Mild thermal stimulation and thermal triggering cascade type component release anchoring support and preparation method thereof

Abstract

The invention discloses a mild thermal stimulation and thermal triggering cascade type component release anchoring stent, and relates to the technical field of biomedical materials, the anchoring stent comprises a calcium carbonate-polyetherimide mechanical module, and a copper sulfide-polydopamine mild thermal stimulation composite coating on the surface of the calcium carbonate-polyetherimide mechanical module; wherein the copper sulphide is hollow mesoporous copper sulphide, and at least one of a photo-thermal response component, a therapeutic drug and a metal active component is loaded in the copper sulphide. According to the method, by combining thermal stimulation and a thermal triggering cascade type component release system, direct thermal stimulation is carried out on a target interface, in-situ thermal triggering release and regulation of components can be achieved, the problem that in the prior art, in the field of rehabilitation after a ligament reconstruction operation, the requirement for direct wound repair is not met is solved, and the application prospect is wide. The technical effects of tissue repair and rehabilitation acceleration in the field of rehabilitation after the ligament reconstruction operation are achieved.

Description

Technical Field

[0001] The invention relates to the technical field of biomedical materials, and in particular to an anchoring stent capable of mild thermal stimulation and heat-triggered cascade component release and a preparation method thereof. Background Art

[0002] Ligament reconstruction surgery is the standard treatment for severe ligament injuries. An interface scaffold is needed to fix the transplanted ligament or tendon to the bone tissue. During ligament reconstruction, the healing interface between the scaffold and the host bone is the key area. However, the healing process of this interface is complex and lengthy, and is often affected by multiple factors such as surgical techniques, postoperative functional exercise, and biological repair. Especially in the early postoperative stage, the connection between the ligament and the bone is the weakest area, which is prone to poor healing or failure. Therefore, how to accelerate and improve the healing process of this interface and improve the success rate of ligament reconstruction surgery is an urgent problem to be solved.

[0003] With the continuous advancement of tissue engineering technology, the interface scaffold has gone through the development process from metal screws to autologous bone scaffolds and then to biodegradable materials. However, the interface scaffolds currently used in surgery are still plagued by adverse factors such as postoperative secondary inflammatory response, stress shielding, and uneven biodegradation; rehabilitation treatment methods after ligament reconstruction surgery include postoperative functional exercise and physical therapy, which have a positive effect on reducing inflammatory response and promoting motor function recovery after ligament reconstruction surgery, but their effects are limited by postoperative immobilization and treatment penetration depth, and cannot directly act on the surgical wound and cannot fully meet the needs of postoperative rehabilitation. Although certain optimizations have been made in tissue engineering scaffolds by using components such as hydroxyapatite, tantalum metal, and vancomycin, these technologies still fail to meet the needs of rehabilitation methods for mild thermal stimulation of the interface in the field of postoperative rehabilitation of ligament reconstruction surgery, and the release and action mechanism of the components are difficult to accurately control, which leads to unstable treatment effects and may not achieve the expected results.

[0004] Therefore, it is a technical problem that urgently needs to be solved in the art to provide a fixed bracket that can perform mild thermal stimulation at the interface and continuously release multiple types and multiple functions of beneficial biologically active components at the interface. Summary of the invention

[0005] The present invention proposes an anchoring stent with mild thermal stimulation and heat-triggered cascade component release and a preparation method thereof. The method combines thermal stimulation and a heat-triggered cascade component release system to not only perform direct thermal stimulation on the target interface, but also achieve in situ thermally triggered release and regulation of components, thereby solving the problem in the prior art that the need for direct wound repair is not met in the field of rehabilitation after ligament reconstruction surgery, and achieving the technical effects of tissue repair and accelerated rehabilitation in the field of rehabilitation after ligament reconstruction surgery.

[0006] In order to achieve the above object, the present invention adopts the following technical solution:

[0007] An anchoring stent with mild thermal stimulation and heat-triggered cascade component release, the anchoring stent comprising a calcium carbonate-polyetherimide mechanical module and a copper sulfide-polydopamine mild thermal stimulation composite coating on the surface of the calcium carbonate-polyetherimide mechanical module;

[0008] The copper sulfide is hollow mesoporous copper sulfide, and is internally loaded with at least one of a photothermal response component, a therapeutic drug and a metal active component.

[0009] The anchoring stent of the present invention is divided into a mechanical module, a thermal stimulation module and a heat-triggered cascade component release module. The mechanical module stent is composed of a calcium carbonate-polyetherimide 3D printed stent, and the thermal stimulation module is composed of a copper sulfide-polydopamine coating; the thermally triggered component release module is composed of a photothermal response component or a therapeutic drug cascadedly loaded in the copper sulfide hollow mesoporous structure in the copper sulfide-polydopamine coating by adhesion, hollow structure loading and multi-layer loading, etc. The type and amount of the loaded component can be adjusted according to requirements. The layered design of the mechanical module, the mild thermal stimulation module and the heat-triggered cascade component release module can meet the strong demand for early postoperative fixation and match the needs of different healing times and healing processes.

[0010] Preferably, the calcium carbonate-polyetherimide mechanical module is prepared by 3D printing;

[0011] Wherein, the mass ratio of the polyetherimide to the calcium carbonate is 1:0.05-0.3.

[0012] In the preparation of the 3D printed polyetherimide-calcium scaffold, the interior of the prepared 3D printed calcium carbonate-polyetherimide mechanical module is a 3D grid stacking print, and traffic holes are left inside the printed stacking grid, and the traffic holes exist inside the stacking grid mechanical module.

[0013] The calcium carbonate-polyetherimide mechanical module is prepared through 3D printing, which can accurately control the size, shape and internal microstructure of the scaffold to meet the special needs of different ligament reconstruction procedures for fixed scaffolds; at the same time, the calcium carbonate in the scaffold can stimulate the growth of surrounding bone tissue, while polyetherimide ensures the mechanical properties of the scaffold and its good integration with surrounding tissues. The communication hole structure in the scaffold provides sufficient space for the regeneration and growth of bone tissue, which helps to accelerate the repair and reconstruction of bone tissue.

[0014] Preferably, the calcium carbonate-polyetherimide mechanical module further comprises magnesium, and the mass ratio of the magnesium to the polyetherimide is 0.05-0.2:1.

[0015] By doping magnesium particles and other components into the mechanical module, on the one hand, the mechanical properties of the mechanical module can be improved, and a more solid fixation effect can be achieved in the early postoperative period; on the other hand, the degradation and release of magnesium particles can reduce the mechanical strength of the mechanical module and form a micro-nanoscale microporous structure, which is conducive to the ingrowth of new bone tissue and the integration between the scaffold and bone tissue; in addition, magnesium has certain nano-functions of promoting vascularization and collagen, and can regulate postoperative blood supply recovery and tissue healing process in ligament reconstruction and postoperative repair.

[0016] Preferably, the mass ratio of the copper sulfide to the photothermal response component, therapeutic drug or metal active component is 1:1-5;

[0017] The coating rate of the copper sulfide-polydopamine mild thermal stimulation composite coating is 50-90%;

[0018] The mass ratio of the polydopamine to the copper sulfide is 4-10:1.

[0019] Hollow mesoporous copper sulfide has drug-loading space and the ability to graft bioactive components. When combined with the copper sulfide-polydopamine composite coating, it can achieve the effect of heat-triggered cascade component release. Specifically, the copper sulfide-polydopamine composite coating converts the excitation light into heat, thereby promoting the release of the hollow mesoporous copper sulfide and other components enclosed in the coating into the local environment. Then, drug components such as curcumin carried in the hollow mesoporous copper sulfide can be further released from the copper sulfide, thereby achieving higher loading concentration, wider action area and better action effect.

[0020] Preferably, the photothermal response component or therapeutic drug includes curcumin, TiO 2 , and at least one of gold nanoparticles.

[0021] By loading TiO in the thermally triggered component release module 2 components or drugs, which can give them other biological functions such as antibacterial properties. For example, CuO can capture TiO 2 The photogenerated electrons generated reduce the recombination rate of electron-hole pairs, thereby improving the photocatalytic efficiency; CuO and TiO 2 The combination can enhance the stability of the structure.

[0022] According to the above-mentioned method for preparing an anchoring stent with mild thermal stimulation and heat-triggered cascade component release, the method comprises the following steps:

[0023] (1) weighing calcium carbonate and polyetherimide powder according to a mass ratio and mixing them evenly to prepare a calcium carbonate-polyetherimide filament, and then preparing a calcium carbonate-polyetherimide mechanical module by 3D printing the calcium carbonate-polyetherimide filament;

[0024] (2) adding copper sulfide and a photothermal response component and / or a therapeutic drug and / or a metal active component into water to prepare a uniform dispersion, and freeze-drying to obtain copper sulfide loaded with the photothermal response component and / or the therapeutic drug and / or the metal active component;

[0025] (3) adding the prepared copper sulfide loaded with photothermal response components and / or therapeutic drugs and / or metal active components to the dopamine solution and mixing evenly to obtain a mixed solution, placing the calcium carbonate-polyetherimide mechanical module into the mixed solution, and self-polymerizing on the surface of the calcium carbonate-polyetherimide mechanical module to form a copper sulfide-polydopamine mild thermal stimulation composite coating, and after washing and drying, obtaining an anchoring scaffold with mild thermal stimulation and heat-triggered cascade component release.

[0026] Preferably, the diameter of the calcium carbonate-polyetherimide filament in step (1) is 1.50-2.00 mm, and the printing temperature is 380-420°C.

[0027] Preferably, the dispersion in step (2) is prepared by mixing at room temperature for 12-48 hours;

[0028] The concentration of copper sulfide in the dispersion is 0.125-5 mg / mL;

[0029] The freeze-drying condition is drying at -40°C under vacuum conditions for 48 hours.

[0030] Preferably, step (2) further comprises heat treating the obtained copper sulfide loaded with the photothermal response component and / or therapeutic drug at 300° C. for 2 hours.

[0031] Preferably, the final concentration of copper sulfide in step (3) is 0.125-5 mg / mL, and the concentration of the dopamine solution is 2 mg / mL;

[0032] The conditions for the self-polymerization are: 600-800 rpm for 12-48 hours at room temperature, in the dark and ventilated environment;

[0033] Drying conditions: 20-60℃ for 12-24h.

[0034] Preferably, the method for realizing the thermal stimulation and the release of the heat-triggered components in the anchoring stent is:

[0035] 1) After the anchoring stent is anchored, the stent is irradiated with near-infrared light 2-3 times a week, each time for 5-10 minutes;

[0036] 2) During the irradiation process, use an infrared thermometer to strictly monitor the temperature of the irradiated area and the surrounding area, and control the regional temperature within the range of 40.0-43.0℃ to avoid excessive thermal stimulation.

[0037] Compared with the prior art, the present invention has the following beneficial effects:

[0038] (1) The raw materials of the present invention include calcium carbonate, polyetherimide, copper sulfide and dopamine, which have good biocompatibility. By optimizing the scaffold design and load position, these components can achieve direct sustained release and heat-triggered release at the tendon-bone healing interface. Specifically, the sustained release mechanism is achieved by controlling the distribution and release rate of these components in the scaffold. When the scaffold is placed at the tendon-bone healing interface, these components can be released into the surrounding tissues to provide necessary nutrition and support for the healing process. At the same time, the heat-triggered release mechanism can accelerate the release of components through an external excitation source (such as infrared irradiation) when necessary to meet the needs of different healing stages.

[0039] (2) The copper sulfide-polydopamine composite mild thermal stimulation coating used in the present invention has good photothermal conversion efficiency and directly performs photothermal stimulation at the tendon-bone healing interface. When an external excitation source (such as infrared irradiation) is used to irradiate the stent, the copper sulfide-polydopamine composite coating will quickly convert light energy into heat energy, producing a local heating effect. This heating effect can promote the release of drugs or bioactive substances and accelerate the healing process; at the same time, local heating can also reduce the patient's pain, improve the treatment effect and the patient's comfort. Moreover, by loading gold nanoparticles in the mild thermal stimulation module, the photothermal conversion efficiency of the mild thermal stimulation module can be further improved, achieving a smaller excitation light power requirement and avoiding possible side effects.

[0040] (3) The present invention can meet the strong demand for postoperative fixation in the early stage and match the needs of different healing times and healing processes through the layered design of mechanical module, mild thermal stimulation module and heat-triggered cascade component release module. The mechanical module is mainly responsible for providing stability and fixation force in the early stage after surgery. It is composed of a calcium carbonate-polyetherimide 3D printed bracket, which can ensure that the bracket will not shift or loosen in the early stage after surgery. As the healing process proceeds and components such as calcium carbonate are released, the mechanical module gradually integrates with the growing new bone tissue; the mild thermal stimulation module is responsible for mediating the stimulation of the external excitation source and generating heat, producing a direct mild thermal stimulation effect at the wound interface; the heat-triggered component release module is responsible for layering the loading components, and can control the release of drugs or other components according to the needs of the healing time and healing process; in the early stage of healing, the loading module can release a large amount of angiogenic components and anti-inflammatory drugs to promote blood supply recovery and reduce inflammatory response; in the later stage of healing, the release amount can be gradually reduced to avoid unnecessary stimulation to the surrounding tissues. This layered design makes the treatment effect more accurate and effective. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. The drawings in this description are only embodiments of the present invention.

[0042] Figure 1 Schematic diagram of a module of a bracket of Example 4 of the present invention, wherein a is a top view and b is a cross-sectional view;

[0043] Figure 2 This is a surface morphology diagram of the bracket of Example 4 of the present invention;

[0044] Figure 3 This is a diagram showing the temperature change of the stent in Example 4 of the present invention when it is stimulated in an animal model;

[0045] Figure 4 This is a diagram of ALP activity analysis of the scaffolds of Examples 1-4 of the present invention;

[0046] Figure 5 This is a diagram for analyzing the proliferation activity of scaffold cells in Examples 1-4 of the present invention. DETAILED DESCRIPTION

[0047] Embodiments of the present invention are described below. Examples of the embodiments are shown in the accompanying drawings. The embodiments described with reference to the accompanying drawings are exemplary and are intended to be used to explain the present invention, but are not to be construed as limiting the present invention.

[0048] Example 1

[0049] The present invention provides a method for preparing an anchoring stent capable of mild thermal stimulation and heat-triggered cascade component release, comprising the following steps:

[0050] (1) mixing polyetherimide powder and calcium carbonate powder in a mass ratio of 1:0.10 to obtain a calcium carbonate-polyetherimide mixed powder, adding the fully dried calcium carbonate-polyetherimide mixed powder to the feed port of a twin-screw extruder, and obtaining a calcium carbonate-polyetherimide filament with a diameter of 1.70 mm after extrusion, placing the filament in a 3D printer, adjusting the printer temperature to 380° C., and obtaining a cylindrical calcium carbonate-polyetherimide mechanical module with a diameter of 3 mm, a height of 6 mm, an internal traffic hole diameter of 600 μm, and a filling rate of 40% after 3D printing;

[0051] (2) the hollow mesoporous copper sulfide and curcumin were fully mixed in ultrapure water at a mass ratio of 1:2 to form a uniform dispersion, the concentration of copper sulfide in the dispersion was 0.5 mg / mL, and the dispersion was kept at room temperature for 24 hours. After the loading was completed, the hollow mesoporous copper sulfide powder loaded with curcumin was obtained by freeze drying at -40°C vacuum conditions for 48 hours, and the obtained powder was heat treated at 300°C for 2 hours;

[0052] (3) Weigh dopamine to prepare a dopamine solution with a pH of 8.5 and a concentration of 2 mg / mL, add the curcumin-loaded hollow mesoporous copper sulfide powder prepared in step (2) to the dopamine solution in an amount of 0.5 mg / mL copper sulfide final concentration to obtain a mixed solution, completely immerse the calcium carbonate-polyetherimide mechanical module in the mixed solution, perform surface coating modification under light-proof and ventilated conditions, stir at a speed of 600 rpm for 24 hours, and the coating rate of the composite coating is 80%, wash the precipitate with ultrapure water three times, and dry it at 60° C. for 24 hours to obtain a copper sulfide-polydopamine composite mild thermal stimulation coating modified stent.

[0053] Example 2

[0054] The present invention provides a method for preparing an anchoring stent with mild thermal stimulation and heat-triggered cascade component release, which differs from Example 1 in that in step (1), polyetherimide, calcium carbonate and magnesium particles with a mass ratio of 1:0.1:0.05 are evenly mixed, and the operation is exactly the same as that of Example 1.

[0055] Example 3

[0056] The present invention provides a method for preparing an anchoring stent capable of mild thermal stimulation and heat-triggered cascade component release, which differs from Example 2 in that the stent modified with a copper sulfide-polydopamine composite mild thermal stimulation coating obtained in step (3) is immersed in a 1.0 mg / mL fully dispersed gold nanoparticle suspension, stirred at room temperature for 5 minutes, and washed and dried to obtain a stent modified with a copper sulfide-polydopamine composite mild thermal stimulation coating loaded with gold nanoparticles.

[0057] Example 4

[0058] The present invention provides a method for preparing an anchoring stent with mild thermal stimulation and heat-triggered cascade component release, which is different from Example 3 in that step (3) comprises: weighing dopamine to prepare a dopamine solution with a pH of 8.5 and a concentration of 2 mg / mL, and adding a hollow mesoporous copper sulfide loaded with curcumin with a final concentration of 0.5 mg / mL of copper sulfide and a TiO 2 The calcium carbonate-polyetherimide mechanical module was fully dispersed in the solution to obtain a mixed solution, and the calcium carbonate-polyetherimide mechanical module was completely immersed in the mixed solution. The surface coating was modified under light-proof and ventilation conditions. The stirring speed was 600 rpm for 24 hours. The precipitate was washed with ultrapure water for 3 times and dried at 60 ° C for 24 hours to obtain a TiO 2 The copper sulfide-polydopamine composite mild thermal stimulation coating modified stent, the top view and cross-sectional view of the relevant stent are shown in Figure 1, wherein 1 is a calcium carbonate-polyetherimide mechanical module, 2 is a copper sulfide-polydopamine composite mild thermal stimulation coating, and 3 is a cascade component release module. Figure 2 : is a surface morphology diagram of the stent in this embodiment. It can be seen from the figure that the mechanical module composed of the calcium carbonate-polyetherimide 3D printed stent has a grid structure, which can ensure that the stent will not be displaced or loosened in the early postoperative period. As the healing process proceeds and components such as calcium carbonate are released, the mechanical module gradually integrates with the growing new bone tissue;

[0059] The bone defect drug delivery bodies prepared by Examples 1-4 and the existing product (CN103751840B, a titanium alloy stent with porous controllable low modulus) as comparative examples were subjected to performance tests, and the test results are shown in Table 1;

[0060] Table 1 Performance test results of Examples 1-4 and existing products

[0061]

[0062] It can be seen from the data in the above table that the bone defect drug delivery body prepared by the present invention has a compression modulus close to that of the titanium alloy stent and has photothermal conversion capability; at the same time, the composite coating of the delivery body has a more excellent drug loading capacity.

[0063] The thermal stimulation and release of the heat-triggered components are achieved by the following steps:

[0064] (1) After anchoring with the anchoring stent, use near-infrared light to irradiate the stent 2-3 times a week, each time for 5-10 minutes;

[0065] (2) During the irradiation process, an infrared thermometer was used to strictly monitor the temperature of the irradiated area and the surrounding area, and the regional temperature was controlled within the range of 40.0-43.0°C to avoid excessive thermal stimulation;

[0066] Figure 3 This is a diagram showing the temperature change of the stent in Example 4 of the present invention in an animal model. As can be seen from the figure, the bone defect drug delivery body prepared by the present invention can stimulate thermal stimulation in vivo, and the thermal stimulation temperature range can be controlled by controlling the excitation light power;

[0067] Figure 4 : is an analysis diagram of the ALP activity of the scaffolds of Examples 1-4 of the present invention. The specific method is to inoculate MC3T3-E1 cells onto the surface of the scaffolds, and after culturing for 4 and 7 days, use an ALP quantification kit to quantify the ALP expression of the cells. As can be seen from the figure, compared with Examples 1, 2 and 3, the product of Example 4 has the best performance in promoting osteogenic differentiation of MC3T3-E1 cells;

[0068] Figure 5 3 is an analysis diagram of cell proliferation activity of the scaffolds of Examples 1-4 of the present invention. The specific method is to inoculate MC3T3-E1 cells onto the surface of the scaffold, and after 5 days of co-culture, use a CCK-8 kit to quantify cell viability. It can be seen from the figure that compared with Examples 1, 2 and 3, Example 4 has the best cell viability.

[0069] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. An anchoring stent with mild thermal stimulation and heat-triggered cascade component release, characterized in that: The anchoring bracket comprises a calcium carbonate-polyetherimide mechanical module and a copper sulfide-polydopamine mild thermal stimulation composite coating on the surface of the calcium carbonate-polyetherimide mechanical module; The copper sulfide is hollow mesoporous copper sulfide, and is internally loaded with at least one of a photothermal response component, a therapeutic drug and a metal active component.

2. An anchoring stent with mild thermal stimulation and heat-triggered cascade component release according to claim 1, characterized in that: The calcium carbonate-polyetherimide mechanical module is prepared by 3D printing; Wherein, the mass ratio of the polyetherimide to the calcium carbonate is 1:0.05-0.

3.

3. An anchoring stent with mild thermal stimulation and heat-triggered cascade component release according to claim 1, characterized in that: The calcium carbonate-polyetherimide mechanical module also includes magnesium, and the mass ratio of the magnesium to the polyetherimide is 0.05-0.2:

1.

4. An anchoring stent with mild thermal stimulation and heat-triggered cascade component release according to claim 1, characterized in that: The mass ratio of the copper sulfide to the photothermal response component, therapeutic drug or metal active component is 1:1-5; The coating rate of the copper sulfide-polydopamine mild thermal stimulation composite coating is 50-90%; The mass ratio of the polydopamine to the copper sulfide is 4-10:

1.

5. The anchoring stent with mild thermal stimulation and heat-triggered cascade component release according to claim 1, characterized in that: The photothermal response component, therapeutic drug and metal active component include at least one of curcumin, TiO2 and gold nanoparticles.

6. A method for preparing an anchoring stent with mild thermal stimulation and heat-triggered cascade component release according to any one of claims 1 to 5, characterized in that: The following steps are involved: (1) weighing calcium carbonate and polyetherimide powder according to a mass ratio and mixing them evenly to prepare a calcium carbonate-polyetherimide filament, and then preparing a calcium carbonate-polyetherimide mechanical module by 3D printing the calcium carbonate-polyetherimide filament; (2) adding copper sulfide and a photothermal response component and / or a therapeutic drug and / or a metal active component into water to prepare a uniform dispersion, and freeze-drying to obtain copper sulfide loaded with the photothermal response component and / or the therapeutic drug and / or the metal active component; (3) adding the prepared copper sulfide loaded with photothermal response components and / or therapeutic drugs and / or metal active components to the dopamine solution and mixing evenly to obtain a mixed solution, placing the calcium carbonate-polyetherimide mechanical module into the mixed solution, and self-polymerizing on the surface of the calcium carbonate-polyetherimide mechanical module to form a copper sulfide-polydopamine mild thermal stimulation composite coating, and after washing and drying, obtaining an anchoring scaffold with mild thermal stimulation and heat-triggered cascade component release.

7. The method for preparing an anchoring stent with mild thermal stimulation and heat-triggered cascade component release according to claim 6, characterized in that: The diameter of the calcium carbonate-polyetherimide filament in step (1) is 1.50-2.00 mm, and the printing temperature is 380-420° C.

8. The method for preparing an anchoring stent with mild thermal stimulation and heat-triggered cascade component release according to claim 6, characterized in that: The preparation conditions of the dispersion in step (2) are mixing at room temperature for 12-48 hours; The concentration of copper sulfide in the dispersion is 0.125-5 mg / mL; The freeze-drying condition is drying at -40°C under vacuum conditions for 48 hours.

9. The method for preparing an anchoring stent with mild thermal stimulation and heat-triggered cascade component release according to claim 6, characterized in that: Step (2) also includes heat treating the obtained copper sulfide loaded with photothermal response components and / or therapeutic drugs at 300° C. for 2 hours.

10. The method for preparing an anchoring stent with mild thermal stimulation and heat-triggered cascade component release according to claim 6, characterized in that: The final concentration of the copper sulfide in step (3) is 0.125-5 mg / mL, and the concentration of the dopamine solution is 2 mg / mL; The conditions for the self-polymerization are: at room temperature, in the dark and ventilated environment, at 600-800 rpm for 12-48 hours; Drying conditions: 20-60℃ for 12-24h.

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