CN115895280A - Photosensitive silk fibroin hydrogel and preparation method and application thereof - Google Patents
Photosensitive silk fibroin hydrogel and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of biomedical engineering, and discloses a photosensitive silk fibroin hydrogel and a preparation method and application thereof. The photosensitive silk fibroin hydrogel comprises the following components in percentage by mass: 10 percent of 4- (4-hydroxymethyl-2-methoxy-5-nitrophenoxy) butyric acid modified silk fibroin, 1 to 10 percent of [ Ru (AAm-tpy) (Biq) (Cl) ] Cl and the balance of ultrapure water. The preparation method comprises the following steps: and uniformly mixing all the components of the photosensitive silk fibroin hydrogel dressing, and irradiating for 3-5min by using ultraviolet light to obtain the photosensitive silk fibroin hydrogel. The photosensitive silk fibroin hydrogel can be used as a medical dressing, and the medical dressing has antibacterial and anti-tumor functions under the condition of white light or natural light irradiation.
Description
Technical Field
The invention belongs to the field of biomedical engineering, and relates to a photosensitive silk fibroin hydrogel and a preparation method and application thereof.
Background
Currently, the clinical treatment of melanoma relies primarily on surgical resection. However, the residual tumor cells after surgery are very likely to cause tumor recurrence in patients. Meanwhile, in the operation process or the healing stage of an operation incision, the wound of a patient is very easily infected by bacteria such as staphylococcus aureus, so that the wound cannot be well healed, even chronic inflammation or sepsis is caused, and the life of the patient is seriously threatened. Therefore, it is necessary to develop a multifunctional wound dressing having both good anti-tumor and anti-bacterial properties.
Silk fibroin is a naturally-occurring protein, has good bioactivity, and can promote the repair of skin wound tissues, however, the lack of an antibacterial function is one of the main disadvantages of most pure silk fibroin biomedical materials as wound care products. In the photodynamic therapy, the photosensitizer releases active oxygen to kill bacteria or tumor cells under the condition of illumination. Compared with antibiotics, photodynamic therapy has good curative effect on drug-resistant bacterial infection.
However, existing photosensitizers often rely on near infrared light (660 nm-1200 nm) irradiation to release reactive oxygen species to kill bacteria or tumor cells. In nature and normal living environment, the near infrared radiation intensity is relatively low and is not enough to activate the photosensitizer, so special light source equipment and a complicated process are needed for treating the patient. Therefore, in clinical practical application, it is urgently needed to develop a wound dressing which is simpler and more convenient, has good anti-tumor and antibacterial properties under the white light condition, and can improve the wound repair of melanoma surgery patients.
Disclosure of Invention
The invention mainly aims to develop a photosensitive silk fibroin hydrogel, a precursor solution of the hydrogel can be gelled in situ at a wound under the ultraviolet illumination condition, and the silk fibroin hydrogel dressing which can obviously resist bacteria and kill tumor cells under the white light and natural light illumination conditions can inhibit tumor recurrence after operation, treat postoperative wound infection and promote good repair of the wound.
The invention provides a photosensitive silk fibroin hydrogel which comprises the following components in percentage by mass: 10 percent of 4- (4-hydroxymethyl-2-methoxy-5-nitrophenoxy) butyric acid modified silk fibroin, 1 to 10 percent of [ Ru (AAm-tpy) (Biq) (Cl) ] Cl and the balance of ultrapure water.
The invention provides a preparation method of the photosensitive silk fibroin hydrogel, which is characterized in that all components of the photosensitive silk fibroin hydrogel dressing are uniformly mixed, and then the ultraviolet light is irradiated for 3-5min to obtain the photosensitive silk fibroin hydrogel.
Further, the preparation method of the silk fibroin modified by 4- (4-hydroxymethyl-2-methoxy-5-nitrophenoxy) butyric acid comprises the following steps: dissolving silk fibroin in hexafluoroisopropanol, adding 4- (4-hydroxymethyl-2-methoxy-5-nitrophenoxy) butyric acid, stirring at room temperature in the dark until the solution is completely dissolved, reacting, removing the solvent by rotary evaporation after the reaction is finished, adding water for dissolving, dialyzing, and freeze-drying to obtain the silk fibroin modified by the 4- (4-hydroxymethyl-2-methoxy-5-nitrophenoxy) butyric acid.
Furthermore, the dosage ratio of the silk fibroin, the hexafluoroisopropanol and the 4- (4-hydroxymethyl-2-methoxy-5-nitrophenoxy) butyric acid is 0.45g (3 mL) (0.2-2) g, the reaction time is 24h, and the dialysis time is 3 days.
Further, the preparation method of the [ Ru (AAm-tpy) (Biq) (Cl) ] Cl comprises the following steps:
s1. Synthesis of NH2-tpy: dissolving potassium hydroxide in DMSO, heating to 65 ℃, dropwise adding 3-amino-1-propanol while stirring, stirring for a period of time after dropwise adding, adding 4 '-chloro-2,2': 6', 2' -terpyridine for reaction, cooling to room temperature after reaction, pouring into deionized water, extracting with dichloromethane, drying with anhydrous sodium sulfate, decompressing and spin-drying the solvent, and recrystallizing with ethyl acetate to obtain NH 2 -tpy；
S2. Synthesis of AAM-tpy: dissolving NH2-tpy and triethylamine in tetrahydrofuran, adding acryloyl chloride under the condition of ice-water bath and under the protection of nitrogen, reacting completely at room temperature, removing a solvent by rotary evaporation after the reaction is finished, dissolving in dichloromethane, washing with saturated salt water to remove impurities, drying, removing dichloromethane by rotary evaporation to obtain a crude product, and purifying the crude product by using an alumina column chromatography to obtain AAM-tpy;
S3.Ru(Aam-tpy)Cl 3 the synthesis of (2): ruCl is added 3 Dissolving H2O and AAm-tpy in ethanol for reflux reaction, cooling to room temperature after reaction, filtering, and filtering to obtain solidThe resulting solid was washed with ethanol and diethyl ether in this order, followed by vacuum drying to give Ru (Aam-tpy) Cl 3 ；
S4.[Ru(AAm-tpy)(Biq)(Cl)]And (3) Cl synthesis: ru (Aam-tpy) Cl 3 And 2,2' -biquinoline are dissolved in the mixed solvent of ethanol and water, degassed with nitrogen for 5min, and refluxed in the dark under the protection of nitrogen, after the reaction is finished, filtered, collected filtrate is decompressed, and the solvent is removed, and then purified to obtain [ Ru (AAm-tpy) (Biq) (Cl)]Cl。
Further, in step S1, the dosage ratio of potassium hydroxide, DMSO, 3-amino-1-propanol, 4' -chloro-2,2 ':6',2 ″ -terpyridine was 0.298g, 0.42g.
Further, in step S2, the amount ratio of NH2-tpy, triethylamine, tetrahydrofuran, and acryloyl chloride was 0.362g.
Further, in step S3, ruCl 3 The ratio of H2O, AAm-tpy to ethanol was 0.163g.
Further, in step S4, ru (Aam-tpy) Cl 3 2,2' -biquinoline and the mixed solvent of ethanol and water, wherein the volume ratio of ethanol to water in the mixed solvent of ethanol and water is 1:1, the ratio of the used amount of the mixed solvent of ethanol and water is 0.33g.
Furthermore, the invention provides application of the photosensitive silk fibroin hydrogel or the photosensitive silk fibroin hydrogel prepared by the preparation method in medical dressings, and the medical dressings have antibacterial and anti-tumor functions under the conditions of white light or natural light irradiation.
Further, the white light is 100mWcm -2 White light.
Compared with the prior art, the precursor solution of the hydrogel can form gel in situ at the wound under the ultraviolet illumination condition, can kill more than 85 percent of tumor cells in an in-vitro experiment within 10min under white light or natural light, effectively inhibits tumor recurrence, can treat bacterial infection of the wound, has the illumination sterilization rate of more than 95 percent on staphylococcus aureus at the wound, and promotes wound repair after tumor resection.
Drawings
FIG. 1 is a graph showing the results of in vitro test of the capability of the hydrogel obtained in example 2 to kill tumor cells by irradiation;
FIG. 2 is a graph showing the results of the in vivo antibacterial property test of the hydrogel obtained in example 2.
Detailed Description
The invention will be better understood from the following examples. However, it is easily understood by those skilled in the art that the descriptions of the embodiments are only for illustrating the present invention and should not be construed as limiting the present invention as detailed in the claims.
Example 1
Dissolving 0.45g of silk fibroin in 3mL of hexafluoroisopropanol, adding 4- (4-hydroxymethyl-2-methoxy-5-nitrophenoxy) butyric acid (0.2 g), stirring away from light at room temperature until the solution is completely dissolved, reacting for 24h, removing the solvent by rotary evaporation, adding water for dissolving, dialyzing for 3 days, freeze-drying to obtain the silk fibroin modified by 4- (4-hydroxymethyl-2-methoxy-5-nitrophenoxy) butyric acid, dissolving the silk fibroin modified by 4- (4-hydroxymethyl-2-methoxy-5-nitrophenoxy) butyric acid in ultrapure water to obtain a solution with the concentration of 10w/v%, adding [ Ru (AAm-tpy) (Biq) (Cl) ] into the solution according to the mass ratio of the silk fibroin modified by 4- (4-hydroxymethyl-2-methoxy-5-nitrophenoxy) butyric acid to [ Ru (AAm-tpy) (Biq) (Cl) ] Cl to obtain 1:1, and stirring until the solution is completely dissolved. Forming hydrogel under 365nm ultraviolet light (50 mW/cm 2) for 5 min.
Example 2
Dissolving 0.45g of silk fibroin in 3mL of hexafluoroisopropanol, adding 4- (4-hydroxymethyl-2-methoxy-5-nitrophenoxy) butyric acid (2 g), stirring at room temperature in the dark until the silk fibroin is completely dissolved, reacting for 24h, removing the solvent by rotary evaporation, adding water for dissolving, dialyzing for 3 days, freeze-drying to obtain the silk fibroin modified by 4- (4-hydroxymethyl-2-methoxy-5-nitrophenoxy) butyric acid, dissolving the silk fibroin modified by 4- (4-hydroxymethyl-2-methoxy-5-nitrophenoxy) butyric acid in ultrapure water to obtain a solution with the concentration of 10w/v%, adding [ Ru (AAm-tpy) (Biq) (3236) (Cl) ] Cl into the solution according to the mass ratio of the silk fibroin modified by 4- (4-hydroxymethyl-2-methoxy-5-nitrophenoxy) butyric acid to [ Ru (AAm-tpy) (Biq) (Cl) ] Cl, and stirring until the silk fibroin is completely dissolved. Forming hydrogel under 365nm ultraviolet light (50 mW/cm 2) for 5 min.
Example 3
Dissolving 0.45g of silk fibroin in 3mL of hexafluoroisopropanol, adding 4- (4-hydroxymethyl-2-methoxy-5-nitrophenoxy) butyric acid (2 g), stirring in the dark at room temperature until complete dissolution, reacting for 24h, removing the solvent by rotary evaporation, adding water for dissolution, dialyzing for 3 days, lyophilizing to obtain 4- (4-hydroxymethyl-2-methoxy-5-nitrophenoxy) butyric acid modified silk fibroin protein, dissolving the 4- (4-hydroxymethyl-2-methoxy-5-nitrophenoxy) butyric acid modified silk fibroin protein in ultrapure water to obtain a solution with a concentration of 10w/v%, adding [ Ru (AAm-tpy) (Biq) (Cl) ] into the solution according to a mass ratio of the 4- (4-hydroxymethyl-2-methoxy-5-nitrophenoxy) butyric acid modified silk fibroin to [ Ru (AAm-tpy) (Biq) (Cl) ] Cl of 1.1, and stirring until complete dissolution. Forming hydrogel under 365nm ultraviolet light (50 mW/cm 2) for 5 min.
Test example 1
Compressive strength testing of hydrogels: the hydrogel obtained in examples 1 to 3 was formed into a cylinder having a diameter of 1.5cm and a height of 1cm, and compressed at a displacement rate of 5mm/min by using an electronic universal material tester until the hydrogel was fractured, and the compressive strengths thereof were measured to be 0.03MPa, 0.1MPa, and 0.89MPa, respectively.
Test example 2
The in vitro tumor cell culture is utilized to test the performance of the product for killing the tumor cells under the white light irradiation. B16F10 melanoma cells were seeded on the hydrogel prepared in example 2 using LED white light (100 mWcm) -2 ) And after irradiating the hydrogel by natural light for 10 minutes, detecting the Cell viability by using a Cell CountingKit-8 kit, and comparing the Cell viability with that of the unirradiated hydrogel. Due to [ Ru (AAm-tpy) (Biq) (Cl)]Cl can absorb visible light and release active oxygen to kill bacteria and tumor cells, as shown in figure 1, the product is in LED white light (100 mWcm) -2 ) Or more than 85% of tumor cells can be killed by irradiating under natural light for 10 min.
Test example 3
The product is tested to kill staphylococcus aureus under white light irradiation by using a mouse back skin injury drug-resistant bacteria infection model. Filling of the golden color with the hydrogel prepared in example 2Back wound of Staphylococcus infected rat by LED white light (100 mWcm) -2 ) And irradiating hydrogel on the affected part with natural light for 10 minutes, and after 3 days, taking the affected part tissue for bacteria culture and comparing with the mouse tissue without irradiation treatment. As shown in figure 2, after the treatment of white light or natural light, the number of drug-resistant bacteria at the wound is obviously reduced, the sterilization rate of the product under the white light or natural light is more than 90%, and the antibacterial effect is obvious.
Claims (10)
1. The photosensitive silk fibroin hydrogel is characterized by comprising the following components in percentage by mass: 10 percent of 4- (4-hydroxymethyl-2-methoxy-5-nitrophenoxy) butyric acid modified silk fibroin, 1 to 10 percent of [ Ru (AAm-tpy) (Biq) (Cl) ] Cl and the balance of ultrapure water.
2. The method for preparing the photosensitive silk fibroin hydrogel of claim 1, wherein the photosensitive silk fibroin hydrogel is obtained by uniformly mixing the components of the photosensitive silk fibroin hydrogel dressing and irradiating the mixture for 3-5min by using ultraviolet light.
3. The method of claim 2, wherein the 4- (4-hydroxymethyl-2-methoxy-5-nitrophenoxy) butyric acid modified silk fibroin is prepared by: dissolving silk fibroin in hexafluoroisopropanol, adding 4- (4-hydroxymethyl-2-methoxy-5-nitrophenoxy) butyric acid, stirring at room temperature in the dark until the solution is completely dissolved, reacting, removing the solvent by rotary evaporation after the reaction is finished, adding water for dissolving, dialyzing, and freeze-drying to obtain the silk fibroin modified by the 4- (4-hydroxymethyl-2-methoxy-5-nitrophenoxy) butyric acid.
4. The preparation method of claim 3, wherein the ratio of the amounts of the silk fibroin, the hexafluoroisopropanol and the 4- (4-hydroxymethyl-2-methoxy-5-nitrophenoxy) butyric acid is 0.453 mL (0.2-2) g, the reaction time is 24h, and the dialysis time is 3 days.
5. The method of claim 2, wherein the [ Ru (AAm-tpy) (Biq) (Cl) ] Cl ] is prepared by a method comprising the steps of:
s1. Synthesis of NH2-tpy: dissolving potassium hydroxide in DMSO, heating to 65 ℃, dropwise adding 3-amino-1-propanol while stirring, stirring for a period of time after dropwise adding, adding 4 '-chloro-2,2': 6', 2' -terpyridine for reaction, cooling to room temperature after reaction, pouring into deionized water, extracting with dichloromethane, drying with anhydrous sodium sulfate, decompressing and spin-drying the solvent, and recrystallizing with ethyl acetate to obtain NH 2 -tpy；
S2. Synthesis of AAM-tpy: dissolving NH2-tpy and triethylamine in tetrahydrofuran, adding acryloyl chloride under the condition of ice-water bath and under the protection of nitrogen, reacting completely at room temperature, removing a solvent by rotary evaporation after the reaction is finished, dissolving in dichloromethane, washing with saturated salt water to remove impurities, drying, removing dichloromethane by rotary evaporation to obtain a crude product, and purifying the crude product by using an alumina column chromatography to obtain AAM-tpy;
S3.Ru(Aam-tpy)Cl 3 the synthesis of (2): adding RuCl 3 Dissolving H2O and AAm-tpy in ethanol for reflux reaction, cooling to room temperature after the reaction is finished, filtering, washing the filtered solid with ethanol and diethyl ether in sequence, and drying in vacuum to obtain Ru (Aam-tpy) Cl 3 ；
S4.[Ru(AAm-tpy)(Biq)(Cl)]And (3) Cl synthesis: ru (Aam-tpy) Cl 3 And 2,2' -biquinoline are dissolved in the mixed solvent of ethanol and water, degassed with nitrogen for 5min, and refluxed in the dark under the protection of nitrogen, after the reaction is finished, filtered, collected filtrate is decompressed, and the solvent is removed, and then purified to obtain [ Ru (AAm-tpy) (Biq) (Cl)]Cl。
6. The method of claim 5, wherein in step S1, the ratio of potassium hydroxide, DMSO, 3-amino-1-propanol, 4' -chloro-2,2 ':6',2 "-terpyridine is 0.298g.
7. The preparation method according to claim 5, wherein in step S2, the ratio of the amount of NH2-tpy to the amount of triethylamine, tetrahydrofuran and acryloyl chloride is 0.362g, and the amount of each of the components is 1.8 mL.
8. The method of claim 5, wherein in step S3, ruCl is added 3 The ratio of H2O, AAm-tpy to ethanol was 0.163g.
9. The process according to claim 5, wherein in step S4, ru (Aam-tpy) Cl 3 2,2' -biquinoline and the mixed solvent of ethanol and water, wherein the volume ratio of ethanol to water is 1:1, the dosage ratio of 0.33g.
10. The use of the photosensitive silk fibroin hydrogel of claim 1 or the photosensitive silk fibroin hydrogel prepared by the preparation method of any one of claims 2-9 in a medical dressing having antibacterial and anti-tumor functions under the irradiation of white light or natural light.
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| CN115028903A (en) * | 2022-07-07 | 2022-09-09 | 广州创赛生物医用材料有限公司 | Hydrogel and preparation method and application thereof |
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| CN107987287A (en) * | 2017-11-15 | 2018-05-04 | 华东理工大学 | Photic nitroso cross-linked hydrogel material and preparation method and application |
| CN115028903A (en) * | 2022-07-07 | 2022-09-09 | 广州创赛生物医用材料有限公司 | Hydrogel and preparation method and application thereof |
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