Dopamine / oxidized sodium alginate composite photo-thermal hydrogel fiber and preparation method thereof

Abstract

The invention discloses a dopamine / oxidized sodium alginate composite photo-thermal hydrogel fiber and a preparation method thereof, and belongs to the field of functional fibers. A sodium alginate solution is used as a substrate, sodium alginate is partially oxidized, and dopamine and oxidized sodium alginate are combined to form Schiff base, so that the stability and the utilization rate of dopamine are improved; and the dopamine / oxidized sodium alginate composite photo-thermal hydrogel fiber is prepared through wet spinning. The dopamine in the prepared dopamine / oxidized sodium alginate composite photo-thermal hydrogel fiber is high in utilization rate.

Description

Technical Field

[0001] The invention relates to a dopamine / oxidized sodium alginate composite photothermal water gel fiber and a preparation method thereof, belonging to the field of functional fibers. Background Art

[0002] Hydrogel fibers differ significantly from traditional polymer fibers in many aspects. Hydrogel fibers are fibers with high water content. Their core feature is that they can absorb and release large amounts of water while maintaining their structure in water. Hydrogel fibers have both the performance characteristics of hydrogels and the structural advantages of fiber materials, making them a good drug delivery platform. The high specific surface area of ​​hydrogel fibers gives them better hygroscopicity, moisture retention, and breathability. They can simulate the microfiber structure of human tissues by regulating their size, such as nerve cells, muscle fibers, tendons, ligaments, and other tissues.

[0003] At present, hydrogel fibers are widely used in photothermal therapy. Photothermal therapy (PTT) is an emerging tumor treatment strategy that uses the photothermal effect of photothermal conversion materials (PTAs) to harvest energy from light of a specific wavelength and convert light energy into heat, thereby increasing the temperature of the surrounding environment, inhibiting tumor metastasis, and inducing the death of cancer cells. At the same time, PTT can also be used for photothermal therapy, achieving the effect of local rapid warming through natural light. In the current research process, good photothermal conversion effects are mostly achieved through dopamine.

[0004] Dopamine has good antioxidant, anti-inflammatory, antibacterial, antiviral and other drug activities, and can be oxidized and rearranged under specific conditions to self-polymerize to form polydopamine. Good biodegradability, photostability, and high photothermal conversion efficiency enable dopamine to participate in fiber modification, making it widely used in the field of biomedical materials; for example:

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

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

[0007] However, due to its strong hydrophilicity, dopamine is easy to seep out during the wet spinning process, resulting in a low utilization rate in hydrogel fibers; therefore, electrospinning is often used to prepare hydrogel fibers containing dopamine in the actual production process. However, the solvents used in electrospinning are mostly toxic organic solvents, which are very harmful; during the production process, the solution requires a long solidification time, and the operation involves high voltage, which places higher requirements on the equipment, making electrospinning more complicated and costly in the industrial process.

[0008] From the perspective of practical application, it is very necessary to prepare a dopamine / oxidized sodium alginate composite photothermal water gel fiber prepared by wet spinning with high dopamine utilization. Summary of the invention

[0009] [Technical issues]

[0010] Dopamine has extremely good hydrophilicity and easily seeps out during the wet spinning process, resulting in extremely low utilization rate.

[0011] [Technical solution]

[0012] In order to solve the above problems, the present invention uses sodium alginate solution as a substrate, partially oxidizes sodium alginate, combines dopamine and oxidized sodium alginate to form a Schiff base, so as to improve the stability and utilization rate of dopamine; and prepares dopamine / oxidized sodium alginate composite photothermal water gel fiber by wet spinning. The dopamine / oxidized sodium alginate composite photothermal water gel fiber prepared by the present invention has a high utilization rate of dopamine.

[0013] The first object of the present invention is to provide a method for preparing dopamine / oxidized sodium alginate composite photothermal water gel fiber, comprising the following steps:

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

[0015] (2) The spinning solution is wet-spinned to prepare dopamine / oxidized sodium alginate photothermal hydrogel fibers.

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

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

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

[0019] Adding sodium periodate solution to sodium alginate ethanol solution to carry out oxidation reaction; after a period of time, adding ethylene glycol to terminate the reaction, dialyzing and freeze-drying to obtain oxidized sodium alginate;

[0020] Wherein, 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] The sodium alginate ethanol solution is a mixed solution of sodium alginate and anhydrous ethanol; the dosage ratio of sodium alginate and anhydrous ethanol is 10-50 g:100 mL;

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

[0023] The sodium periodate solution is added by slow injection at a rate of 0.6-1 mL / min.

[0024] The oxidation reaction is carried out under light-proof conditions at 25 to 30° C. and stirring at 300 to 800 rpm for 2 to 6 hours.

[0025] Dialysis refers to dialysis using a MWCO3500Da dialysis bag for 1 to 5 days, with deionized water replaced at regular intervals.

[0026] Freeze drying is freeze drying at -40°C for 12-24h.

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

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

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

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

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

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

[0033] As an embodiment of the present invention, the extrusion speed of the spinning solution in the wet spinning 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 object of the present invention is the dopamine / oxidized sodium alginate composite photothermal water gel fiber prepared by the method described in the present invention.

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

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

[0037] The third object of the present invention is to use the dopamine / oxidized sodium alginate composite photothermal water gel fiber of the present invention in textile materials.

[0038] As an embodiment of the present invention, the textile material includes materials prepared by textile processing techniques such as knitting, weaving, braiding, and non-woven.

[0039] The fourth objective of the present invention is the application of the dopamine / oxidized sodium alginate composite photothermal water gel fiber of the present invention in the field of biomedicine.

[0040] As an 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, and the generated heat energy can be used to destroy cancer cells.

[0041] The fifth object of the present invention is a photothermal therapy patch, which adopts the dopamine / oxidized sodium alginate composite photothermal water gel fiber of the present invention.

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

[0043] The seventh object of the present invention is to provide a method for improving the photothermal effect of hydrogel fiber under both sunlight and infrared light, which adopts the dopamine / oxidized sodium alginate composite photothermal water gel fiber described in the present invention.

[0044] [Beneficial Effects]

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

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

[0047] (3) The dopamine / oxidized sodium alginate composite photothermal water gel fiber prepared by the present invention has excellent photothermal effect, as well as many excellent properties such as good biocompatibility and controllable biodegradability, and has important scientific research value and practical significance in the field of photothermal therapy. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] Figure 1 This is the infrared spectrum of the oxidized sodium alginate prepared in Example 1.

[0049] Figure 2 This is an electron micrograph of the dopamine / oxidized sodium alginate composite photothermal water gel fiber prepared in Example 1.

[0050] Figure 3 This is a thermal infrared thermal heating trend diagram of the dopamine / oxidized sodium alginate photothermal water gel nonwoven fabric prepared in Example 2.

[0051] Figure 4 This is a solar thermal heating trend diagram of the dopamine / sodium alginate oxide photothermal water gel nonwoven fabric prepared in Example 2.

[0052] Figure 5 This is an analysis of the antioxidant activity of the dopamine / oxidized sodium alginate composite photothermal water gel fiber nonwoven fabric prepared in Example 3.

[0053] Figure 6 This is a photothermal effect diagram of the dopamine / oxidized sodium alginate composite photothermal water gel fiber nonwoven fabric prepared in Example 3. DETAILED DESCRIPTION

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

[0055] Test method:

[0056] 1. DPPH test:

[0057] Add 1 mL of DPPH to ethanol in a dark environment; then weigh 5 mg of the sample and place it in a 2 mL centrifuge tube. Add 1 mL of 0.04 mg / mL DPPH ethanol solution to the above centrifuge tube and incubate at room temperature in a dark environment for 1 hour. Use an ELISA reader to test the absorbance of the solution at 517 nm.

[0058] 2. Photothermal test:

[0059] Cut the test sample into 1cm 2 The size was fixed, and the light source was provided by a solar simulator and thermal infrared light, respectively. The thermal infrared imager recorded the temperature change and heat transfer on the sample surface. Under room temperature conditions, the temperature was raised for 5 to 10 minutes and then lowered for 5 to 10 minutes to record the temperature change on the sample surface.

[0060] 3. Biocompatibility test:

[0061] Weigh 2 mg of sample and place it in a centrifuge tube, then add 800 μL of PBS to the 200 μm red blood cell suspension and incubate in a 37°C incubator for 1 hour. After the sample is incubated in a 37°C incubator for 1 hour, centrifuge at 5000 rpm for 5 minutes, aspirate the supernatant, and measure the absorbance of the supernatant at 540 nm using an ELISA reader.

[0062] 4. Determination of oxidation degree:

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

[0064] Prepare 0.25 mol / L hydroxylamine hydrochloride-methyl orange solution, add 0.1 g of oxidized alginic acid to 25 mL of hydroxylamine hydrochloride-methyl orange solution, calibrate the solution with NaOH, and record the volume of sodium hydroxide consumed and the pH value when the color changes.

[0065] Sodium alginate, dopamine hydrochloride, sodium periodate, ethylene glycol, MWCO3500Da dialysis bag, and calcium oxide are all commercially available.

[0066] The % involved in the examples without specific meaning refers to mass percentage, and the solution involved without specific solvent is water as the solvent.

[0067] Example 1

[0068] A method for preparing dopamine / oxidized sodium alginate composite photothermal water gel fiber comprises the following steps:

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

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

[0071] 100 mL of sodium periodate solution was slowly injected (at a rate of 0.8 mL / min) into 100 mL of sodium alginate ethanol solution, and the mixture was stirred evenly at 800 rpm at 30 °C for 4 h in a dark environment for oxidation reaction;

[0072] Afterwards, 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 oxidized sodium alginate;

[0073] (2) adding oxidized sodium alginate and dopamine hydrochloride to a sodium alginate aqueous solution with a mass concentration of 2%, stirring at 60° C. for 6 hours to form a Schiff base, thereby obtaining a spinning solution;

[0074] Wherein, the mass ratio of oxidized sodium alginate and dopamine hydrochloride is 1:1;

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

[0076] (3) A calcium chloride aqueous solution with a mass concentration of 3% was used as a coagulation bath for wet spinning, and wet spinning was performed on a flexible drawing spinning platform to prepare dopamine / oxidized sodium alginate photothermal water gel fibers (fineness of 37 μm); the wet spinning method used a syringe with a needle inner diameter of 0.21 mm, a propulsion speed of 0.8 min / mL, and a fluid circulation speed of 1.32 m / 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 test:

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

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

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

[0082] Example 2

[0083] A method for preparing a hydrogel nonwoven fabric using the dopamine / oxidized sodium alginate photothermal hydrogel fiber of Example 1 comprises the following steps:

[0084] The dopamine / sodium alginate oxide photothermal hydrogel fibers of Example 1 are wet-laid, uniformly precipitated, prepared into a hydrogel nonwoven fabric, and naturally air-dried to obtain a hydrogel nonwoven fabric;

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

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

[0087] Thermal infrared provides light source, and the thermal infrared imager records the temperature change and heat transfer of the sample surface. Finally, the temperature rise and fall trend is plotted using drawing software. The results are as follows: Figure 3 .

[0088] from Figure 3 It can be seen that the nonwoven fabric can quickly convert light energy into heat energy when the temperature rises from 28°C to 106°C within 5 minutes, indicating that the present invention has good light-to-heat conversion capability.

[0089] The same method is used to replace the light source with a solar simulator. The temperature rise and fall trend results are as follows: Figure 4 :

[0090] from Figure 4 It can be seen that the temperature of the nonwoven fabric rises from 34° C. to 81° C. within 5 minutes. The present 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 the sodium alginate aqueous solution in step (3) of Example 1 was adjusted to 1%, 3%, and 5%, and the other conditions were kept consistent with Example 1 to obtain hydrogel fibers; and then a 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 of antioxidant activity are as follows Figure 5 ;

[0095] from Figure 5 It can be seen that the nonwoven fabric has good antioxidant activity, and the antioxidant activity increases with the increase of dopamine content. When the mass concentration of dopamine in the sodium alginate aqueous solution is 1%, the DPPH free radical scavenging rate is 80.5%, when the mass concentration of dopamine in the sodium alginate aqueous solution is 3%, the DPPH free radical scavenging rate is 76.3%, and when the mass concentration of dopamine in the 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] Plexus 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°C to 45°C within 5 minutes; when the mass concentration of dopamine in the sodium alginate aqueous solution is 3%, the temperature rises from 34°C to 74°C within 5 minutes; when the mass concentration of dopamine in the sodium alginate aqueous solution is 5%, the temperature rises from 34°C to 72°C within 5 minutes; it can be seen that the photothermal performance difference between the concentrations of 3% and 5% is not large. From the perspective of cost saving, the mass concentration of dopamine in the spinning solution is selected to be 3%.

[0098] Comparative Example 1

[0099] The oxidized sodium alginate in the raw material of Example 1 was omitted, and other conditions or parameters were the same as those of Example 1 to obtain hydrogel fibers. Then, a nonwoven fabric was prepared according to Example 2.

[0100] The test results are as follows:

[0101] During the process of heating up for 5 minutes and cooling down for 5 minutes, the sample was heated up by 38°C when the thermal infrared light source was used, and by 15°C when the simulated sunlight light source was used.

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

[0103] Comparative Example 2

[0104] The oxidized sodium alginate and dopamine hydrochloride in Example 1 were omitted, and the sodium alginate solution was directly used as the spinning solution; other conditions or parameters were consistent with those 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 as above in the form of a preferred embodiment, it is not intended to limit the present invention. Anyone familiar with this technology can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be based on the definition of the claims.

Claims

1. A method for preparing dopamine / oxidized sodium alginate composite photothermal water gel fiber, characterized in that: The steps include: (1) mixing oxidized sodium alginate, dopamine, and a sodium alginate aqueous solution to react to form a Schiff base to obtain a spinning solution; (2) The spinning solution is wet-spinned to prepare dopamine / oxidized sodium alginate photothermal hydrogel fibers.

2. The method according to claim 1, characterized in that The degree of oxidation of the sodium alginate in step (1) is 10% to 40%.

3. The method according to claim 1, characterized in that: In step (1), the mass concentration of oxidized sodium alginate in the sodium alginate aqueous solution is 1% to 5%.

4. The method according to claim 1, characterized in that The reaction in step (1) is carried out at 40-80° C. for 2-10 hours.

5. Dopamine / oxidized sodium alginate composite photothermal water gel fiber prepared by the method according to any one of claims 1 to 4.

6. Use of the dopamine / oxidized sodium alginate composite photothermal water gel fiber according to claim 5 in textile materials.

7. Application of the dopamine / oxidized sodium alginate composite photothermal water gel fiber according to claim 5 in the field of biomedicine.

8. A photothermal therapy patch, characterized in that: It adopts the dopamine / oxidized sodium alginate composite photothermal water gel fiber described in claim 5.

9. A method for improving the utilization of dopamine in wet-spun hydrogel fibers, characterized in that: It adopts the dopamine / oxidized sodium alginate composite photothermal water gel fiber described in claim 5.

10. A method for improving the photothermal effect of hydrogel fibers under both sunlight and infrared light, characterized in that: It adopts the dopamine / oxidized sodium alginate composite photothermal water gel fiber described in claim 5.

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