A photocured conductive hybrid nanohydrogel based on MPN-PEDOT:PSS and a preparation method and application thereof

By photocuring and crosslinking MPN-PEDOT:PSS with GelMA, a conductive nano-hydrogel framework is formed, which solves the problems of insufficient conductivity, bioactivity and stability of traditional hydrogels and achieves efficient tissue repair and regeneration effects.

CN121154926BActive Publication Date: 2026-02-17SICHUAN UNIV
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Patent Information

Application Number
CN202511721510.2
Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Filing Date
2025-11-21
Publication Date
2026-02-17
Estimated Expiration
2045-11-21

AI Technical Summary

Technical Problem

Traditional hydrogels have shortcomings in conductivity, bioactivity, and stability, making it difficult to meet the requirements for electrical signal transmission in myocardial tissue engineering and nerve repair.

Method used

Through the hybrid cross-linking reaction of MPN network formed by organic matter containing phenolic hydroxyl groups and Mg2+ with PEDOT:PSS, combined with the photocuring cross-linking of GelMA, a conductive nano-hydrogel framework is formed, which enhances conductivity and anti-inflammatory and antioxidant capabilities.

Benefits of technology

It achieves high conductivity, anti-inflammatory and antioxidant properties, enhances the mechanical stability of the hydrogel, and has the ability to release drugs/biological factors in a controlled manner, making it suitable for tissue regeneration and repair.

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Abstract

The application provides a light-cured conductive hybrid nanohydrogel based on MPN-PEDOT:PSS, a preparation method and application thereof, and relates to the field of biomedical materials.The light-cured conductive hybrid nanohydrogel based on MPN-PEDOT:PSS comprises a hydrogel skeleton formed through hybrid cross-linking reaction of an organic substance containing phenolic hydroxyl groups, Mg2+ and PEDOT:PSS, and the hydrogel skeleton is loaded on GelMA and cross-linked into glue through light curing. 2+ The application forms MPN through dynamic coordination reaction between the organic substance containing phenolic hydroxyl groups and Mg2+, and the surface of the MPN is modified by PEDOT:PSS through hydrogen bonding and covalent bonding to form a nanometer network system, so that the hydrogel skeleton formed in this way is loaded on GelMA and cured into glue through light curing, and the hydrogel has high-efficiency conductivity, anti-inflammatory and antioxidant capacity; and the application improves the tissue repair microenvironment by endowing the hydrogel with the capacity of removing free radicals and inhibiting inflammation through MPN, and can be applied to the preparation of products for promoting tissue regeneration and repair.
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Description

Technical Field

[0001] This invention relates to the field of biomedical materials, and more specifically, to a photocurable conductive hybrid nanohydrogel based on MPN-PEDOT:PSS, its preparation method, and its application. Background Technology

[0002] Hydrogels are widely used in the biomedical field due to their high water content, three-dimensional network structure, and good biocompatibility. However, traditional hydrogels have the following shortcomings:

[0003] 1. Insufficient conductivity: Most natural or synthetic hydrogels lack conductivity, failing to meet the requirements for electrical signal transmission in applications such as myocardial tissue engineering and nerve repair. To improve conductivity, researchers have attempted to introduce conductive polymers such as polypyrrole, polyaniline, and PEDOT:PSS, or conductive nanomaterials (such as graphene and carbon nanotubes) into hydrogels. However, the poor dispersion and weak interfacial bonding of conductive materials in hydrogels often lead to decreased conductivity and insufficient stability.

[0004] 2. Lack of bioactivity: Although conductive polymer materials can improve electrical properties, they generally lack bioactivity, making it difficult to inhibit inflammatory responses and improve oxidative stress environments, thus limiting their application in the repair of damaged tissues.

[0005] 3. Insufficient mechanical strength and stability: The single-network hydrogel structure is fragile and prone to collapse or degradation too quickly in complex in vivo environments, making it difficult to play a long-term role.

[0006] In recent years, metal-polyphenol network (MPN) materials have attracted widespread attention due to their anti-inflammatory, antioxidant, metal-chelating, and good biocompatibility properties. MPNs can scavenge free radicals, alleviate inflammatory responses, and possess good potential for functional modification. However, MPNs themselves have limited conductivity, making it difficult to meet the requirements of tissue electrical stimulation conduction.

[0007] PEDOT:PSS is a high-performance conductive polymer with excellent electron transport capabilities and flexibility, but its stability and functionality are limited in biological systems. Therefore, developing a multifunctional hydrogel using PEDOT:PSS that combines conductivity, anti-inflammation, antioxidant properties, and photocuring ability to solve the problem of existing conductive hydrogels failing to balance functionality and stability is of great significance for advancing tissue repair and regenerative medicine. Summary of the Invention

[0008] The purpose of this invention is to provide a photocurable conductive hybrid nanohydrogel based on MPN-PEDOT:PSS, which utilizes phenolic hydroxyl-containing organic compounds and Mg... 2+MPN, formed through dynamic coordination reaction, and PEDOT:PSS modify the surface of MPN through hydrogen bonding and covalent bonding to form a conductive nanosystem. The resulting hydrogel framework is loaded onto GelMA and cured by photopolymerization, exhibiting high conductivity, anti-inflammatory and antioxidant capabilities.

[0009] The technical problem solved by this invention is achieved by the following technical solution.

[0010] In a first aspect, embodiments of the present invention provide a photocurable conductive hybrid nanohydrogel based on MPN-PEDOT:PSS, comprising organic compounds containing phenolic hydroxyl groups, Mg... 2+ The hydrogel framework is formed by hybrid crosslinking reaction of PEDOT:PSS and then loaded onto GelMA and crosslinked by photocuring.

[0011] In some embodiments of the present invention, the above-mentioned hydrogel is composed of organic compounds containing phenolic hydroxyl groups and Mg. 2+ The precursor liquid, composed of PEDOT:PSS, GelMA and photoinitiator, is cross-linked into a gel by photocuring.

[0012] In some embodiments of the present invention, the above-mentioned organic compounds containing phenolic hydroxyl groups are any one or more of dopamine, tannic acid, and EGCG.

[0013] Secondly, embodiments of the present invention provide a method for preparing a photocurable conductive hybrid nanohydrogel based on MPN-PEDOT:PSS, comprising the following steps:

[0014] S1: By mass fraction, dissolve 10-15 parts of organic matter containing phenolic hydroxyl groups and 200-250 parts of magnesium chloride in deionized water, adjust the pH to 7-11, and stir at 400-800 rpm for 20-30 h at room temperature to obtain a uniform MPN solution. Then, wash with anhydrous ethanol and deionized water alternately and freeze dry to obtain MPN powder.

[0015] S2: Dissolve the above MPN powder in PBS buffer to prepare MPN solution, then mix the above MPN solution with PEDOT:PSS solution, sonicate for 30 min and stir at room temperature for 10-15 h to obtain MPN-PEDOT conductive nanoparticle solution.

[0016] S3: Dissolve GelMA in PBS buffer, stir at 40°C until completely dissolved, then add the above MPN-PEDOT conductive nanoparticle solution, and sonicate to obtain GelMA@MPN-PEDOT solution.

[0017] S4: Add a photoinitiator to the above GelMA@MPN-PEDOT solution and stir at room temperature for 0.5-1h to obtain a precursor solution. Crosslink the above precursor solution under ultraviolet light irradiation for 5-10min to obtain a photocurable conductive hybrid nanohydrogel containing MPN-PEDOT conductive nanoparticles.

[0018] Furthermore, in step S1, the stirring rate is 600 rpm, the reaction time is 24 h, and the mixture is washed three times alternately with anhydrous ethanol and deionized water.

[0019] Furthermore, in step S2, the concentration of the MPN solution is 5-20 mg / ml, the concentration of the PEDOT:PSS solution is 0.1% w / v, and the mixing ratio of the MPN solution and the PEDOT:PSS solution is 1-20:1.

[0020] Furthermore, in step S3, the concentration of the MPN-PEDOT conductive nanoparticle solution is 0.1%-0.5% w / v.

[0021] Furthermore, in step S4, the photoinitiator is any one or more of 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenyl ketone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and 2,4,6-trimethylbenzoyl lithium phosphite.

[0022] Furthermore, in the above-mentioned precursor solution, the mixing ratio of the above-mentioned photoinitiator and the above-mentioned GelMA@MPN-PEDOT solution is 1:200-500.

[0023] Thirdly, the embodiments of the present invention provide the application of the above-mentioned photocurable conductive hybrid nanohydrogel based on MPN-PEDOT conductive nanoparticles in the regeneration and repair of tissues in the inflammatory microenvironment.

[0024] Compared with the prior art, the embodiments of the present invention have at least the following advantages or beneficial effects:

[0025] 1. This invention utilizes MPN, PEDOT:PSS formed by dynamic coordination reaction between phenolic hydroxyl-containing organic compounds and Mg2+ to modify the MPN surface, forming an MPN-PEDOT nanonetwork system. This system possesses excellent conductivity and can effectively improve the conductivity of hydrogels.

[0026] 2. This invention endows hydrogels with the ability to scavenge free radicals and inhibit inflammation through MPN, thereby improving the tissue repair microenvironment; the combination of GelMA photocuring crosslinking and MPN drug loading capacity enables the controlled release of drugs / biological factors and enhances the mechanical stability of the hydrogel;

[0027] 3. The preparation method of this invention is simple and easy to implement, and the raw materials are safe, non-toxic, biodegradable, easy to recycle, and environmentally friendly. Attached Figure Description

[0028] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0029] Figure 1 These are SEM images of the MPN nanomaterials in Example 1 of this invention;

[0030] Figure 2 The images shown are SEM images and physical photos of the EGCG-Mgcl2 MPN photocurable conductive hybrid nanohydrogel in Example 4 of this invention.

[0031] Figure 3 The conductivity of each group of hydrogels in Example 5 of this invention;

[0032] Figure 4 This is a diagram showing the intracellular ROS distribution in each group of cells in Example 6 of the present invention;

[0033] Figure 5 These are healing diagrams of the injury sites in each group of rats in Example 7 of the present invention at 6 and 12 weeks of age;

[0034] Figure 6 This is a graph showing the change in EGCG release rate in Example 8 of the present invention. Detailed Implementation

[0035] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0036] It should be noted that, unless otherwise specified, the embodiments and features described in this application can be combined with each other. The present invention will now be described in detail with reference to specific embodiments.

[0037] In the various embodiments of the present invention, the various abbreviations respectively represent:

[0038] EGCG: Epigallocatechin gallate;

[0039] TA: Tannic acid;

[0040] DA: Dopamine;

[0041] MPN: Metal-Polyphenol Network;

[0042] PEDOT: Poly(3,4-ethylenedioxythiophene);

[0043] PSS: Polystyrene sulfonate;

[0044] GelMA: Methacrylated gelatin.

[0045] Example 1

[0046] This embodiment will illustrate a method for preparing a photocurable conductive hybrid nanohydrogel based on MPN-PEDOT:PSS, including the following steps:

[0047] S1. Preparation of EGCG-Mg 2+ MPN nanoparticles.

[0048] First, weigh out 10-15 mg of EGCG powder and 200-250 mg of magnesium chloride solid particles, dissolve them completely in an appropriate amount of deionized water, add an appropriate amount of sodium hydroxide to adjust the pH to 7-11, and stir the reaction at 600 rpm for 24 hours at room temperature to obtain a homogeneous EGCG-Mg MPN solution. Then, wash the MPN solution three times alternately with anhydrous ethanol and deionized water, and freeze-dry the resulting powder to obtain Mg-EGCG MPN nanoparticles.

[0049] pass Figure 1 It can be seen that EGCG-Mg 2+ MPN nanoparticles exhibit an irregular crystalline structure because Mg 2+ A rapid dynamic coordination reaction occurs between EGCG and EGCG, forming a stable chelate structure. However, due to the fast rate of the coordination reaction and the diverse intermolecular forces, it is difficult to form a regular and ordered crystal. In addition, the numerous hydroxyl groups on the EGCG molecule can form a dense network of hydrogen bonds with each other, as well as with surrounding water molecules or substrate surface groups, further enhancing the stability of the structure. Furthermore, π-π stacking can occur between the benzene ring structures of EGCG. This interaction facilitates intermolecular aggregation and orderly arrangement, making the entire structure more stable.

[0050] S2. Preparation of MPN-PEDOT conductive nanoparticle network.

[0051] freeze-dried EGCG-Mg 2+MPN nanoparticle powder was dissolved in PBS buffer at a concentration of 5 mg / ml to prepare MPN solution; 0.1% w / v PEDOT:PSS mixed solution was taken, and then the MPN solution and PEDOT:PSS solution were mixed in a 1:1 ratio, sonicated for 30 min and stirred at room temperature for 12 h to obtain MPN-PEDOT conductive nanoparticle solution.

[0052] It should be noted that in this step, PSS, as a water-soluble dopant and stabilizer, uses its sulfonic acid group (-SO3H) to perform "p-type doping" on PEDOT, thereby significantly improving its conductivity. PEDOT: PSS modifies the MPN surface through hydrogen bonding and covalent bonding, forming a stable conductive nanosystem.

[0053] S3. Prepare GelMA@MPN-PEDOT solution.

[0054] Dissolve 100 mg of GelMA in 1 ml of PBS buffer and stir at 40 °C until completely dissolved. Add 10 mg / ml of MPN-PEDOT conductive nanoparticle solution and sonicate for 10 min to mix thoroughly to obtain GelMA@MPN-PEDOT solution.

[0055] S4. Prepare photocurable GelMA@MPN-PEDOT hydrogel.

[0056] A photoinitiator was added to the GelMA@MPN-PEDOT solution and stirred at room temperature for 0.5-1 h to obtain a precursor solution. The precursor solution was then subjected to crosslinking reaction under 405 nm ultraviolet light for 5-10 min to obtain a photocurable conductive hybrid nanohydrogel containing MPN-PEDOT conductive nanoparticles.

[0057] Optionally, the photoinitiator can be any one of 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenyl ketone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, or 2,4,6-trimethylbenzoyl lithium phosphite.

[0058] Example 2

[0059] The steps in this embodiment are basically the same as those in Embodiment 1, with the only difference being:

[0060] In step S1, first weigh 10-15 mg of DA powder and 200-250 mg of magnesium chloride solid granules, dissolve them completely in an appropriate amount of deionized water, add an appropriate amount of sodium hydroxide to adjust the pH to 7-11, and stir the mixture at 600 rpm for 24 hours at room temperature to obtain a homogeneous DA-Mg. 2+The MPN solution was then washed three times alternately with anhydrous ethanol and deionized water. The resulting powder after lyophilization was DA-Mg. 2+ MPN nanoparticles.

[0061] Example 3

[0062] The steps in this embodiment are basically the same as those in Embodiment 1, with the only difference being:

[0063] In step S1, first weigh 10-15 mg of TA powder and 200-250 mg of magnesium chloride solid granules, dissolve them completely in an appropriate amount of deionized water, add an appropriate amount of sodium hydroxide to adjust the pH to 7-11, and stir the mixture at 600 rpm for 24 hours at room temperature to obtain a homogeneous TA-Mg. 2+ The MPN solution was then washed three times alternately with anhydrous ethanol and deionized water. The resulting powder after lyophilization was TA-Mg. 2+ MPN nanoparticles.

[0064] Example 4

[0065] This embodiment further observed the internal structure and surface morphology of the photocurable conductive hybrid nanohydrogel containing MPN-PEDOT conductive nanoparticles (GPM group) prepared in Example 1, and set up two control groups, one of which was pure water GelMA hydrogel (G group), and the other was PEDOT:PSS hydrogel without MPN (GP group). The experimental results are as follows. Figure 2 As shown, after the addition of PEDOT, EGCG-Mgcl2 and MPN to the polymer, the appearance of the GelMA hydrogel changed from white and translucent to black. This indicates that the porous morphology of the hydrogel significantly promoted the deposition of the EGCG-Mgcl2-PEDOT nanoparticle network system on the interpenetrating pore walls.

[0066] Example 5

[0067] This embodiment tests the conductivity of the photocurable conductive hybrid nanohydrogels containing MPN-PEDOT conductive nanoparticles prepared in Examples 1-3, and sets up two control groups, one of which is pure water GelMA hydrogel and the other is PEDOT:PSS hydrogel without MPN. A four-probe tester is used to uniformly contact the probes with the hydrogel surface at room temperature, and the conductivity is as follows: Figure 3As shown in the figure, there are significant differences in conductivity among the different hydrogel systems. The G group (GelMA) without MPN and PEDOT:PSS has the lowest conductivity, at approximately 0.05 S / m. The GP group (GelMA / PEDOT) without MPN has a conductivity of approximately 0.47 S / m. After introducing DA-Mgcl2MPN (DA-Mgcl2 group), the conductivity increases to approximately 0.68 S / m; the conductivity of TA-Mgcl2MPN (TA-Mgcl2 group) and EGCG-Mgcl2MPN (EGCG-Mgcl2 group) further increases, reaching approximately 1.07 S / m and 1.24 S / m, respectively. This demonstrates that the conductivity of the hydrogel is significantly improved with the addition and increase of MPN concentration. These results indicate that the conductivity of photocurable conductive hybrid nanohydrogels containing MPN-PEDOT conductive nanoparticles is much higher than that of ordinary hydrogels.

[0068] Example 6

[0069] This embodiment tested the anti-inflammatory and antioxidant properties of the photocurable conductive hybrid nanohydrogels containing MPN-PEDOT conductive nanoparticles prepared in Examples 1-3. The main method involved co-culturing the hydrogels with RSC cells and then inducing RSC inflammation with lipopolysaccharide (LPS), and evaluating the effect of the hydrogel extract on clearing intracellular ROS. The specific steps were as follows:

[0070] Set up a blank control group (Control group): Standard culture medium containing only RSC cells;

[0071] LPS model group (LPS group): RSC cells + LPS, used to confirm that LPS successfully induced the inflammation and oxidative stress model, and served as a positive damage control;

[0072] GelMA group (G group): RSC cells + GelMA hydrogel extract + LPS, used to evaluate whether the basic hydrogel material itself has a protective or effect on cells;

[0073] GelMA+PEDOT group (GP group): RSC cells + GelMA / PEDOT composite hydrogel extract + LPS, used to evaluate the antioxidant effect of PEDOT component;

[0074] GelMA+DA-Mgcl2MPN-PEDOT group (GP+DA-Mgcl2 group): RSC cells + GelMA / DA-Mgcl2-PEDOT nanocomposite hydrogel extract + LPS, used to evaluate the antioxidant performance enhanced by DA-Mgcl2 nanoparticles.

[0075] GelMA+TA-Mgcl2MPN-PEDOT group (GP+TA-Mgcl2 group): RSC cells + GelMA / TA-Mgcl2-PEDOT nanocomposite hydrogel extract + LPS, used to evaluate the antioxidant performance enhanced by TA-Mgcl2 nanoparticles.

[0076] GelMA+EGCG-Mgcl2MPN-PEDOT group (GP+EGCG-Mgcl2 group): RSC cells + GelMA / EGCG-Mgcl2-PEDOT nanocomposite hydrogel extract + LPS, used to evaluate the antioxidant performance enhanced by EGCG-Mgcl2 nanoparticles.

[0077] The GelMA+MPN-PEDOT group plus electrical stimulation (GPM+ES group) was used to evaluate the antioxidant properties of hydrogels enhanced with MPN-PEDOT nanoparticles under exogenous electrical stimulation.

[0078] Then, fluorescent labeling was used to label the ROS in the cells of the eight test groups. The experimental results are as follows: Figure 4 As shown in the figure, the LPS-stimulated group exhibited significant green fluorescence, indicating a high level of ROS production in RSC cells, which can serve as a positive damage control. The G and GP groups still showed significant green fluorescence, indicating that these hydrogels were less effective at scavenging ROS, meaning that GelMA and PEDOT did not enhance the antioxidant capacity of the hydrogel. In contrast, the three groups with added MPN showed a significant decrease in green fluorescence, indicating a significant reduction in intracellular ROS content. Comparing the G, GP, and GPM groups, it can be concluded that the presence of MPN significantly improved the antioxidant performance of the hydrogel. Furthermore, the GPM+ES group showed even less green fluorescence, indicating that exogenous electrical stimulation could further enhance the antioxidant capacity of the GelMA@MPN-PEDOT hydrogel, further demonstrating that the GelMA@MPN-PEDOT hydrogel possesses conductivity, anti-inflammatory, and antioxidant capabilities.

[0079] Example 7

[0080] This embodiment further verifies the tissue repair ability of the photocurable conductive hybrid nanohydrogel containing MPN-PEDOT conductive nanoparticles prepared in Example 1, including the following steps:

[0081] SD rats were randomly divided into four groups: a blank control group (G group), a GelMA+PEDOT group (GP group), a GelMA+EGCG-Mgcl2MPN-PEDOT group (GP+EGCG-Mgcl2 group), and a GelMA+MPN-PEDOT group plus electrical stimulation (GPM+ES group), with six rats in each group. The skin of the anesthetized SD rats was incised along the midline to expose the skull, and two 5 mm diameter holes were drilled in the skull. After bone removal, equal amounts of hydrogel were used to fill the defects in each group, and then the incisions were closed and the skin sutured to form a skull bone defect model. SD rats were sacrificed at 6 and 12 weeks post-surgery. The skulls of the SD rats were scanned using micro-CT, and three-dimensional images of the bones were reconstructed using 3DSlicer software. The experimental results are as follows: Figure 5 As shown, the critical-sized defects in the blank control group and group G remained unhealed at weeks 6 and 12, indicating no bone regeneration. However, the defects in the GP, GPM, and GPM+ES groups showed significant healing, indicating bone regeneration. The GPM and GPM+ES groups exhibited relatively higher healing rates, demonstrating that GelMA@MPN-PEDOT hydrogel can promote bone regeneration, with even better results under exogenous electrical stimulation. This proves that GelMA@MPN-PEDOT hydrogel possesses conductivity, meeting the requirements for electrical signal transmission, and also demonstrates its applicability in tissue repair with excellent repair effects. Based on these characteristics, photocurable conductive hybrid nanohydrogels containing MPN-PEDOT conductive nanoparticles can be used to prepare products that promote tissue regeneration and repair. The specific product form can be selected by those skilled in the art according to actual needs.

[0082] Example 8

[0083] This embodiment further tests the controlled release capability of the photocurable conductive hybrid nanohydrogel containing MPN-PEDOT conductive nanoparticles prepared in Example 1, including the following steps:

[0084] 100 mg of the prepared photocurable conductive hybrid nanogel containing EGCG-MgCl2 MPN conductive nanoparticles was placed in 25 mL of PBS solution, the pH was adjusted to 6.8-7.4, and the sample was incubated at 37°C with shaking at 100 rpm. At a predetermined time, 1 mL of buffer was removed, and the same volume of buffer was added back at 37°C. The EGCG content of the sample was measured at 274 nm using UV-Vis. The experimental results are as follows. Figure 6As shown, EGCG exhibits a typical sustained-release characteristic of "fast at first, then slow": rapid release from 0 to 5 days; followed by a significant decrease in release rate, which tends to plateau after 30 days, with a final release rate of approximately 78%. This indicates that the hydrogel has a significant sustained-release effect on EGCG: gentle release in the initial stage, avoiding a sudden peak; and slow release over a long period in the middle and later stages, maintaining an effective concentration. Therefore, the photocurable conductive hybrid nanohydrogel containing MPN-PEDOT conductive nanoparticles can achieve effective controlled release of EGCG, with significantly better results than the instantaneous release behavior of ordinary hydrogels. This controlled-release capability allows drugs / biological factors to be loaded onto the hydrogel of this invention, achieving a controlled release effect.

[0085] In summary, the embodiments of the present invention provide a photocurable conductive hybrid nanohydrogel based on MPN-PEDOT:PSS, which utilizes Mg 2+ - PEDOT: PSS modifies the surface of MPN nanoparticles through hydrogen bonding and covalent bonding to form an MPN-PEDOT nanonetwork system, which has excellent conductivity and can effectively improve the conductivity of hydrogels.

[0086] This invention endows hydrogels with the ability to scavenge free radicals and inhibit inflammation through MPN, thereby improving the tissue repair microenvironment; the combination of GelMA photocuring crosslinking and MPN drug loading capacity enables the controlled release of drugs / biological factors and enhances the mechanical stability of the hydrogel.

[0087] The preparation method of this invention is simple and easy to implement, and the raw materials are safe, non-toxic, biodegradable, easy to recycle, and environmentally friendly.

[0088] The embodiments described above are some, but not all, embodiments of the present invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

Claims

1. A photocurable conductive hybrid nanohydrogel based on MPN-PEDOT:PSS, characterized in that, Including organic compounds containing phenolic hydroxyl groups and Mg 2+ A metal-polyphenol network is formed, and the metal-polyphenol network and PEDOT:PSS are cross-linked to form a hydrogel framework, which is loaded on GelMA and cross-linked by photocuring to form a gel.

2. The photocurable conductive hybrid nanohydrogel based on MPN-PEDOT:PSS according to claim 1, characterized in that, The organic compound containing a phenolic hydroxyl group is any one or more of dopamine, tannic acid, and EGCG.

3. A method for preparing a photocurable conductive hybrid nanohydrogel based on MPN-PEDOT:PSS, characterized in that, Includes the following steps: S1: By mass fraction, dissolve 10-15 parts of organic matter containing phenolic hydroxyl groups and 200-250 parts of magnesium chloride in deionized water, adjust the pH to 7-11, and stir at 400-800 rpm for 20-30 hours at room temperature to obtain a uniform MPN solution. Then, wash with anhydrous ethanol and deionized water alternately and freeze-dry to obtain MPN powder. S2: Dissolve the MPN powder in PBS buffer to prepare an MPN solution. Then mix the MPN solution with a PEDOT:PSS solution, sonicate for 30 min, and stir at room temperature for 10-15 h to obtain an MPN-PEDOT nanoparticle solution. S3: Dissolve GelMA in PBS buffer, stir at 40°C until completely dissolved, then add the MPN-PEDOT conductive nanoparticle solution, and sonicate to obtain GelMA@MPN-PEDOT solution. S4: Add a photoinitiator to the GelMA@MPN-PEDOT solution and stir at room temperature for 0.5-1h to obtain a precursor solution. Crosslink the precursor solution under ultraviolet light for 5-10min to obtain a photocurable conductive hybrid nanohydrogel containing MPN-PEDOT conductive nanoparticles.

4. The method for preparing a photocurable conductive hybrid nanohydrogel based on MPN-PEDOT:PSS according to claim 3, characterized in that, In step S1, the stirring rate is 600 rpm, the reaction time is 24 h, and the mixture is washed three times with alternating anhydrous ethanol and deionized water.

5. The method for preparing a photocurable conductive hybrid nanohydrogel based on MPN-PEDOT:PSS according to claim 4, characterized in that, In step S2, the concentration of the MPN solution is 5-20 mg / mL, the concentration of the PEDOT:PSS solution is 0.1% w / v, and the mixing ratio of the MPN solution and the PEDOT:PSS solution is 1-20:

1.

6. The method for preparing a photocurable conductive hybrid nanohydrogel based on MPN-PEDOT:PSS according to claim 5, characterized in that, In step S3, the concentration of the MPN-PEDOT conductive nanoparticle solution is 0.1%-0.5% w / v.

7. The method for preparing a photocurable conductive hybrid nanohydrogel based on MPN-PEDOT:PSS according to claim 6, characterized in that, In step S4, the photoinitiator is any one or more of 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenyl ketone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and 2,4,6-trimethylbenzoyl lithium phosphite.

8. The method for preparing a photocurable conductive hybrid nanohydrogel based on MPN-PEDOT:PSS according to claim 7, characterized in that, In the precursor solution, the mixing ratio of the photoinitiator and the GelMA@MPN-PEDOT solution is 1:200-500.

9. The application of the photocurable conductive hybrid nanohydrogel based on MPN-PEDOT:PSS as described in claim 1 in the preparation of products for promoting tissue regeneration and repair.

Citation Information

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