-methyl orange solution. Standardize the solution with NaOH, and record the volume of sodium hydroxide consumed and the pH value at which the color changes. Raw materials used in the examples:

[0065] Sodium alginate, dopamine hydrochloride, sodium periodate, ethylene glycol, MWCO 3500Da dialysis bags, and calcium oxide are all commercially available.

[0066] Unless otherwise specified, the percentages mentioned in the examples refer to mass percentages, and unless otherwise specified, the solvent used in the solutions is water.

[0067] Example 1

[0068] A method for preparing dopamine / sodium oxidized alginate composite photothermal hydrogel fiber includes the following steps:

[0069] (1) Add 20g of sodium alginate to 100mL of anhydrous ethanol to obtain sodium alginate ethanol solution;

[0070] Dissolve 16g of sodium periodate in 100mL of deionized water to obtain a sodium periodate solution;

[0071] Slowly inject 100 mL of sodium periodate solution (at a rate of 0.8 mL / min) into 100 mL of sodium alginate ethanol solution, and carry out the oxidation reaction by stirring uniformly at 30 °C and 800 rpm for 4 hours in a dark environment.

[0072] Then, 5 mL of ethylene glycol was added to the reaction mixture to terminate the reaction, and the mixture was dialyzed for 3 days using an MWCO3500Da dialysis bag; the dialysate was freeze-dried at -40°C for 18 h to obtain sodium alginate oxide.

[0073] (2) Add sodium alginate oxide and dopamine hydrochloride to a sodium alginate aqueous solution with a mass concentration of 2% and stir at 60°C for 6 hours to form a Schiff base and obtain the spinning solution.

[0074] The mass ratio of sodium alginate oxide to dopamine hydrochloride is 1:1.

[0075] The mass concentration of oxidized sodium alginate in sodium alginate aqueous solution is 3%;

[0076] (3) A calcium chloride aqueous solution with a mass concentration of 3% was used as the coagulation bath for wet spinning. Wet spinning was carried out through a flexible drawing spinning platform to prepare dopamine / sodium alginate photothermal gel fiber (fineness of 37μm). The wet spinning was carried out using a syringe with an inner diameter of 0.21mm, a push speed of 0.8min / mL, and a fluid circulation speed of 1.32m / s.

[0077] The obtained oxidized sodium alginate and hydrogel fibers were subjected to performance tests, and the test results are as follows:

[0078] (1) Infrared testing:

[0079] The oxidation degree of sodium alginate was calculated using hydroxylamine hydrochloride-methyl orange, and determined by FTIR. Figure 1 .

[0080] from Figure 1 It can be seen that the oxidation degree of sodium alginate is 32%.

[0081] (2) Scanning electron microscopy of hydrogel fibers, such as Figure 2 .

[0082] Example 2

[0083] A method for preparing hydrogel nonwoven fabric using dopamine / sodium alginate photothermal hydrogel fibers as described in Example 1 includes the following steps:

[0084] The dopamine / sodium alginate photothermal hydrogel fiber from Example 1 was wet-laid, uniformly settled, and then naturally air-dried to obtain the hydrogel nonwoven fabric.

[0085] The specification of the hydrogel nonwoven fabric is 63.585cm. 2 The weight is 215.5 g / m³. 2 .

[0086] The obtained hydrogel nonwoven fabric was subjected to performance tests, and the test results are as follows:

[0087] A thermal infrared light source is used to record the temperature changes and heat transfer on the sample surface using a thermal infrared imager. Finally, plotting software is used to draw the temperature rise and fall trends, and the results are as follows: Figure 3 .

[0088] from Figure 3 It can be seen that the nonwoven fabric can rapidly convert light energy into heat energy by rising from 28°C to 106°C within 5 minutes, indicating that the present invention has a good photothermal conversion capability.

[0089] Using the same method, the light source was replaced with a solar simulator, and the results of the temperature rise and fall trends were as follows: Figure 4 :

[0090] from Figure 4 It can be seen that the nonwoven fabric rises from 34°C to 81°C within 5 minutes. This invention can still efficiently convert light energy into heat energy without providing a specific light source.

[0091] Example 3

[0092] The mass concentration of oxidized sodium alginate in sodium alginate aqueous solution in step (3) of Example 1 was adjusted to 1%, 3%, and 5%, while other steps remained the same as in Example 1, to obtain hydrogel fibers; then, nonwoven fabric was prepared according to Example 2.

[0093] The obtained nonwoven fabric was tested, and the test results are as follows;

[0094] The test results for antioxidant activity are as follows: Figure 5 ;

[0095] from Figure 5 It can be seen that nonwoven fabrics have good antioxidant activity, and the antioxidant activity increases with the increase of dopamine content. When the mass concentration of dopamine in sodium alginate aqueous solution is 1%, the DPPH free radical scavenging rate is 80.5%; when the mass concentration of dopamine in sodium alginate aqueous solution is 3%, the DPPH free radical scavenging rate is 76.3%; and when the mass concentration of dopamine in sodium alginate aqueous solution is 5%, the DPPH free radical scavenging rate is 89.6%.

[0096] The test results of the photothermal effect are as follows: Figure 6 ;

[0097] Cong Figure 6It can be seen that when the mass concentration of dopamine in the sodium alginate aqueous solution is 1%, the temperature rises from 34℃ to 45℃ within 5 minutes; when the mass concentration of dopamine in the sodium alginate aqueous solution is 3%, the temperature rises from 34℃ to 74℃ within 5 minutes; and when the mass concentration of dopamine in the sodium alginate aqueous solution is 5%, the temperature rises from 34℃ to 72℃ within 5 minutes. Therefore, the difference in photothermal performance between 3% and 5% concentrations is not significant. From a cost-saving perspective, a mass concentration of 3% dopamine in the spinning solution is chosen.

[0098] Comparative Example 1

[0099] Omit the sodium alginate oxidase from the raw materials in Example 1, and keep other conditions or parameters the same as in Example 1 to obtain hydrogel fibers. Then, nonwoven fabrics were prepared according to Example 2.

[0100] The test results are as follows:

[0101] During the heating and cooling process, the sample was heated by 38°C when thermal infrared light was used as the light source, and by 15°C when simulated sunlight was used as the light source.

[0102] In Example 1, during the heating and cooling process of 5 minutes, the sample heated by thermal infrared light source increased by 78°C, which is 105% higher than that of hydrogel nonwoven fabric without oxidized sodium alginate; the sample heated by simulated sunlight light source increased by 47°C, which is 213% higher than that of hydrogel nonwoven fabric without oxidized sodium alginate.

[0103] Comparative Example 2

[0104] The sodium alginate oxide and dopamine hydrochloride in Example 1 are omitted, and sodium alginate solution is used directly as the spinning solution; other conditions or parameters are the same as in Example 1.

[0105] The results showed that the spinning solution dissolved in the coagulation bath, and the fibers could not be formed.

[0106] Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make various modifications and alterations without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be determined by the claims.

Claims

1. A method for preparing dopamine / sodium oxidized alginate composite photothermal hydrogel fibers, characterized in that, Includes the following steps: (1) Add 20 g of sodium alginate to 100 mL of anhydrous ethanol to obtain sodium alginate ethanol solution; Dissolve 16g of sodium periodate in 100mL of deionized water to obtain a sodium periodate solution; 100 mL of sodium periodate solution was slowly injected into 100 mL of sodium alginate ethanol solution at a rate of 0.8 mL / min, and the oxidation reaction was carried out by stirring uniformly at 30 °C and 800 rpm for 4 h in the dark. Then, 5 mL of ethylene glycol was added to the reaction mixture to terminate the reaction, and the mixture was dialyzed for 3 days using a MWCO3500Da dialysis bag; the dialysate was freeze-dried at -40 °C for 18 h to obtain sodium alginate oxidized. The oxidation degree of sodium alginate is 32%. (2) Add sodium alginate oxide and dopamine hydrochloride to a sodium alginate aqueous solution with a mass concentration of 2% and stir at 60 °C for 6 h to form a Schiff base and obtain the spinning solution. The mass ratio of sodium alginate oxide to dopamine hydrochloride is 1:

1. The mass concentration of oxidized sodium alginate in sodium alginate aqueous solution is 3%; (3) Using a calcium chloride aqueous solution with a mass concentration of 3% as the coagulation bath for wet spinning, wet spinning was carried out through a flexible drawing spinning platform to prepare dopamine / sodium oxidized alginate photothermal gel fiber with a fineness of 37 μm. The wet spinning process uses a syringe with an inner diameter of 0.21 mm, an advance speed of 0.8 min / mL, and a fluid circulation speed of 1.32 m / s.

2. The dopamine / sodium oxidized alginate composite photothermal hydrogel fiber prepared by the method of claim 1.

3. The application of the dopamine / sodium alginate composite photothermal hydrogel fiber as described in claim 2 in textile materials.

4. A photothermal therapy patch, characterized in that, It uses the dopamine / sodium oxidized alginate composite photothermal hydrogel fiber as described in claim 2.

5. A method for improving the utilization rate of dopamine in wet-spun hydrogel fibers, characterized in that, It uses the dopamine / sodium oxidized alginate composite photothermal hydrogel fiber as described in claim 2.

6. A method for enhancing the photothermal effect of hydrogel fibers under both sunlight and infrared light, characterized in that, It uses the dopamine / sodium oxidized alginate composite photothermal hydrogel fiber as described in claim 2.

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