A method for making a flexible patterned fuel cell patch, and products and applications thereof

Abstract

The application discloses a preparation method of a flexible patterned fuel cell patch, which comprises the following steps: preparing PtNi alloy nanochain PtNi ANC; preparing PtNi alloy nanocage chain PtNi APNCC as a cathode catalyst; preparing a lipoic acid grafted chitosan LAMC; adding TSPBA and GPTMS into a polar organic solvent, and heating to obtain an epoxy hyperbranched polymer PTBPS; dissolving the LAMC and the PTBPS in water, and performing ultraviolet irradiation to form a hydrogel; adding the PtNi ANC and the PtNi APNCC to the LIG to serve as an anode and a cathode respectively, and then performing freeze transfer printing on the LIG to the hydrogel to obtain the flexible patterned fuel cell patch. The application further provides the flexible patterned fuel cell patch prepared according to the above method and application of the flexible patterned fuel cell patch in nerve repair and myocardial injury repair. The flexible patterned fuel cell patch prepared by the application has good flexibility and adhesion, and can provide effective in-situ electrical stimulation and a low-oxygen microenvironment in the application in nerve repair and myocardial injury repair.

Description

Technical Field

[0001] The present invention belongs to the technical field of biomedical materials, and specifically relates to a preparation method of a flexible patterned fuel cell patch, and its product and application. Background Art

[0002] Exogenous electrical stimulation can restore disrupted endogenous electric fields after injury, promote cell migration, activate intercellular communication pathways, and facilitate the repair of damaged tissue. However, exogenous electrical stimulation typically requires open wounds, transdermal wires, and bulky power sources, making it unsuitable for long-term treatment due to the increased risk of infection. For example, lithium-ion batteries, the most commonly used implantable power source, require complex packaging and secondary surgery to remove the battery. Therefore, there is a need to develop stable, miniature, and flexible implantable self-powered batteries for in situ electrical stimulation.

[0003] Currently, new and promising implantable self-powered technologies, such as piezoelectric nanogenerators (PENGs), triboelectric nanogenerators (TENGs), and fuel cells, have been widely developed. Both TENGs and PENGs require packaging and mechanical stimulation, which makes the design and use of these devices very inconvenient. In addition, the AC output is unstable. In contrast, enzyme-based implantable fuel cells are a better choice because they can directly use endogenous substances in body fluids as fuel and gently convert chemical energy into electrical energy. For example, the Chinese patent publication number CN114122437A discloses a flexible fiber biofuel cell that can be implanted in the brain, and its preparation method and application: using carbon nanotube fibers as a substrate, loading electron transfer agents and glucose oxidase as the anode, loading platinum carbon catalyst as the cathode, and generating a polydopamine-phosphocholine hydrophilic layer on the surface of the cathode and anode through in situ chemical reaction; the fiber biofuel cell prepared by this invention can achieve power output in a physiological concentration glucose solution and exhibit anti-bioadsorption performance in a bovine serum albumin solution; the biofuel cell can be used as a power source through minimally invasive implantation in the mouse brain for power output, and has anti-bioadsorption performance and the ability to maintain power output performance in the brain, showing good prospects for in vivo application, and providing a new solution to the problem of unstable energy supply of implantable electronic devices.

[0004] However, the potential inactivation of enzymes in enzymatic fuel cells leads to a short lifespan and high storage costs. Non-enzymatic fuel cells, on the other hand, typically use rigid packaging to achieve good electrochemical performance, resulting in poor flexibility, stretchability, and adhesion, making their adaptation to tissue morphology and designed patterned electric fields challenging. To produce package-free fuel cells, catalysts with high activity, good stability, and strong anti-interference capabilities are required. Package-free fuel cells can easily generate patterned electric fields by adjusting the electrode pattern. LIG technology is a new method for preparing conductive graphene. Laser-induced defective graphene electrodes can be induced on carbon-based materials, making it relatively easy to achieve personalized electrode pattern design and large-scale production. Many researchers have found that external electric fields that match the endogenous electric field of damaged tissue can guide cell migration to the damaged area and promote tissue repair (Endogenous Electric Fields-Coupled Electrospun Short Fiber Via Collecting Wound Exudation[J]. Advanced Materials[2024-10-14].). Therefore, package-free, non-enzymatic patterned fuel cells will greatly expand the biological applications of fuel cells.

[0005] Biopatch with good flexibility and adhesion is another key component of patterned electric field functionality. When subjected to large deformations, the substrate, lacking flexibility and adhesion, does not match the tissue surface, resulting in a poorly formed electrode-tissue interface and difficulty generating effective in situ electrical stimulation. Therefore, ensuring the flexibility and adhesion of biopatch is a pressing technical challenge. Summary of the Invention

[0006] The purpose of the present invention is to provide a method for preparing a flexible patterned fuel cell patch. The prepared flexible patterned fuel cell patch has good flexibility and adhesion, and can provide effective in situ electrical stimulation and a hypoxic microenvironment, and is used in nerve repair and myocardial injury repair to promote tissue repair.

[0007] The purpose of the present invention is achieved through the following technical solutions:

[0008] A method for preparing a flexible patterned fuel cell patch, the method comprising:

[0009] (1) Platinum acetylacetonate, nickel acetylacetonate, glucose, and hexadecyltrimethylammonium bromide were added to an oleylamine solution and heated to obtain PtNi alloy nanochains (PtNi ANCs) as an anode catalyst;

[0010] (2) PtNi ANC was added to a dilute nitric acid solution and heated and etched to obtain a PtNi alloy nanocage chain PtNiAPNCC as a cathode catalyst;

[0011] (3) Chitosan and lipoic acid are dissolved separately and then mixed, and then 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide are added, and the resulting mixture is reacted in the dark to obtain lipoic acid-grafted chitosan LAMC;

[0012] (4) adding a quaternary ammonium salt of phenylboronic acid derivative TSPBA and 3-(2,3-epoxypropyloxy)propyltrimethoxysilane GPTMS to a polar organic solvent, and heating the resulting mixture to obtain an epoxy hyperbranched polymer PTBPS;

[0013] (5) LAMC and PTBPS were dissolved in water and formed into a hydrogel under ultraviolet light irradiation;

[0014] (6) PtNi ANC and PtNi APNCC were added to laser-induced graphene LIG as the anode and cathode, respectively, and LIG was then transferred to the hydrogel by freeze transfer to obtain a flexible patterned fuel cell patch.

[0015] In the present invention, PtNi alloy nanoparticles inherit the high catalytic activity of nanoparticles and the high stability of nanowires, while Ni doping greatly improves anti-interference performance, resulting in a class of electrocatalysts with high catalytic activity. PtNi ANC and PtNiAPNCC can efficiently catalyze glucose oxidation and oxygen reduction reactions, respectively, to construct fuel cells and achieve the conversion of chemical energy to electrical energy. At the same time, the large-scale consumption of oxygen reduces the local oxygen concentration, creating a hypoxic environment that can induce an increase in tissue HIF-1α expression. HIF-1α plays an important role in promoting angiogenesis, inhibiting myocardial fibrosis, and promoting tissue repair.

[0016] In this invention, the chitosan hydrogel's inherent mechanical properties and flexibility, combined with the tissue adhesion provided by lipoic acid disulfide bonds, give the LAMC hydrogel a unique combination of mechanical properties, flexibility, and adhesion. This allows the flexible, patterned fuel cell patch to perfectly match the surface topography of diverse tissues and withstand significant deformation without falling off. The unpackaged fuel cell patch can generate a programmable patterned electric field and directional current based on the patterned LIG electrodes.

[0017] Therefore, the present invention can generate a patterned electric field and directional electrical stimulation that matches the endogenous electric field of the tissue, and synergistically achieve neural repair and myocardial damage repair in combination with a hypoxic microenvironment.

[0018] Preferably, in step (1), the molar ratio of platinum acetylacetonate to nickel acetylacetonate is 1:2-2:1. When the content of either is too high, a large amount of elemental nanoparticles will be generated, which will weaken the electronic effect and synergistic effect between the PtNi alloy and reduce the activity and stability of the catalyst.

[0019] Preferably, in step (1), the mixed solution is continuously heated in an oil bath at 160-200° C. for 10-18 hours to obtain the product.

[0020] Preferably, in step (2), the mixed solution is continuously heated in an oil bath at 60°C for 2-10 hours. As the heating time increases, the free Ni element is dissolved, forming a nanocage structure, which improves the oxygen mass transfer effect. However, excessive heating time will destroy the structure of the PtNi alloy and reduce the stability of the catalyst.

[0021] Preferably, in step (3), the mass of lipoic acid is 5-30% of the mass of chitosan.

[0022] Specifically, chitosan is dissolved in an acetic acid solution with a concentration of 1%-5%, and lipoic acid is dissolved in an ethanol solution with a concentration of 30%-50%.

[0023] Preferably, in step (3), the mixed solution after the reaction needs to be dialyzed for purification and freeze-dried, using deionized water as the dialysis solvent.

[0024] Preferably, in step (3), the freeze-dried LAMC is stored in a -20°C refrigerator away from light.

[0025] Preferably, in step (4), the mass of TSPBA is 10-50% of the mass of GPTMS; and the mixture is reacted continuously in an oil bath at 80-120°C for 6-12 hours. A large amount of TSPBA will reduce the epoxy group content in PTBPS. A small amount of TSPBA will reduce the molecular weight of PTBPS. A prolonged reaction time will increase the molecular weight of PTBPS and reduce its water solubility.

[0026] Preferably, in step (4), the precipitate after the reaction needs to be dialyzed for purification and freeze-dried, and deionized water is used as the dialysis solvent.

[0027] Preferably, in step (5), the mass ratio of LAMC to PTBPS is 20:1-5:1. Under 365nm ultraviolet light irradiation, the disulfide bonds of LAMC break, generating two sulfhydryl radicals, which can react with the epoxy groups of PTBPS or with the sulfhydryl radicals on the chitosan chain to form a hydrogel cross-linked network. When the input amount of PTBPS is low, the cross-linking density of the hydrogel is low and the mechanical properties are poor. When the input amount of PTBPS is high, the cross-linking density of the hydrogel is high and the flexibility of the hydrogel is poor.

[0028] Specifically, in step (6), a carbon dioxide laser engraver is used to induce laser-induced graphene (LIG) on a polyimide film, and then PtNi ANC and PtNi APNCC are dispersed in an isopropyl alcohol / water solution, respectively, and the dispersion is dropped onto the LIG.

[0029] Preferably, in step (6), the loading amount of PtNi ANC and PtNi APNCC on the LIG electrode is 0.05-0.5 mg / cm 2 With the increase of PtNi alloy catalyst loading, the output performance of the patterned fuel cell patch improved, but the biocompatibility decreased.

[0030] The present invention also provides a flexible patterned fuel cell patch obtained by the above preparation method.

[0031] The present invention also provides a use of the above-mentioned flexible patterned fuel cell patch in the preparation of products for nerve repair and myocardial injury repair.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] The raw materials of the present invention are safe in source, and both chitosan and lipoic acid have good biocompatibility. The prepared LAMC hydrogel has good flexibility and adhesion, which can adapt to a variety of tissue morphologies and achieve stable adhesion, forming a good tissue-electronic interface. The PtNi alloy catalyst synthesized by the present invention has high catalytic activity, high stability, and strong anti-interference ability. The flexible patterned fuel cell patch provided by the present invention is a package-free fuel cell patch. The matching electrode pattern can be designed according to the endogenous electric field distribution of the damaged tissue, generating an adaptive patterned electric field and directional current to promote tissue repair. At the same time, the cathode of the fuel cell patch consumes a large amount of oxygen, creating a hypoxic microenvironment, increasing HIF-1α expression, and expanding the biological application of fuel cells.

[0034] In summary, the patterned fuel cell patch prepared by the present invention has good flexibility, high mechanical strength and strong adhesion stability in various environments, can provide effective in situ electrical stimulation and hypoxic microenvironment, and has good stability and durability, and has broad application prospects in the field of tissue repair. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 is a TEM image of the PtNi ANC in Example 1.

[0036] Figure 2 is the XRD pattern of PtNi ANC in Example 1.

[0037] Figure 3 This is a power density curve of the PtNi ANC in Example 1.

[0038] Figure 4 1 is the cyclic voltammetry curve of glucose catalyzed by PtNi ANC in Example 1.

[0039] Figure 5 is a TEM image of the PtNi APNCC in Example 1.

[0040] Figure 6 1 is the cyclic voltammetry curve and linear voltammetry scanning diagram of the PtNi APNCC catalyzing oxygen in Example 1.

[0041] Figure 7 This is a diagram of the power density of the fuel cell composed of PtNi APNCC and PtNi ANC in Example 1.

[0042] Figure 8 Graph showing the anti-interference performance of the fuel cell composed of PtNi APNCC and PtNi ANC in Example 1.

[0043] Figure 9 This is the infrared spectrum of LAMC in Example 1.

[0044] Figure 10 is the PTBPS in Example 1 1 H-NMR spectrum.

[0045] Figure 11 Graphs showing the tensile strength and adhesion strength of the LAMC hydrogel in Example 1.

[0046] Figure 12 This is the rheological properties diagram of the LAMC hydrogel in Example 1.

[0047] Figure 13 is a picture of the LIG electrode in Example 1.

[0048] Figure 14 1 is a power density curve diagram of the flexible patterned fuel cell patch inside and outside the body in Example 1.

[0049] Figure 15 1 is a bar graph showing the tensile stability, dry stability, and wet stability of the flexible patterned fuel cell patch in Example 1.

[0050] Figure 16 Graph showing the oxygen consumption capability of the flexible patterned fuel cell patch in Example 1.

[0051] Figure 17 This is a diagram showing the effect of the flexible patterned fuel cell patch in Example 1 repairing sciatic nerve damage.

[0052] Figure 18 This is a diagram showing the effect of the flexible patterned fuel cell patch in Example 1 repairing myocardial damage. DETAILED DESCRIPTION

[0053] In order to make the purpose and technical solution of the present invention clearer, the present invention is further described in detail below with reference to the accompanying drawings. The following examples are only used to illustrate the present invention and should not be construed as limiting the scope of the present invention. Where specific techniques or conditions are not specified in the examples, they are carried out according to the techniques or conditions described in the literature in this field or according to the product specifications.

[0054] Example 1

[0055] (1) Preparation of PtNi ANC

[0056] 39.3 mg of platinum acetylacetonate and 15.6 mg of nickel acetylacetonate were dispersed in 30 mL of oleylamine solution, and then 180 mg of glucose and 600 mg of hexadecyltrimethylammonium bromide were added. The mixture was ultrasonically dispersed for 1 hour and heated to 180 ° C within 40 minutes. After heating for 18 hours, the mixture was naturally cooled, centrifuged (40 ° C, 9000 rpm), and then washed five times with ethanol (15 ° C, 9000 rpm) to obtain PtNi ANC, named Pt 1.5 The same method was used to prepare PtNi ANCs with a feed ratio of 1:0, 2:1, 1:1, 2:3 and 1:2 for platinum acetylacetonate and nickel acetylacetonate. The prepared products were named Pt NWs, Pt2Ni, PtNi, PtNi 1.5 , PtNi2.

[0057] like Figure 1 Shown are TEM images of PtNi ANC with different feed ratios ( Figure 1Where af is PtNi ANC with the feed ratio of platinum acetylacetonate: nickel acetylacetonate of 1:0, 2:1, 3:2, 1:1, 2:3 and 1:2 respectively. With the increase of nickel acetylacetonate input, PtNi ANC changes from nanowire morphology to nanochain morphology, and when the nickel acetylacetonate input is high, the size of the nanoparticles on the nanochain is uneven.

[0058] like Figure 2 As shown in FIG, the XRD spectra of PtNi ANC with different feed ratios are obtained. It can be found that with the increase of the amount of nickel acetylacetonate input, an obvious Ni element peak appears on the XRD spectrum.

[0059] like Figure 3 As shown, it is the power density curve of the fuel cell assembled with PtNi ANC at different feed ratios. LIG loaded with PtNi ANC and LIG loaded with Pt / CNT were both inserted into a PBS solution with a glucose concentration of 10 mmol / L as the anode and cathode of the fuel cell, and then connected to the two electrodes of the electrochemical workstation. The linear voltammetry test method was selected for testing at a scan rate of 5 mV / s, and the obtained voltage was multiplied by the current density to obtain the power density curve. The PtNi ANC with a feed ratio of platinum acetylacetonate: nickel acetylacetonate of 3:2 has the highest peak power density. Therefore, in this embodiment, a flexible patterned fuel cell patch is prepared with PtNi ANC with a feed ratio of 3:2.

[0060] like Figure 4 As shown in Figure 2, the isopropanol / water dispersion of PtNi ANC was dropped onto the glassy carbon electrode as the working electrode, and the loading amount of PtNi ANC was 0.2 mg / cm 2 A platinum electrode and an Ag / AgCl electrode were used as the counter and reference electrodes, respectively. The three electrodes were inserted into a PBS solution containing 10 mmol / L glucose and connected to the corresponding electrodes on an electrochemical workstation. Cyclic voltammetry (CV) was performed at a scan rate of 50 mV / s to obtain the cyclic voltammetry curve of the PtNi ANC in glucose solution. A distinct glucose oxidation peak was observed near 0 V, demonstrating the excellent catalytic performance of the PtNi ANC in glucose oxidation.

[0061] (2) Preparation of PtNi APNCC

[0062] 10 mg of PtNi ANC catalyst was introduced into 10 mL of 0.5 M nitric acid solution and heated at 100° C. for 0–10 h. The mixture was then centrifuged and washed five times with ethanol (15° C., 12,000 rpm) to obtain the PtNi APNCC catalyst.

[0063] like Figure 5Shown are TEM images of PtNi APNCC with different etching times ( Figure 5 Where af is the PtNi APNCC with a feed ratio of 0h, 2h, 4h, 6h, 8h and 10h for platinum acetylacetonate: nickel acetylacetonate, respectively. As the etching time increases, the unstable elemental Ni is dissolved by nitric acid, and a nanocage structure appears in the PtNi APNCC. When the etching time exceeds 10 hours, the PtNiAPNCC structure dissolves to a certain extent, which is not conducive to the preparation of highly active and stable catalysts. In this example, PtNi APNCC with an etching time of 8 hours is selected to prepare a flexible patterned fuel cell patch.

[0064] like Figure 6 As shown in Figure 2, the isopropanol / water dispersion of PtNi APNCC was added dropwise to the glassy carbon electrode as the working electrode. The loading amount of PtNi APNCC was 0.2 mg / cm 2 , and then a platinum electrode and an Ag / AgCl electrode were selected as the counter electrode and reference electrode, respectively. The three electrodes were inserted into an oxygen-saturated PBS solution and connected to the three corresponding electrodes of the electrochemical workstation. The cyclic voltammetry test method was selected, and the cyclic voltammetry curve of PtNi APNCC in oxygen-saturated solution was scanned at a scan rate of 50mV / s. Then the linear voltammetry test method was selected, and the linear voltammetry scan curve was obtained by scanning at a scan rate of 20mV / s. PtNi APNCC showed a clear oxygen reduction peak at approximately 0.55V, and the half-wave potential obtained by linear sweep voltammetry was 0.704V. This value is much higher than that of commercial Pt / C (0.602V), indicating that PtNi APNCC has excellent oxygen reduction catalytic performance.

[0065] like Figure 7 As shown, LIG ​​loaded with PtNi ANC and LIG loaded with PtNi APNCC were inserted into a PBS solution with a glucose concentration of 10 mmol / L as the anode and cathode of the fuel cell. Then, the two electrodes of the electrochemical workstation were connected and the linear voltammetry test method was selected to test at a scan rate of 5 mV / s. The obtained voltage was multiplied by the current density to obtain the power density curve of the fuel cell composed of PtNi ANC and PtNi APNCC. The open circuit potential of the fuel cell using PtNi alloy as the electrocatalyst was 0.75 V, which was close to that of the Pt / CNT fuel cell. However, the peak power density of the PtNi alloy fuel cell (79.6 μW / cm 2 ) is much larger than the 60.5 μW / cm of Pt / CNT fuel cells. 2 .

[0066] like Figure 8As shown, the fuel cell composed of PtNi ANC and PtNi APNCC has strong anti-interference capabilities. After adding NaCl, KCl, CaCl2, and lactic acid to the glucose PBS solution of the fuel cell composed of PtNiANC and PtNi APNCC, the open circuit voltage and peak power density of the fuel cell remained essentially unchanged. After adding NaHCO3, the performance of the fuel cell increased by 10%. After adding cysteine ​​alone, the performance of the fuel cell decreased by 9.8%, indicating its excellent anti-interference performance.

[0067] (3) Preparation of LAMC

[0068] 1.8g chitosan (Mw=300000) is dissolved in 90mL acetic acid solution (1.5%). Then, 0.45g lipoic acid is dissolved in 60mL ethanol. These solutions are then mixed, and 1.2g 1-ethyl-(3-dimethylaminopropyl) carbodiimide and 0.3g N-hydroxysuccinimide are then added. After 6 hours of dark reaction, the resulting mixture is dialyzed with deionized water in a dialysis bag (3500Da) for 5 days. The dialyzed solution is then frozen and lyophilized for 3 days to obtain LAMC.

[0069] like Figure 9 As shown in FIG, it is the FT-TR spectrum of chitosan, lipoic acid and LAMC in the example of the present invention. Figure 9 As can be seen from the figure, the infrared spectra of LAMC and chitosan are basically consistent. Since the grafting rate of lipoic acid on LAMC is not high, only at 875 cm -1 A weaker characteristic peak of the disulfide bond in lipoic acid appeared nearby, proving the successful synthesis of LAMC.

[0070] (4) Preparation of PTBPS

[0071] Phenyl borate quaternary ammonium salt (0.55g) and 3-glycidoxypropyltrimethoxysilane (0.47g) are dissolved among the 30mL NMP, and under nitrogen atmosphere, heated at 100 ℃ for 10 hours.Then, the mixture is naturally cooled, centrifuged and washed (8000rpm, 15 ℃) to obtain a white solid. The solid is dissolved in water, and in a dialysis bag (3500Da), it is dialyzed 3 days with deionized water. The dialyzate is then frozen and lyophilized for 3 days to obtain PTBPS.

[0072] like Figure 10 As shown, it is the phenyl borate quaternary ammonium salt and PTBPS in the example of the present invention. 1 H-NMR spectrum. PTBPS basically has the characteristic NMR peaks of phenylboronic acid quaternary ammonium salt, and the characteristic peak of epoxy group appears at 3.2ppm, which proves the successful synthesis of PTBPS.

[0073] (5) Preparation of flexible patterned fuel cell patches

[0074] LAMC (90 mg) and PTBPS (9 mg) were dissolved in 3 mL of deionized water. The resulting solution was added to the mold and exposed to ultraviolet light (365 nm, 3 W / cm 2 ) for 30 seconds to obtain LAMC hydrogel. The electrocatalyst suspension was printed on different LIG electrodes as anode and cathode, with a catalyst loading of 0.2 mg / cm 2 The PI film containing LIG was placed directly in contact with the LAMC hydrogel. The hydrogel was then frozen in liquid nitrogen. After 20 seconds, the hydrogel was brought to room temperature and the PI film was carefully peeled off. Finally, the LIG pattern was perfectly transferred to the hydrogel surface, resulting in a flexible patterned fuel cell patch.

[0075] like Figure 11 The following figure shows the mechanical and adhesive properties of the LAMC hydrogel of the present invention. A 30×10×1 mm LAMC hydrogel strip was fixed to the fixture of a universal testing machine, and the tensile test method was selected to record the tensile curve. The LAMC hydrogel exhibited a tensile strength of 5 kPa and a maximum tensile strain of 24%, indicating weak mechanical properties. With the addition of PTBPS, both the tensile strain and tensile strength of the hydrogel increased dramatically. When the mass ratio of LAMC to PTBPS was 10:1, the tensile strength and maximum tensile strain were 24 kPa and 71%, respectively, and the Young's modulus was 35 kPa.

[0076] A 10×10×1 mm LAMC hydrogel was placed between two adhesive substrates (polypropylene sheet, iron sheet, glass sheet, porcine skin, and porcine loin, respectively). After 10 minutes, the substrates were secured to the fixture of a universal testing machine. The tensile test was performed, and the test was stopped when the two substrates separated. The maximum stress recorded was the hydrogel's adhesion strength. The LAMC hydrogel exhibited strong adhesion to biological tissues, such as porcine skin and porcine loin, reaching 52 kPa, meeting the requirements for in vivo applications.

[0077] like Figure 12Shown are the rheological properties of the LAMC hydrogel of the present invention. The LAMC hydrogel was subjected to a 5-minute time scan, a 25-50°C temperature scan, and a 0.1-100 rad / s frequency scan using a rheometer to test the storage modulus and loss modulus of each hydrogel. All hydrogels with different PTBPS contents remained cross-linked (G'>G"). The higher the PTBPS content, the higher the G' value, but the smaller the shear strain. When the mass ratio of LAMC to PTBPS was 10:1, the hydrogel had high modulus and shear strain. During the scanning process, when the temperature, shear rate, and time changed, the G' and G" values ​​of the LAMC hydrogel remained basically unchanged, confirming the stability of the hydrogel.

[0078] like Figure 13 , which is an image of the LIG electrode of the present invention. Figure 13 The SEM images in FIG1 show that the LIG technology used in the present invention can achieve high-precision preparation of various patterned electrodes.

[0079] like Figure 14 The figure shows the power density curve of the flexible patterned fuel cell patch in the present invention in vitro and in vivo. The patch can show an open circuit voltage of 0.42V and a power density of 59.01μW / cm 2 Furthermore, after subcutaneous implantation in rats, the patch can generate an open circuit voltage of 0.403 V and a peak power density of 51.55 μW / cm 2 The peak power density is in line with the electrical stimulation intensity requirements for in situ repair of rat heart and nerve tissue.

[0080] like Figure 15 The following graphs show the tensile stability, dry stability, and wet stability of the flexible patterned fuel cell patch of the present invention. The open-circuit voltage of the flexible patterned fuel cell patch was tested after a certain number of stretching cycles, after being placed in a moisturizing environment for a period of time, and after being immersed in a PBS solution for a period of time. In all three cases, the open-circuit voltage of the patch decreased slowly, demonstrating its excellent stability.

[0081] like Figure 16 Figure 2 shows the oxygen consumption capacity of the flexible patterned fuel cell patch of the present invention. When the glucose concentration was 10 mM, the dissolved oxygen concentration in the solution dropped rapidly to 4 mg / L within 10 minutes, and then slowly dropped to 2 mg / L within 30 minutes, demonstrating the patch's ability to create an oxygen-deficient environment.

[0082] like Figure 17The figure shows the effect of the flexible patterned fuel cell patch in the present invention on the regeneration of sciatic nerve defects. The flexible patterned fuel cell patch was rolled into a catheter shape and transplanted to the sciatic nerve defect site as a nerve conduit. Three months after implantation, the sciatic nerve regeneration of SD rats was evaluated. After statistical analysis of the gastrocnemius muscle wet weight, walking footprints and electrophysiological test results, the sciatic nerve recovery index (SFI), gastrocnemius muscle wet weight, nerve conduction velocity and compound action potential amplitude of the patterned fuel cell patch group were significantly greater than those of the hydrogel group, and better than the autologous transplantation group, reflecting its excellent repair effect.

[0083] like Figure 18 Figure 2 shows the effectiveness of the flexible patterned fuel cell patch of the present invention for myocardial damage repair. The flexible patterned fuel cell patch was adhered to the surface of the infarcted heart of SD rats, and the chest was sutured. Myocardial damage repair was assessed 28 days after implantation. Figure 18 The sham group was a sham operation group, the MI group was a myocardial infarction group, the Hydrogel group was a LAMC hydrogel group adhered to the myocardial infarction area, the FCP group was a non-patterned fuel cell group adhered to the myocardial infarction area, and the PFCP group was a patterned fuel cell group adhered to the myocardial infarction area. Cardiac ultrasound showed that the patterned fuel cell patch group had the best recovery. In the MI group, electrocardiogram examination observed pathological Q wave deepening, T wave inversion, and prolonged QRS duration, indicating that fibrosis affects the depolarization and repolarization processes. Compared with other experimental treatments, the patterned fuel cell patch can reduce ST segment elevation, shorten the QRS interval duration, and regulate cardiac electrophysiological behavior with a significantly shorter QRS duration. At the same time, Masson staining images also demonstrated that the hearts in the patterned fuel cell patch group had the smallest fibrosis area and the largest left ventricular wall thickness.

[0084] Depend on Figure 17 and Figure 18 It can be seen that flexible patterned fuel cell patches have great potential in tissue repair.

[0085] It should be understood that the application of the present invention is not limited to the above examples. For those skilled in the art, improvements or changes can be made based on the above description. All these improvements and changes should fall within the scope of protection of the claims attached to the present invention.

Claims

1. A method for preparing a flexible patterned fuel cell patch, characterized in that: The preparation method comprises: (1) Platinum acetylacetonate, nickel acetylacetonate, glucose, and hexadecyltrimethylammonium bromide were added to an oleylamine solution and heated to obtain PtNi alloy nanochains (PtNi ANCs) as an anode catalyst; (2) PtNi ANC was added to a dilute nitric acid solution and heated and etched to obtain PtNi alloy nanocage chain PtNi APNCC as a cathode catalyst; (3) Chitosan and lipoic acid are dissolved separately and then mixed, and then 1-ethyl-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide are added, and the resulting mixture is reacted in the dark to obtain lipoic acid-grafted chitosan LAMC; (4) adding a quaternary ammonium salt of phenylboronic acid derivative TSPBA and 3-(2,3-epoxypropyloxy)propyltrimethoxysilane GPTMS to a polar organic solvent, and heating the resulting mixture to obtain an epoxy hyperbranched polymer PTBPS; (5) LAMC and PTBPS were dissolved in water and formed into a hydrogel under ultraviolet light irradiation; (6) PtNi ANC and PtNi APNCC were added to laser-induced graphene LIG as the anode and cathode, respectively, and LIG was then transferred to the hydrogel by freeze transfer to obtain a flexible patterned fuel cell patch.

2. The method for preparing a flexible patterned fuel cell patch according to claim 1, wherein: In step (1), the molar ratio of platinum acetylacetonate to nickel acetylacetonate is 1:2-2:

1.

3. The method for preparing a flexible patterned fuel cell patch according to claim 1, wherein: In step (1), the mixed solution is continuously heated in an oil bath at 160-200° C. for 10-18 hours to obtain PtNi ANC.

4. The method for preparing a flexible patterned fuel cell patch according to claim 1, wherein: In step (2), the mixed solution is continuously heated in an oil bath at 60° C. for 2-10 hours to obtain PtNi APNCC.

5. The method for preparing a flexible patterned fuel cell patch according to claim 1, wherein: In step (3), the mass of the lipoic acid is 5-30% of the mass of the chitosan; and the mixed solution is reacted in a water bath at 15-40° C. in the dark for 4-12 hours.

6. The method for preparing a flexible patterned fuel cell patch according to claim 1, wherein: In step (4), the mass of the TSPBA is 10-50% of the mass of the GPTMS; the mixed solution is reacted continuously in an oil bath at 80-120°C for 6-12 hours.

7. The method for preparing a flexible patterned fuel cell patch according to claim 1, wherein: In step (5), the mass ratio of LAMC to PTBPS is 20:1-5:

1.

8. The method for preparing a flexible patterned fuel cell patch according to claim 1, wherein: In step (6), the loading of PtNi ANC and PtNi APNCC on the LIG electrode was 0.05-0.5 mg / cm 2 .

9. A flexible patterned fuel cell patch prepared by the preparation method according to any one of claims 1 to 8.

10. Use of the flexible patterned fuel cell patch according to claim 9 in the preparation of nerve repair and myocardial injury repair products.

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