Photoelectric response hydrogel materials for promoting wound healing, preparation methods and applications

Abstract

The present invention discloses a photo - electro - responsive hydrogel material for promoting wound healing, a preparation method thereof, and an application thereof. The photo - electro - responsive hydrogel material includes: a porous silicon membrane, the porous silicon membrane is provided with an N - doped region and a P - doped region; and a hydrogel, the hydrogel wraps the porous silicon membrane. Thereby, the wound healing speed is greatly improved, and by using the porous silicon membrane to achieve photo - electric conversion, the adverse effects of the photo - electro - responsive hydrogel material on the body are avoided to the greatest extent.

Description

Technical Field

[0001] The present invention belongs to the field of electrochemical energy storage, and particularly relates to a photoelectric response hydrogel material for promoting wound healing, a preparation method thereof, and an application thereof. Background Art

[0002] At present, some chronic wounds (especially the refractory wounds of diabetic patients) are difficult to repair by themselves, so there is an urgent need for a new treatment method to promote wound healing. Hydrogels have been widely used in wound repair due to their rich water content. They can not only remove necrotic tissues, absorb wound exudates, but also perform material exchange of CO2, O2, and H2O.

[0003] Recently, stimulus-responsive hydrogels have received increasing attention. Stimulus-responsive intelligent hydrogels refer to a class of materials that can rapidly respond to endogenous (pH, temperature, enzymes, etc.) or exogenous (light, magnetism, sound, etc.) stimuli, and the carrier itself undergoes specific physical or chemical changes to achieve controlled drug release. Compared with pH- and glucose-responsive hydrogels that need to rely on the physiological microenvironment of skin injury sites to play their roles, photoresponsive hydrogels have great controllability both in time and space due to the adjustable intensity and wavelength. Ultraviolet light has very limited applications in the biomedical field because it is harmful to some cell types. Near-infrared light (NIR), on the other hand, not only has little damage to cell tissues but also has good penetrability.

[0004] Therefore, it is of great significance to construct a photoelectric response hydrogel material with good biocompatibility. Summary of the Invention

[0005] The present invention aims to solve at least one of the technical problems in the related art to some extent. For this purpose, the object of the present invention is to provide a photoelectric response hydrogel material for promoting wound healing, a preparation method thereof, and an application thereof. Thereby, the wound healing speed is greatly improved, and by using a porous silicon membrane for photoelectric conversion, the adverse effects of the photoelectric response hydrogel material on the body are minimized.

[0006] In one aspect of the present invention, a photoelectric response hydrogel material for promoting wound healing is provided. According to an embodiment of the present invention, it includes:

[0007] A porous silicon membrane provided with an N-doped region and a P-doped region;

[0008] A hydrogel that wraps the porous silicon membrane.

[0009] For the optoelectronic response hydrogel material for promoting wound healing according to the above embodiments of the present invention, an N-doped region and a P-doped region in the porous silicon film form a PN junction, which endows the porous silicon film with optoelectronic conversion ability, thereby generating an electrical stimulation effect at the wound surface and promoting wound healing through electrical stimulation. The hydrogel is used to wrap the porous silicon film, enabling the porous silicon film to better adhere to the surfaces of tissues and wounds. Compared with traditional near-infrared light response materials, the advantages of the porous silicon film include: (1) Silicon has high biological safety, good biocompatibility, and can be biodegradable in the body without causing harm to the body; (2) In a liquid environment, the porous silicon film is not easily oxidized and degraded, and has good optoelectronic conversion stability; (3) The ultra-thin porous silicon film minimizes the impact on the body; (4) During the wound repair process, the porous silicon film with a porous structure is conducive to the circulation and exchange of nutrients and the like. Thus, the wound healing speed is greatly improved, and by using the porous silicon film to achieve optoelectronic conversion, the adverse effects of the optoelectronic response hydrogel material on the body are minimized to the greatest extent.

[0010] In addition, the optoelectronic response hydrogel material for promoting wound healing according to the above embodiments of the present invention may further have the following technical features:

[0011] In some embodiments of the present invention, the doping element of the N-doped region is phosphorus, and the doping element of the P-doped region is boron.

[0012] In some embodiments of the present invention, the concentration ratio of phosphorus element to nitrogen element in the porous silicon film is (10 15 -10 16 ) : (10 18 -10 20 ).

[0013] In some embodiments of the present invention, the pore diameter of the porous silicon film is 100 - 400 microns.

[0014] In some embodiments of the present invention, the thickness of the porous silicon film is 2 - 5 microns.

[0015] In some embodiments of the present invention, silicon pillars are provided in the porous silicon film.

[0016] In some embodiments of the present invention, the height of the silicon pillar is 2 - 3 microns.

[0017] In some embodiments of the present invention, the diameter of the silicon pillar is 1 - 3 microns.

[0018] In some embodiments of the present invention, the arrangement of the silicon pillars inside the porous silicon film is a matrix arrangement.

[0019] In some embodiments of the present invention, the hydrogel includes at least one of a body temperature-setting hydrogel and a room temperature-setting hydrogel.

[0020] In some embodiments of the present invention, the body temperature-setting hydrogel includes at least one of a chitosan thermosensitive hydrogel and a methylcellulose thermosensitive hydrogel.

[0021] In some embodiments of the present invention, the room temperature-setting hydrogel includes at least one of an agarose thermosensitive hydrogel and an F127 thermosensitive hydrogel.

[0022] In a second aspect of the present invention, the present invention provides a method for preparing the photo-responsive hydrogel material for promoting wound healing described in the above embodiments. According to the embodiments of the present invention, the method includes:

[0023] (1) Doping the porous silicon membrane to form an N-doped region and a P-doped region on the porous silicon membrane;

[0024] (2) Wrapping the hydrogel around the porous silicon membrane to form the photo-responsive hydrogel material.

[0025] According to the method of the above embodiments of the present invention, by doping the porous silicon membrane, an N-doped region and a P-doped region are formed on the porous silicon membrane. The PN junction endows the porous silicon membrane with the ability of photoelectric conversion, and then an electric stimulation effect is generated at the wound surface, and the wound healing is promoted through electric stimulation; by wrapping the hydrogel around the porous silicon membrane, it is beneficial to better fit the porous silicon membrane on the surface of tissues and wounds. Thus, the wound healing speed is greatly improved, and by using the porous silicon membrane to achieve photoelectric conversion, the adverse effects of the photo-responsive hydrogel material on the body are avoided to the greatest extent.

[0026] In addition, the method according to the above embodiments of the present invention may further have the following technical features:

[0027] In some embodiments of the present invention, the method of wrapping the hydrogel around the porous silicon membrane includes: covering the porous silicon membrane on the wound, and then using the hydrogel to wrap the porous silicon membrane; using 3D printing to print the hydrogel around the porous silicon membrane; using a mold to wrap the hydrogel around the porous silicon membrane.

[0028] In a third aspect of the present invention, there is provided a wound repair material, which includes the optoelectronic response hydrogel material for promoting wound healing described in the above embodiments or the optoelectronic response hydrogel material prepared by the method for preparing the optoelectronic response hydrogel material for promoting wound healing. Thus, the wound repair material is simple to manufacture, low in cost, and simple in structure, greatly improving the wound healing speed. Moreover, by using a porous silicon membrane for optoelectronic conversion, the adverse effects on the body are minimized to the greatest extent, and it has great market potential.

[0029] Additional aspects and advantages of the present invention will be given in part in the following description, become apparent in part from the following description, or be learned through the practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] The above and / or additional aspects and advantages of the present invention will become apparent and be readily understood from the description of the embodiments in conjunction with the following drawings, in which:

[0031] Figure 1 is a schematic structural diagram of a porous silicon membrane according to an embodiment of the present invention;

[0032] Figure 2 is a flowchart of a method for preparing an optoelectronic response hydrogel material for promoting wound healing according to an embodiment of the present invention;

[0033] Figure 3 is a flowchart of a method for preparing a porous silicon membrane according to an embodiment of the present invention;

[0034] Figure 4 is a comparison chart of the healing effects of mice in Example 1 and Comparative Example 1 of the present invention.

[0035] Reference Signs:

[0036] 100 - porous silicon membrane; 200 - hydrogel; 300 - silicon column. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0037] Embodiments of the present invention will be described in detail below. Examples of the embodiments are shown in the drawings, where the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The embodiments described below by referring to the drawings are exemplary and are intended to explain the present invention, and should not be construed as limiting the present invention.

[0038] In one aspect of the present invention, there is provided an optoelectronic response hydrogel material for promoting wound healing. According to an embodiment of the present invention, with reference to the attached Figure 1, the above-mentioned optoelectronic response hydrogel material includes: a porous silicon membrane 100, the porous silicon membrane 100 is provided with an N-doped region and a P-doped region; a hydrogel 200, the hydrogel 200 wraps the porous silicon membrane 100. The N-doped region and the P-doped region in the porous silicon membrane 100 form a PN junction, and the PN junction enables the porous silicon membrane 100 to have optoelectronic conversion ability, thereby generating an electrical stimulation effect at the wound surface, and promoting the healing of the wound through electrical stimulation. The hydrogel 200 is used to wrap the porous silicon membrane 100, so that the porous silicon membrane can better adhere to the surface of tissues and wounds. Thus, the healing speed of the wound is greatly improved, and by using the porous silicon membrane to achieve optoelectronic conversion, the adverse effects of the optoelectronic response hydrogel material on the body are avoided to the greatest extent.

[0039] The principle by which the optoelectronic response hydrogel material proposed by the present invention can achieve the above beneficial effects will be described in detail below:

[0040] The PN junction enables the porous silicon membrane to have optoelectronic conversion ability. After being irradiated by external light, the photo-generated carriers inside the porous silicon membrane will accumulate at the interface between the porous silicon membrane and the body fluid. The cations and anions in the body fluid will accumulate around the porous silicon membrane due to electrostatic action, and an electrical stimulation effect will be generated locally at the wound surface. By adjusting cell adhesion, growth and proliferation through this electrical stimulation, etc., the healing of the wound is promoted; using a flexible hydrogel to wrap the porous silicon membrane not only helps the hydrogel to wrap the brittle and fragile porous silicon membrane, thereby realizing the flexibility of the optoelectronic response hydrogel material, but also because of the injectability and fluidity of the hydrogel, the porous silicon membrane can better adhere to the surface of tissues and wounds.

[0041] Compared with traditional near-infrared light-responsive materials, the advantages of the porous silicon membrane include: (1) Silicon has high biological safety, good biocompatibility, and can be biodegradable in the body without causing harm to the body. In contrast, gallium arsenide in traditional near-infrared light-responsive materials contains arsenic elements, which has safety risks and the gallium arsenide material cannot be degraded in the body; (2) In a liquid environment, the porous silicon membrane is not easily oxidized and degraded, and has good optoelectronic conversion stability. In contrast, although the P3HT organic material can also achieve the near-infrared light-responsive effect, the P3HT organic material is easily oxidized and hydrolyzed in a liquid environment, resulting in unstable optoelectronic performance; (3) The ultra-thin porous silicon membrane minimizes the impact on the body; (4) During the wound repair process, the porous silicon membrane with a porous structure is conducive to the circulation and exchange of nutrients, etc.; (5) As the first-generation semiconductor material, the preparation process of silicon is mature and reliable.

[0042] In the embodiment of the present invention, the doping elements of the above N-doped region and the doping elements of the above P-doped region are not particularly limited. As a preferred technical solution, the doping element of the above N-doped region is phosphorus, and the doping element of the above P-doped region is boron.

[0043] According to a specific embodiment of the present invention, the concentration ratio of phosphorus element to nitrogen element in the above-mentioned porous silicon film is (10 15 -10 16 ):(10 18 -10 20 ). Thus, controlling the concentration ratio of phosphorus element to nitrogen element in the above-mentioned porous silicon film within the above range is beneficial to ensuring the formation of a PN junction on the porous silicon film, enabling the porous silicon film to have a high photoelectric conversion efficiency, and further being beneficial to improving the wound healing speed.

[0044] According to another specific embodiment of the present invention, the pore diameter of the above-mentioned porous silicon film is 100 - 400 microns. Thus, controlling the pore diameter of the porous silicon film within the above range is beneficial to the circulation and exchange of nutrients and the like in the organism.

[0045] According to yet another specific embodiment of the present invention, the thickness of the above-mentioned porous silicon film is 2 - 5 microns. Thus, controlling the thickness of the above-mentioned porous silicon film within the above range not only ensures the flexibility and good photoelectric conversion efficiency of the porous silicon film, but also avoids the problem of poor adhesion between the skin tissue and the porous silicon film. The inventor found that if the porous silicon film is too thin, it is not conducive to absorbing external light sources, resulting in a decrease in photoelectric conversion efficiency; if the porous silicon film is too thick, the flexibility of the porous silicon film is poor and it is fragile, which is not conducive to close adhesion with the skin tissue.

[0046] In the embodiment of the present invention, the volume of the above-mentioned porous silicon film is not particularly limited and can be selected according to the actual wound area to achieve a better healing effect.

[0047] In yet another specific embodiment of the present invention, referring to the attached Figure 1 , silicon columns 300 are provided in the above-mentioned porous silicon film 100. By providing the silicon columns 300, it is beneficial to both improve the adhesion degree between the photoelectric response type hydrogel material and in-vivo cells and regulate cell adhesion, growth, proliferation, etc.

[0048] Specifically, after silicon columns are provided inside the porous silicon film, a photoelectric response type hydrogel scaffold can be formed. The above-mentioned photoelectric response type hydrogel scaffold has a good adhesion degree with in-vivo tissues; compared with a planar structure, the setting of the silicon columns enables the photoelectric response type hydrogel material to better regulate the cell structure, thereby improving the cell adhesion, growth, and proliferation speed, etc.

[0049] According to yet another specific embodiment of the present invention, the height of the above-mentioned silicon column is 2 - 3 microns, and the diameter of the above-mentioned silicon column is 1 - 3 microns. Thus, controlling the height and diameter of the above-mentioned silicon column within the above range is beneficial to regulating the cell morphology, making it easier for cells to adhere to the surface of the porous silicon film and adhere more tightly.

[0050] In an embodiment of the present invention, the arrangement of the above-mentioned silicon pillars inside the above-mentioned porous silicon film is not particularly limited. The arrangement of the above-mentioned silicon pillars inside the above-mentioned porous silicon film can be a matrix arrangement. Thus, it is further beneficial to adjust the stretching of cells, and then improve the adhesion, growth, and proliferation rates of cells.

[0051] In an embodiment of the present invention, the number of the above-mentioned silicon pillars is not particularly limited and can be selected according to the volume of the porous silicon film to achieve a better healing effect.

[0052] In an embodiment of the present invention, the specific type of the above-mentioned hydrogel is not particularly limited. For example, the above-mentioned hydrogel includes natural hydrogels and synthetic hydrogels. Natural hydrogels include chitosan-based natural hydrogels, collagen, gelatin, and hyaluronic acid-based hydrogels. Synthetic hydrogels include polyacrylic acid hydrogels, polyvinyl alcohol hydrogels, and polyacrylamide hydrogels.

[0053] According to another specific embodiment of the present invention, the above-mentioned hydrogel includes at least one of a body temperature-setting hydrogel and a room temperature-setting hydrogel, preferably a body temperature-setting hydrogel. The body temperature-setting hydrogel can be solidified at physiological temperature. Therefore, the body temperature-setting hydrogel can be directly injected onto the wound surface provided with the porous silicon film, which is applicable to both irregular and regular wound surfaces.

[0054] According to another specific embodiment of the present invention, the above-mentioned body temperature-setting hydrogel includes at least one of a chitosan thermosensitive hydrogel and a methylcellulose thermosensitive hydrogel, preferably a chitosan thermosensitive hydrogel. Thus, it not only ensures that the chitosan thermosensitive hydrogel will solidify at physiological temperature, which is beneficial to improving the good fitting degree between the above-mentioned photo-responsive hydrogel scaffold and the in-vivo tissue, but also because chitosan has a certain antibacterial effect, the chitosan thermosensitive hydrogel can prevent the occurrence of post-traumatic infection. More preferably, the chitosan thermosensitive hydrogel is a chitosan / β-glycerophosphate gel.

[0055] According to another specific embodiment of the present invention, the above-mentioned room temperature-setting hydrogel includes at least one of an agarose thermosensitive hydrogel and an F127 thermosensitive hydrogel.

[0056] In a second aspect of the present invention, the present invention provides a method for preparing a photo-responsive hydrogel material for promoting wound healing. According to an embodiment of the present invention, referring to the attached Figure 2 , the above method includes:

[0057] S100: Set an N-doped region and a P-doped region on the porous silicon film

[0058] In this step, by doping the porous silicon membrane, an N-doped region and a P-doped region are formed on the porous silicon membrane. The PN junction endows the porous silicon membrane with the ability of photoelectric conversion, and then an electric stimulation effect is generated at the wound surface, and the wound healing is promoted through the electric stimulation.

[0059] As a specific example, referring to the appendix Figure 3 , the specific steps for preparing a porous silicon membrane with silicon pillars are as follows: (1) Inject phosphorus ions and nitrogen ions into the upper and lower surfaces of silicon respectively, and (2) Use photolithography and ion etching techniques to etch silicon pillars on the surface of the porous silicon membrane. It should be noted that: if the silicon to be injected with ions is itself a porous silicon membrane containing phosphorus ions, only nitrogen ions need to be injected on the other side of the porous silicon membrane away from the phosphorus ions.

[0060] S200: Wrap the hydrogel around the porous silicon membrane

[0061] In this step, by wrapping the hydrogel around the porous silicon membrane, it is beneficial to better fit the porous silicon membrane on the surfaces of tissues and wounds. Thereby, the wound healing speed is greatly improved, and by using the porous silicon membrane to achieve photoelectric conversion, the adverse effects of the photoelectric response type hydrogel material on the body are avoided to the greatest extent.

[0062] According to another specific embodiment of the present invention, the above-mentioned hydrogel is a chitosan thermosensitive hydrogel, specifically it can be a chitosan / β-glycerophosphate gel. Thus, it not only ensures that the chitosan / β-glycerophosphate gel will solidify at physiological temperature, which is beneficial to improving the good fitting degree between the above-mentioned photoelectric response type hydrogel scaffold and in-vivo tissues, but also because chitosan has a certain antibacterial effect, the chitosan / β-glycerophosphate gel can prevent the occurrence of post-traumatic infection.

[0063] As a specific example, the method for preparing the chitosan / β-glycerophosphate gel includes: (1) Mix chitosan and an acid to form an acid solution of chitosan; (2) Mix the β-glycerophosphate solution and the acid solution of chitosan to form a mixed solution; (3) Adjust the pH of the above-mentioned mixed solution to 7-8 to obtain the chitosan / β-glycerophosphate gel. The type of the above-mentioned acid is not particularly limited, for example, it can be acetic acid.

[0064] According to another specific embodiment of the present invention, the mass ratio of chitosan to β-glycerophosphate in the chitosan / β-glycerophosphate gel is (1.8-2.5):(2-10), preferably (2-2.5):4. The inventor found that if the content of β-glycerophosphate is too low, the gelation time of the chitosan / β-glycerophosphate hydrogel will be prolonged and even no gel will be formed; if the content of β-glycerophosphate is too high, it may cause strong toxicity to the human body.

[0065] In some embodiments of the present invention, the method of wrapping the above hydrogel around the above porous silicon membrane includes: (1) covering the wound with the above porous silicon membrane, and then injecting or directly applying the above hydrogel to the wound to achieve the effect of wrapping the above porous silicon membrane; (2) printing the above hydrogel around the above porous silicon membrane by 3D printing; (3) using a mold to wrap the above hydrogel around the above porous silicon membrane. It should be noted that if the hydrogel is a body temperature curable hydrogel, the above three methods can be used to achieve the hydrogel wrapping around the porous silicon membrane. If the non-body temperature curable hydrogel is wrapped around the above porous silicon membrane by method (1), since the curing temperature of the non-body temperature curable hydrogel is not the physiological temperature, the wrapping effect may be deteriorated.

[0066] In the third aspect of the present invention, the present invention provides a wound repair material, which includes the above-mentioned photo-responsive hydrogel material for promoting wound healing described in the above embodiments or the photo-responsive hydrogel material prepared by the method for preparing the above-mentioned photo-responsive hydrogel material for promoting wound healing. Thus, the wound repair material is simple to manufacture, low in cost, and simple in structure, greatly improving the wound healing speed. Moreover, by using the porous silicon membrane to achieve photoelectric conversion, the adverse effects on the body are avoided to the greatest extent, and it has great market potential.

[0067] In the embodiments of the present invention, the application fields of the above-mentioned wound repair material include but are not limited to the healing of intractable wounds in humans and the healing of intractable wounds in animals, preferably the healing of intractable wounds in humans.

[0068] The embodiments of the present invention are described in detail below. It should be noted that the embodiments described below are exemplary and are only used to explain the present invention and should not be construed as a limitation of the present invention. Additionally, if not explicitly stated, all reagents used in the following embodiments are commercially available or can be synthesized according to the methods described herein or known methods. For the reaction conditions not listed, they are also easily obtained by those skilled in the art.

[0069] Example 1

[0070] This example provides a method for preparing a photo-responsive hydrogel material for promoting wound healing, and the steps are as follows:

[0071] (l) Preparing a porous silicon membrane: Refer to the appendix Figure 3 , (1-1) First, select an SOI structure, and sequentially set a reticular structure Si, an insulating material (silicon dioxide), and a porous silicon membrane from bottom to top. The thickness of the topmost porous silicon membrane is about 2 microns, and the pore diameter of the topmost porous silicon membrane is 300 microns; (1-2) Inject n-type phosphorus ions and p-type boron ions into the upper and lower surfaces of the porous silicon membrane respectively. The concentration ratio of n-type phosphorus ions to p-type boron ions in the porous silicon membrane is 1015 : 10 18 : (1 - 3) Use photolithography and ion etching techniques to etch silicon pillars on the surface of the porous silicon membrane. The silicon pillars are arranged in a matrix pattern inside the porous silicon membrane. The height of the silicon pillars is about 2 microns, and the diameter of the silicon pillars is about 2 microns; (1 - 4) Use wet etching with hydrofluoric acid to remove the insulating material (silicon dioxide); (1 - 5) Transfer the porous silicon membrane to the bottom of a customized Teflon cylindrical mold (thickness about 0.8 mm, diameter about 6 mm), and the porous silicon membrane can be transferred to the target area;

[0072] (2) Prepare a temperature - sensitive hydrogel system (chitosan / β - glycerophosphate gel): (2 - 1) Use acetic acid solution to ultrasonically dissolve chitosan to prepare a chitosan acid solution with a w / v (weight - volume ratio) of 2.5%, and then place the above - mentioned chitosan acid solution at 4°C overnight; (2 - 2) Prepare β - glycerophosphate with a w / v (weight - volume ratio) of 40% using an aqueous solution, and gradually add the above - mentioned β - glycerophosphate drop - by - drop to the chitosan acid solution that has been kept overnight at 4°C. Mix them in a ratio of 9 mL of chitosan acid solution to 1 mL of β - glycerophosphate to obtain a solution with a w / v (weight - volume ratio) of 2.25% chitosan and a w / v (weight - volume ratio) of 4% β - glycerophosphate, thereby obtaining a chitosan / β - glycerophosphate mixed solution; (2 - 3) Use ammonia water to adjust the pH of the chitosan / β - glycerophosphate mixed solution to about 7.4 to obtain a chitosan / β - glycerophosphate gel. The mass ratio of chitosan to β - glycerophosphate in the chitosan / β - glycerophosphate gel is 2.25:4. Place the chitosan / β - glycerophosphate gel in a 37°C water bath to solidify;

[0073] (3) Refer to Appendix Figure 3 , use a Teflon cylindrical mold to transfer the porous silicon membrane into the hydrogel, thereby obtaining a photo - electro - responsive hydrogel material for promoting wound healing;

[0074] (4) Experimental design: Use streptozotocin to induce c57bl / 6 mice into diabetic mice, and then make a wound with a diameter of about 1 cm on their backs. Use this model to represent a refractory wound. Apply the above - mentioned photo - electro - responsive hydrogel material and near - infrared light stimulation. Take pictures and measure the wounds of the mice on days 3, 10, 14, 21, and 28 respectively. The statistical results are as Figure 4 shown. It is easy to see that the wound healing rate of the mice is relatively fast, and the final healing degree is relatively high.

[0075] Example 2

[0076] This example provides a preparation method of a photo - electro - responsive hydrogel material for promoting wound healing. The difference between this example and Example 1 is only that:

[0077] In step (1-1), the thickness of the top Si film is about 4 microns, and the pore size of the top Si film is 100 microns;

[0078] In step (1-2), the n-type phosphorus ions and p-type boron ions in the Si film are 10 16 :10 20 ;

[0079] In step (1-3), the height of the Si column is about 2.5 microns, and the diameter of the Si column is about 1 micron;

[0080] All other contents are the same as those in Example 1.

[0081] It is known through setting that the wound healing rate of the mice is basically the same as that of Example 1, and the final healing degree is relatively high.

[0082] Example 3

[0083] This example provides a preparation method of a photo-responsive hydrogel material for promoting wound healing. The difference between this example and Example 1 is only that:

[0084] In step (1-1), the thickness of the top Si film is about 5 microns, and the pore size of the top Si film is 400 microns;

[0085] In step (1-3), the height of the Si column is about 3 microns, and the diameter of the Si column is about 3 microns;

[0086] All other contents are the same as those in Example 1.

[0087] It is known through setting that the wound healing rate of the mice is basically the same as that of Example 1, and the final healing degree is relatively high.

[0088] Comparative Example 1

[0089] This comparative example provides a preparation method of a chitosan / β-glycerophosphate gel, and the steps are as follows:

[0090] (1) Dissolve chitosan by ultrasonic treatment with acetic acid solution to prepare a chitosan acid solution with a w / v (weight / volume ratio) of 2.5%. Then place the above chitosan acid solution at 4°C overnight. Prepare a β-glycerophosphate solution with a w / v (weight / volume ratio) of 40% using an aqueous solution. Dropwise add the above β-glycerophosphate into the chitosan acid solution after overnight storage at 4°C. Mix them in a ratio of 9 mL of chitosan acid solution to 1 mL of β-glycerophosphate to obtain a solution containing chitosan with a w / v (weight / volume ratio) of 2.25% and β-glycerophosphate with a w / v (weight / volume ratio) of 4%, thereby obtaining a chitosan / β-glycerophosphate mixed solution. Adjust the pH of the chitosan / β-glycerophosphate mixed solution to about 7.4 using ammonia water to obtain a chitosan / β-glycerophosphate gel. The mass ratio of chitosan to β-glycerophosphate in the chitosan / β-glycerophosphate gel is 2.25:4;

[0091] (2) Experimental design: Use streptozotocin to induce C57BL / 6 mice into diabetic mice, and then create a wound with a diameter of about 1 cm on their backs. Use this model to represent a refractory wound surface. Apply the above chitosan / β-glycerophosphate gel and near-infrared light stimulation. Take pictures and measure the wounds of the mice on days 3, 10, 14, 21, and 28 respectively. The statistical results are as Figure 4 shown.

[0092] Result analysis: On days 3 and 10, there were significant differences in the wound healing rates between Example 1 and Comparative Example 1. The wound healing rate of Example 1 was significantly higher than that of the control group. As time extended, the wounds of the mice in Comparative Example 1 also began to heal slowly. The final healing degree of Example 1 was slightly higher than that of Comparative Example 1.

[0093] Although the embodiments of the present invention have been shown and described above, it can be understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those of ordinary skill in the art can make changes, modifications, substitutions, and variations to the above embodiments within the scope of the present invention.

Claims

1. A photo-responsive hydrogel material for promoting wound healing, characterized in that, Comprising: A porous silicon membrane, the porous silicon membrane being provided with an N-doped region and a P-doped region, and the N-doped region and the P-doped region forming a PN junction; A hydrogel, the hydrogel wrapping the porous silicon membrane.

2. The optoelectronic response type hydrogel material according to claim 1, wherein The doping element of the N-doped region is phosphorus, and the doping element of the P-doped region is boron.

3. The optoelectronic response type hydrogel material according to claim 2, characterized in that The concentration ratio of phosphorus element to nitrogen element in the porous silicon film is (10 15 -10 16 ): (10 18 -10 20 ).

4. The optoelectronic response type hydrogel material according to claim 1 or 2, characterized in that, The pore size of the porous silicon membrane is 100 - 400 microns; And / or, the thickness of the porous silicon membrane is 2 - 5 microns; And / or, silicon pillars are provided in the porous silicon membrane.

5. The optoelectronic response type hydrogel material according to claim 4, wherein The height of the silicon pillars is 2 - 3 microns; And / or, the diameter of the silicon pillars is 1 - 3 microns; And / or, the arrangement mode of the silicon pillars inside the porous silicon membrane includes matrix arrangement.

6. The optoelectronic response type hydrogel material according to claim 1 or 2, characterized in that, The hydrogel includes at least one of a body temperature-setting hydrogel and a room temperature-setting hydrogel.

7. The optoelectronic response type hydrogel material according to claim 6, characterized in that The body temperature-setting hydrogel includes at least one of a chitosan thermosensitive hydrogel and a methylcellulose thermosensitive hydrogel; And / or, the room temperature-setting hydrogel includes at least one of an agarose thermosensitive hydrogel and an F127 thermosensitive hydrogel.

8. A method for preparing the optoelectronic response type hydrogel material for promoting wound healing according to any one of claims 1-7, characterized in that, Comprising: (1) Doping the porous silicon membrane to form an N-doped region and a P-doped region on the porous silicon membrane; (2) Wrapping the hydrogel around the porous silicon membrane to form the optoelectronic response type hydrogel material.

9. The method according to claim 8, wherein The method of wrapping the hydrogel around the porous silicon membrane includes: covering the porous silicon membrane at the wound, and then using the hydrogel to wrap the porous silicon membrane; printing the hydrogel onto the periphery of the porous silicon membrane by 3D printing; using a mold to wrap the hydrogel around the porous silicon membrane.

10. A wound repair material, characterized in that, Comprising the optoelectronic response type hydrogel material according to any one of claims 1 - 7 or the optoelectronic response type hydrogel material prepared by the method according to claim 8 or 9.

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