A controllable self-destructive hydrogel and its preparation method and application
By mixing functionalized polymers in GO aqueous medium and reacting with histidine to form a controllable self-destructive hydrogel, the problem of inaccurate control of hydrogel degradation in the prior art is solved, and the problem of hydrogel degradation under mild conditions is achieved Rapid glue formation and controllable degradation, suitable for applications such as complex three-dimensional structure construction and cell release.
Patent Information
- Application Number
- CN202410270385.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-03-11
- Publication Date
- 2025-02-14
- Estimated Expiration
- 2044-03-11
AI Technical Summary
The prior art cannot accurately control the degradation position and proportion of hydrogels under mild conditions, limiting its use in engineering applications.
By dissolving cyanoacetate functionalized polymer, benzaldehyde functionalized polymer and hydrophilic PEG or PEG derivatives in GO aqueous medium, a GO mixed functionalized polymer solution is formed and reacted with histidine. Rapidly form a controlled self-destructive hydrogel.
A controllable self-destructive hydrogel that is rapidly formed under mild conditions has fast gel formation, self-healing and good biocompatibility, and can print out any shape of three-dimensional structure in histidine solution, and Degradation at the liquid level shows controllable self-destructive behavior.
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Figure CN118085340B_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the field of controllable self-destructive hydrogels and relates to a hydrogel, in particular to a controllable self-destructive hydrogel and a preparation method and application thereof. Background Art
[0002] Hydrogel is a network structure formed by cross-linking hydrophilic polymers and contains a large amount of water. Its porous network structure, high water content and inherent biocompatibility make it widely used in functional materials and carriers. Constructing hydrogels with special morphology or spatial structure is extremely important for unlocking new applications. The current technology mainly selectively removes certain specific parts of hydrogels by etching, grinding and other methods. Moreover, complex mechanical equipment and strict processing conditions severely limit its wide application. In order to break through the limitations of existing methods, triggering hydrogel degradation through external stimuli such as enzymes, temperature, light, pH, etc. to achieve hydrogel removal is the current main solution strategy, and it has been widely used in smart sensing and drug carriers. Although a variety of strategies have been developed for constructing hydrogels with special morphological structures, current means still cannot accurately control the removal position and proportion of hydrogels. Therefore, developing an intelligent hydrogel system that can precisely control degradation under mild conditions is still a challenge for various engineering applications. Summary of the invention
[0003] The present invention provides a controllable self-destructive hydrogel and a preparation method and application thereof, so as to overcome the defects of the prior art.
[0004] To achieve the above object, the present invention provides a method for preparing a controllable self-destructive hydrogel, which has the following characteristics: adding a GO mixed functionalized polymer solution into a histidine solution to obtain the controllable self-destructive hydrogel; the GO mixed functionalized polymer solution is obtained by mixing a cyanoacetate functionalized polymer, a benzaldehyde functionalized polymer and a hydrophilic PEG or PEG derivative in a GO aqueous medium;
[0005] The structural formula of cyanoacetate functionalized polymer is:
[0006]
[0007] Where n is the degree of polymerization, 50≤n≤1000;
[0008] The structural formula of benzaldehyde functionalized polymer is:
[0009]
[0010] Wherein, m is the degree of polymerization, 10≤m≤500;
[0011] The structural formula of PEG is:
[0012]
[0013] Wherein, p is the degree of polymerization, 50≤p≤1000.
[0014] In the GO aqueous medium, the reaction between the cyanoacetate functionalized polymer and the benzaldehyde functionalized polymer is inhibited, and the GO mixed functionalized polymer solution can remain in a liquid state for several days. Histidine can complex with GO to form a histidine-GO complex, which can quickly trigger the reaction between the cyanoacetate and benzaldehyde functional groups, resulting in the rapid formation of a GO composite hydrogel (controllable self-destructive hydrogel). The addition of hydrophilic PEG or PEG derivatives does not affect the reaction between the cyanoacetate and benzaldehyde functional groups, and thus does not affect the gelation time and mechanical strength of the GO composite hydrogel. The GO composite hydrogel has the advantages of rapid gelation triggered by histidine, self-healing, and good biocompatibility, and the GO mixed functionalized polymer solution can be printed in a histidine solution to obtain a three-dimensional structure of any shape.
[0015] Furthermore, the present invention provides a method for preparing a controllable self-destructive hydrogel, which may also have the following characteristics: wherein the preparation method of the cyanoacetate functionalized polymer is: a polymer containing a hydroxyl group and cyanoacetic acid are dissolved in a solvent, and a condensation reaction is carried out under the catalysis of EDC·HCl and DMAP to obtain the cyanoacetate functionalized polymer; the solvent is dichloromethane, N,N-dimethylformamide, dimethyl sulfoxide, a mixed solvent of dichloromethane and water, a mixed solvent of N,N-dimethylformamide and water, or a mixed solvent of dimethyl sulfoxide and water; the reaction time is 24 to 72 hours, preferably 48 hours; the reaction temperature is 10 to 40°C, preferably 25°C; the molar ratio of the polymer containing a hydroxyl group, cyanoacetic acid, EDC·HCl and DMAP is 1:1 to 5:5:0.25.
[0016] Furthermore, the present invention provides a method for preparing a controllable self-destructive hydrogel, which may also have the following characteristics: wherein the preparation method of the benzaldehyde functionalized polymer is: a polymer containing a hydroxyl group and p-formylbenzoic acid are dissolved in a solvent, and a condensation reaction is carried out under the catalysis of EDC·HCl and DMAP to obtain the benzaldehyde functionalized polymer; the solvent is dichloromethane, N,N-dimethylformamide, dimethyl sulfoxide, a mixed solvent of dichloromethane and water, a mixed solvent of N,N-dimethylformamide and water, or a mixed solvent of dimethyl sulfoxide and water; the reaction time is 24 to 72 hours, preferably 48 hours; the reaction temperature is 10 to 40°C, preferably 25°C; the molar ratio of the polymer containing a hydroxyl group, p-formylbenzoic acid, EDC·HCl and DMAP is 1:1 to 5:5:0.25.
[0017] Furthermore, the present invention provides a method for preparing a controllable self-destructive hydrogel, which may also have the following characteristics: wherein the solvent of the GO mixed functionalized polymer solution is water, saline or buffer solution; the solvent of the histidine solution is water, saline or buffer solution.
[0018] Furthermore, the present invention provides a method for preparing a controllable self-destructive hydrogel, which may also have the following characteristics: wherein the temperature at which the GO mixed functionalized polymer solution and the histidine solution are mixed is 4 to 37°C, preferably 25°C.
[0019] Furthermore, the present invention provides a method for preparing a controllable self-destructive hydrogel, which may also have the following characteristics: wherein, in the GO mixed functionalized polymer solution, the mass-volume concentration of the cyanoacetate functionalized polymer is 5-40%, preferably 10%; the mass-volume concentration of the benzaldehyde functionalized polymer is 5-40%; the mass-volume concentration of GO is 2-30%; the mass-volume concentration of PEG or PEG derivatives is 2-50%; the mass-volume concentration of the histidine solution is 1-30%, preferably 5-15%.
[0020] Furthermore, the present invention provides a method for preparing a controllable self-destructive hydrogel, which may also have the following characteristics: wherein the PEG derivative is PEGDA (polyethylene glycol dimethyl ester).
[0021] The present invention also provides a controllable self-destructive hydrogel prepared by the preparation method.
[0022] The present invention also provides the application of the above-mentioned controllable self-destructive hydrogel in 3D printing, which has the following characteristics: the GO mixed functionalized polymer solution is used as the ink material for 3D printing, printed into a histidine solution to form a controllable self-destructive hydrogel; the controllable self-destructive hydrogel degrades on the liquid surface of the histidine solution.
[0023] Furthermore, the present invention provides the application of the above-mentioned controllable self-destructive hydrogel in 3D printing, which may also have the following characteristics: wherein, the controllable self-destructive hydrogel printed by the GO mixed functionalized polymer solution prepared from the PEG derivative PEGDA, after the liquid surface of the histidine solution is degraded, is blocked by ultraviolet curing to obtain a partially degraded controllable self-destructive hydrogel.
[0024] Therefore, the printed three-dimensional structure can be gradually degraded along the printing route, exhibiting controllable self-destructive behavior, and can simultaneously achieve the construction and controllable degradation of complex three-dimensional structures, the storage and self-clearance of information, and the on-demand release of cells.
[0025] The beneficial effects of the present invention are:
[0026] The present invention dissolves a cyanoacetate functionalized polymer, a benzaldehyde functionalized polymer and a hydrophilic PEG or PEG derivative in an aqueous dispersion medium containing GO to obtain a GO mixed functionalized polymer solution, and then adds histidine to the GO mixed functionalized polymer solution, which can quickly form a dynamic hydrogel material cross-linked by dynamic C=C double bonds, and the preparation process is controllable, the preparation conditions are mild, and the gelation speed is fast. Based on this, when the GO mixed functionalized polymer solution is printed in a histidine solution, a controllable self-destructive hydrogel can be obtained, and when one end of the controllable self-destructive hydrogel contacts the liquid surface of the histidine solution, self-destructive degradation can occur until the controllable self-destructive hydrogel is completely degraded. The mechanism of the self-destruction phenomenon of the hydrogel mainly originates from the diffusion effect caused by the surface tension of the histidine solution and the strong water absorption caused by the addition of PEG or PEG derivatives. By changing different parameters including the composition, surface tension, morphology, etc. of the controllable self-destructive hydrogel, the movement trajectory and self-destruction process of the controllable self-destructive hydrogel can be regulated.
[0027] The preparation process of the present invention is controllable, the preparation conditions are mild, and the gelation speed is fast. With the help of 3D printing technology, the construction and controllable degradation of complex three-dimensional structures, the storage and self-clearance of information, and the on-demand release of cells can be achieved simultaneously, so it has shown great application prospects in soft robots, anti-counterfeiting, controlled drug release and other related fields. Compared with the existing self-destructive hydrogel, the hydrogel of the present invention has the advantages of simple preparation process, good formability, and sensitive response. BRIEF DESCRIPTION OF THE DRAWINGS
[0028] Figure 1 is a hydrogen nuclear magnetic resonance spectrum of the cyanoacetate functionalized polymer (cyanoacetate functionalized dextran DEX-CA) in Example 1;
[0029] Figure 2 is the hydrogen nuclear magnetic resonance spectrum of the benzaldehyde functionalized polymer (benzaldehyde functionalized dextran DEX-BA) in Example 1;
[0030] Figure 3 is the viscosity test result of the GO mixed functionalized polymer solution of Example 1;
[0031] Figure 4 This is a time scanning test diagram of the GO composite hydrogel of Example 1;
[0032] Figure 5 is the viscosity test result of the GO mixed functionalized polymer solution of Example 2;
[0033] Figure 6 is a diagram of the degradation process of the controllable self-destructive hydrogel of Example 9;
[0034] Figure 7is a diagram showing the process of shape fixation of the controllable self-destructive hydrogel of Example 11 under ultraviolet light irradiation;
[0035] Figure 8 is a process diagram of self-elimination and shape fixation of the "B" type controllable self-destructive hydrogel of Example 11;
[0036] Fig. 9 This is the toxicity test result of GO composite hydrogel on NIH 3T3 cells;
[0037] Fig.10 is a cell fluorescence image of the controllable self-destructive hydrogel encapsulating cells in Example 12;
[0038] Fig.11 This is a fluorescence image of cells released from the controllable self-destructive hydrogel encapsulating cells in Example 12 after degradation. DETAILED DESCRIPTION
[0039] The present invention is further described below in conjunction with specific embodiments.
[0040] Example 1
[0041] The present embodiment provides a controllable self-destructive hydrogel, and the preparation method thereof is as follows: dissolving a cyanoacetate functionalized polymer (DEX-CA, number average molecular weight 7000, 15 mg), a benzaldehyde functionalized polymer (DEX-BA, number average molecular weight 7000, 15 mg) and PEG (number average molecular weight 600) in a GO dispersion (5 mg / mL, 150 uL) to obtain a GO mixed functionalized polymer solution, and then adding histidine to obtain a GO composite hydrogel with a gelation time of 1 s.
[0042] The preparation method of the cyanoacetate functionalized polymer is as follows: 5 g of dextran, 0.15 g of DMAP and 3.5 g of cyanoacetic acid are dissolved in 60 mL of DMSO solution, and then 6.71 g of EDC·HCl is added to the reaction system. After reacting at room temperature for 48 hours, the mixture system is dialyzed in water for 3 days and freeze-dried to obtain a light yellow cyanoacetate functionalized dextran DEX-CA. The results of nuclear magnetic resonance analysis of DEX-CA are as follows Figure 1 shown.
[0043] The preparation method of the benzaldehyde functionalized polymer is as follows: 5 g of dextran, 0.15 g of DMAP and 3.5 g of p-formylbenzoic acid are dissolved in 60 mL of DMSO solution, and then 6.71 g of EDC·HCl is added to the reaction system. After reacting at room temperature for 48 hours, the mixture system is dialyzed in water for 3 days and freeze-dried to obtain white benzaldehyde functionalized dextran DEX-BA. The results of nuclear magnetic resonance analysis of DEX-BA are as follows Figure 2 shown.
[0044] The obtained GO mixed functionalized polymer solution was transferred to a rotational rheometer to detect the change of the viscosity of the mixed solution with shear rate. The results are as follows Figure 3 As shown, the viscosity decreases with the increase of shear rate, showing an obvious shear thinning behavior, and its viscosity is 180 Pa·s.
[0045] The obtained GO composite hydrogel was transferred to a rheometer to detect the changes in the storage modulus and loss modulus of the GO composite hydrogel over time. The results are as follows: Figure 4 As shown, during the test time, the storage modulus is always higher than the loss modulus, indicating that the network structure of the GO composite hydrogel is stable and its modulus is 10930Pa.
[0046] Example 2
[0047] The present embodiment provides a controllable self-destructive hydrogel, and the preparation method thereof is as follows: dissolving a cyanoacetate functionalized polymer (DEX-CA, number average molecular weight 7000, 15 mg), a benzaldehyde functionalized polymer (DEX-BA, number average molecular weight 7000, 15 mg) and PEG (number average molecular weight 1000) in a GO dispersion (5 mg / mL, 150 uL) to obtain a GO mixed functionalized polymer solution, and then adding histidine to obtain a GO composite hydrogel.
[0048] The preparation methods of the cyanoacetate functionalized polymer and the benzaldehyde functionalized polymer are the same as those in Example 1.
[0049] The obtained GO mixed functionalized polymer solution was transferred to a rotational rheometer to detect the change of the solution's viscosity with shear rate. Figure 5 As shown, the viscosity decreases with the increase of shear rate, showing obvious shear thinning behavior, and its viscosity is 560 Pa·s.
[0050] The obtained GO composite hydrogel was transferred to a rheometer to detect the changes in the storage modulus and loss modulus of the GO composite hydrogel over time. The results are as follows: Figure 4 As shown, during the test time, the storage modulus is higher than the loss modulus, indicating that the network structure of the GO composite hydrogel is stable and its modulus is 14700Pa.
[0051] Example 3
[0052] The present embodiment provides a controllable self-destructive hydrogel, and the preparation method thereof is as follows: dissolving a cyanoacetate functionalized polymer (DEX-CA, number average molecular weight 7000, 15 mg), a benzaldehyde functionalized polymer (DEX-BA, number average molecular weight 7000, 15 mg) and PEG (number average molecular weight 2000) in a GO dispersion (5 mg / mL, 150 uL) to obtain a GO mixed functionalized polymer solution, and then adding histidine to obtain a GO composite hydrogel.
[0053] The preparation methods of the cyanoacetate functionalized polymer and the benzaldehyde functionalized polymer are the same as those in Example 1.
[0054] Example 4
[0055] The present embodiment provides a controllable self-destructive hydrogel, and the preparation method thereof is as follows: dissolving a cyanoacetate functionalized polymer (DEX-CA, number average molecular weight 7000, 15 mg), a benzaldehyde functionalized polymer (DEX-BA, number average molecular weight 7000, 15 mg) and PEGDA (number average molecular weight 600) in a GO dispersion (5 mg / mL, 150 uL) to obtain a GO mixed functionalized polymer solution, and then adding histidine to obtain a GO composite hydrogel.
[0056] The preparation methods of the cyanoacetate functionalized polymer and the benzaldehyde functionalized polymer are the same as those in Example 1.
[0057] Example 5
[0058] The present embodiment provides a controllable self-destructive hydrogel, and the preparation method thereof is as follows: dissolving a cyanoacetate functionalized polymer (DEX-CA, number average molecular weight 7000, 15 mg), a benzaldehyde functionalized polymer (DEX-BA, number average molecular weight 7000, 15 mg) and PEGDA (number average molecular weight 1000) in a GO dispersion (5 mg / mL, 150 uL) to obtain a GO mixed functionalized polymer solution, and then adding histidine to obtain a GO composite hydrogel.
[0059] The preparation methods of the cyanoacetate functionalized polymer and the benzaldehyde functionalized polymer are the same as those in Example 1.
[0060] Example 6
[0061] The present embodiment provides a controllable self-destructive hydrogel, and the preparation method thereof is as follows: dissolving a cyanoacetate functionalized polymer (DEX-CA, number average molecular weight 7000, 15 mg), a benzaldehyde functionalized polymer (DEX-BA, number average molecular weight 7000, 15 mg) and PEG (number average molecular weight 600) in a GO dispersion (8 mg / mL, 150 uL) to obtain a GO mixed functionalized polymer solution, and then adding histidine to obtain a GO composite hydrogel.
[0062] The preparation methods of the cyanoacetate functionalized polymer and the benzaldehyde functionalized polymer are the same as those in Example 1.
[0063] Example 7
[0064] The present embodiment provides a controllable self-destructive hydrogel, and the preparation method thereof is as follows: dissolving a cyanoacetate functionalized polymer (DEX-CA, number average molecular weight 7000, 15 mg), a benzaldehyde functionalized polymer (DEX-BA, number average molecular weight 7000, 15 mg) and PEG (number average molecular weight 600) in a GO dispersion (10 mg / mL, 150 uL) to obtain a GO mixed functionalized polymer solution, and then adding histidine to obtain a GO composite hydrogel.
[0065] The preparation methods of the cyanoacetate functionalized polymer and the benzaldehyde functionalized polymer are the same as those in Example 1.
[0066] Example 8
[0067] The present embodiment provides a controllable self-destructive hydrogel, and the preparation method thereof is as follows: dissolving a cyanoacetate functionalized polymer (DEX-CA, number average molecular weight 7000, 15 mg), a benzaldehyde functionalized polymer (DEX-BA, number average molecular weight 7000, 15 mg) and PEG (number average molecular weight 600) in a GO dispersion (15 mg / mL, 150 uL) to obtain a GO mixed functionalized polymer solution, and then adding histidine to obtain a GO composite hydrogel.
[0068] The preparation methods of the cyanoacetate functionalized polymer and the benzaldehyde functionalized polymer are the same as those in Example 1.
[0069] Example 9
[0070] This embodiment provides an application of a controllable self-destructive hydrogel in 3D printing: the GO mixed functionalized polymer solution obtained in Example 1 is loaded into a 1 ml syringe, and injected into a histidine solution at a flow rate of 5 ml / h through a syringe pump to obtain a GO composite hydrogel fiber.
[0071] The obtained GO composite hydrogel fiber was always placed in the histidine solution, and then one end of it was exposed to the water / air liquid surface to observe its movement, such as Figure 6 As shown. Figure 6 It can be seen that the GO composite hydrogel fibers exposed to the liquid surface will move and degrade rotationally, and the underwater GO composite hydrogel fibers will continuously float to the surface and repeat the movement and degradation process until the GO composite hydrogel fibers are completely dissipated.
[0072] Example 10
[0073] This embodiment provides an application of a controllable self-destructive hydrogel in 3D printing: the GO mixed functionalized polymer solution obtained in Example 2 is loaded into a 1 ml syringe, and injected into a histidine solution at a flow rate of 5 ml / h through a syringe pump to obtain a GO composite hydrogel fiber.
[0074] The obtained GO composite hydrogel fiber is always placed in the histidine solution, and then one end is exposed to the water / air liquid surface to observe its movement. It can be seen that the GO composite hydrogel fiber exposed to the liquid surface will rotate and degrade, and the GO composite hydrogel fiber underwater will continuously float to the surface and repeat the movement and degradation process until the GO composite hydrogel fiber is completely dissipated.
[0075] Embodiment 11
[0076] This embodiment provides an application of a controllable self-destructive hydrogel in 3D printing: the GO mixed functionalized polymer solution obtained in Example 4 is loaded into a 1 ml syringe, and injected into a histidine solution at a flow rate of 5 ml / h through a syringe pump to obtain a GO composite hydrogel fiber.
[0077] The obtained GO composite hydrogel fiber was always placed in the histidine solution, and then one end was exposed to the water / air liquid surface to observe its movement. It can be seen that the GO composite hydrogel fiber exposed to the liquid surface will rotate and degrade, and the GO composite hydrogel fiber under water will constantly float to the surface and repeat the movement and degradation process. After the GO composite hydrogel fiber has been degraded for a period of time, it is irradiated with ultraviolet light for a few minutes. Figure 7 As shown, the GO composite hydrogel fibers stopped moving and degraded, sinking to the bottom of the histidine solution.
[0078] The GO composite hydrogel fiber was printed into the letter "B" in the histidine solution, and then one end of the letter was lifted to the liquid surface to observe its movement. Figure 8 As shown. Figure 8 It can be seen that with the continuous movement and degradation of one end of the GO composite hydrogel fiber, the letter keeps changing its shape. When only "P" is left, it is fixed with ultraviolet light, and the letter "P" is preserved in the histidine solution.
[0079] Example 12
[0080] This embodiment provides an application of a controllable self-destructive hydrogel in 3D printing and on-demand cell release:
[0081] Mouse embryonic fibroblasts (NIH 3T3) were inoculated in a sterile 96-well plate (1000 cells / well, 200 μL DMEM / well), and then placed in a sterile incubator for culture. After 24 hours, the old culture medium was discarded, and 200 μL of DMEM culture medium containing GO composite hydrogel extract was added to each well. The control group was cultured with DMEM culture medium without GO composite hydrogel extract, and the culture was continued for 24 hours. CCK-8 test was performed, and the absorbance of each well at 450nm was measured using an enzyme reader. The cytotoxicity of different GO composite hydrogels on NIH 3T3 cells is shown in Figure 2. Fig. 9 As shown, the experimental results showed that GO composite hydrogel had no cytotoxicity to normal mouse embryonic fibroblasts.
[0082] Human umbilical vein endothelial cells (HUVEC) (100,000 / mL) were mixed evenly with the GO mixed functionalized polymer solution, and then the cell-mixed GO mixed functionalized polymer solution was extruded in a culture medium DMEM containing a histidine solution to form a cell-encapsulated GO composite hydrogel fiber, such as Fig.10 As shown in Figure 3, the cells maintained a high survival rate and were evenly dispersed in the fibers.
[0083] When a portion of the cell-encapsulated GO composite hydrogel fiber is exposed above the liquid surface, the cell-encapsulated GO composite hydrogel fiber will rotate and degrade until it completely dissipates and releases all the cells into the culture medium. Fig.11 As shown. Fig.11 It can be seen that the cells encapsulated in the GO composite hydrogel fibers are basically completely released, and the cells maintain a high survival rate and proliferation function.
[0084] In the present invention, unless otherwise specified, the scientific and technical terms used herein have the meanings commonly understood by those skilled in the art. In addition, the reagents, materials and operating procedures used herein are reagents, materials and conventional procedures widely used in the corresponding fields.
[0085] It should be noted that the terms such as "upper", "lower", "left", "right", "front", "back", etc. cited in the invention are only for the convenience of description and are not used to limit the scope of implementation of the present invention. Changes or adjustments in their relative relationships should be regarded as the scope of implementation of the present invention without substantially changing the technical content.
[0086] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.
Claims
1. A method for preparing a controllable self-destructive hydrogel, characterized in that: Adding the GO mixed functionalized polymer solution into the histidine solution to obtain the controllable self-destructive hydrogel; The GO mixed functionalized polymer solution is obtained by mixing a cyanoacetate functionalized polymer, a benzaldehyde functionalized polymer and a hydrophilic PEG or PEG derivative in a GO aqueous medium; The structural formula of cyanoacetate functionalized polymer is: Where n is the degree of polymerization, 50≤n≤1000; The structural formula of benzaldehyde functionalized polymer is: Wherein, m is the degree of polymerization, 10≤m≤500; The structural formula of PEG is: Where p is the degree of polymerization, 50≤p≤1000; In the GO mixed functionalized polymer solution, the mass-volume concentration of the cyanoacetate functionalized polymer is 5-40%; the mass-volume concentration of the benzaldehyde functionalized polymer is 5-40%; the mass-volume concentration of GO is 2-30%; the mass-volume concentration of PEG or PEG derivative is 2-50%; and the mass-volume concentration of the histidine solution is 1-30%; The PEG derivative is PEGDA.
2. The method for preparing the controllable self-destructive hydrogel according to claim 1, characterized in that: in, The preparation method of the cyanoacetate functionalized polymer is as follows: a polymer containing a hydroxyl group and cyanoacetic acid are dissolved in a solvent, and a condensation reaction is carried out under the catalysis of EDC·HCl and DMAP to obtain the cyanoacetate functionalized polymer; The solvent is dichloromethane, N,N-dimethylformamide, dimethyl sulfoxide, a mixed solvent of dichloromethane and water, a mixed solvent of N,N-dimethylformamide and water, or a mixed solvent of dimethyl sulfoxide and water.
3. The method for preparing the controllable self-destructive hydrogel according to claim 1, characterized in that: in, The preparation method of the benzaldehyde functionalized polymer is as follows: a polymer containing a hydroxyl group and p-formylbenzoic acid are dissolved in a solvent, and a condensation reaction is carried out under the catalysis of EDC·HCl and DMAP to obtain the benzaldehyde functionalized polymer; The solvent is dichloromethane, N,N-dimethylformamide, dimethyl sulfoxide, a mixed solvent of dichloromethane and water, a mixed solvent of N,N-dimethylformamide and water, or a mixed solvent of dimethyl sulfoxide and water.
4. The method for preparing the controllable self-destructive hydrogel according to claim 1, characterized in that: in, The solvent of the GO mixed functionalized polymer solution is water, physiological saline or buffer solution; The solvent of the histidine solution is water, physiological saline or buffer solution.
5. The method for preparing the controllable self-destructive hydrogel according to claim 1, characterized in that: in, The temperature at which the GO mixed functionalized polymer solution and the histidine solution are mixed is 4-37°C.
6. The controllable self-destructive hydrogel prepared by the preparation method according to any one of claims 1 to 5.
7. The use of the controllable self-destructive hydrogel in 3D printing as claimed in claim 6, characterized in that: The GO mixed functionalized polymer solution is used as an ink material for 3D printing and is printed into a histidine solution to form a controllable self-destructive hydrogel; the controllable self-destructive hydrogel degrades on the liquid surface of the histidine solution.
8. The use of the controllable self-destructive hydrogel in 3D printing according to claim 7, characterized in that: in, The controllable self-destructive hydrogel printed by GO mixed functionalized polymer solution made of PEG derivative PEGDA was degraded at the liquid surface of the histidine solution, and then the degradation was blocked by UV curing to obtain a partially degraded controllable self-destructive hydrogel.