Bionic wound dressing with fluid management and self-power generation, and preparation method and application thereof

Abstract

The application discloses a kind of liquid management and spontaneous power generation dual bionic wound dressing and preparation method and application.The dual bionic wound dressing includes first electrode layer, barrier layer, hygroscopic power generation layer, diffusion antibacterial layer, evaporation power generation layer and second electrode layer stacked in order from bottom to top;The application adopts high biocompatibility electrostatic spinning fiber membrane, realizes the triple function of wound antibacterial, seepage efficient management and stable power generation by combining the liquid transport mechanism of plant transpiration with the ion active transport principle of electric ray power generation cell through bionic design, regulates wound microenvironment, effectively avoids excessive inflammation caused by seepage accumulation, significantly promotes fibroblast migration, angiogenesis and skin appendage regeneration, accelerates wound healing, and is beneficial to restore skin function, provides a new treatment for burn wound repair.

Description

Technical Field

[0001] This invention relates to the field of skin dressings, specifically to a dual biomimetic wound dressing for exudate management and self-generating electricity, as well as its preparation method and application. Background Technology

[0002] Burns are one of the most common and serious traumas worldwide, causing numerous deaths each year, with infection being the leading cause of death. Exudate management is a core challenge in burn wound treatment. Wound exudate is rich in proteins and inflammatory factors; if not promptly removed, it can accumulate, promote bacterial growth, and trigger an excessive inflammatory response, thus delaying wound healing. Therefore, developing wound dressings that can effectively manage exudate, inhibit infection, and promote wound healing has significant clinical implications.

[0003] Currently, traditional passive dressings such as gauze and hydrogel mainly manage exudate through physical absorption, but they have drawbacks such as limited absorption capacity, easy saturation and backflow, and insufficient antibacterial properties. In particular, ordinary gauze tends to stick to the wound after absorbing fluid, and can easily cause secondary damage when changing it.

[0004] In recent years, electrostimulation therapy has been shown to promote fibroblast migration, angiogenesis, and collagen deposition, significantly accelerating wound healing. However, existing electrostimulation devices rely on external power sources, resulting in problems such as large size, inconvenience of use, and high treatment costs, limiting their widespread clinical application. To address this issue, researchers have developed various self-powered dressings, such as materials based on triboelectric, piezoelectric, or thermoelectric effects, which can convert environmental energy such as mechanical and thermal energy into electrical energy. However, these materials generally suffer from technical bottlenecks such as low energy conversion efficiency, unstable output voltage, and short continuous working time. Furthermore, most existing self-powered dressings require external stimulation sources (such as pressure or temperature changes), failing to fully utilize the exudate resources already present in the wound.

[0005] In terms of material selection, existing technologies mostly use precious metal electrodes (such as gold and platinum) or complex nanostructure designs, which not only increases the preparation cost but may also affect the biocompatibility and clinical applicability of the materials.

[0006] In summary, existing wound dressings have significant shortcomings in terms of exudate management, antibacterial properties, and self-powering capabilities. There is an urgent need to develop a novel wound dressing that can simultaneously achieve efficient exudate management, continuous and stable power generation, and excellent biocompatibility. An ideal dressing should eliminate dependence on external devices, fully utilize the characteristics of wound exudate, and achieve integrated "treatment-power generation," providing burn patients with a safer, more effective, and economical treatment option. Summary of the Invention

[0007] The purpose of this invention is to overcome the shortcomings of existing technologies and provide a dual-bionic wound dressing for exudate management and self-generating power, along with its preparation method and application. The dual-bionic wound dressing of this invention consists of a functional layer and an electrode layer. The functional layer includes a barrier layer, a moisture-absorbing power-generating layer, a diffusion-based antibacterial layer, and an evaporative power-generating layer stacked sequentially. The electrode layer is an inert-active asymmetric metal layer or an inert-inert symmetric metal layer. This invention utilizes a highly biocompatible electrospun fiber membrane, combining the liquid transport mechanism of plant transpiration with the active ion transport principle of electric rays, through biomimetic design. This achieves the dual functions of efficient exudate management and stable power generation, thereby regulating the wound microenvironment and promoting wound healing and tissue regeneration.

[0008] To achieve the above objectives, the technical solution designed by the present invention is as follows:

[0009] This invention provides a dual bionic wound dressing for exudate management and self-generating power, the dual bionic wound dressing comprising, from bottom to top, a first electrode layer, a barrier layer, a moisture-absorbing power-generating layer, a diffusion antibacterial layer, an evaporative power-generating layer, and a second electrode layer stacked sequentially.

[0010] The barrier layer is made of polylactic acid and polycaprolactone, wherein the mass ratio of polylactic acid to polycaprolactone is 1:0.5-2.5.

[0011] The hygroscopic power generation layer includes a core layer and a shell layer. The raw materials of the core layer include polyethylene glycol and polydiallyl dimethyl ammonium chloride, and the mass-to-volume ratio of polyethylene glycol and polydiallyl dimethyl ammonium chloride is 1:0.6-2 g / mL. The raw material of the shell layer includes polyacrylonitrile.

[0012] The raw materials for the diffusion antibacterial layer include polyvinyl alcohol and chitosan, wherein the mass ratio of polyvinyl alcohol to chitosan is 1:0.1-0.25;

[0013] The raw materials for the evaporation power generation layer include polyacrylonitrile, polyethylene glycol, ferric acetylacetone, and poly-4-styrene sulfonic acid, wherein the mass ratio of polyacrylonitrile, polyethylene glycol, and ferric acetylacetone is 1:0.5:0.05-0.2; and the mass-volume ratio of polyacrylonitrile and poly-4-styrene sulfonic acid is 1:0.15-1.5 g / mL.

[0014] Furthermore, the mass ratio of polylactic acid to polycaprolactone is 1:1;

[0015] The mass-to-volume ratio of polyethylene glycol and polydiallyl dimethylammonium chloride is 1:1.6 g / mL;

[0016] The mass ratio of polyvinyl alcohol to chitosan is 1:0.15;

[0017] The mass ratio of polyacrylonitrile, polyethylene glycol, and iron acetylacetone is 1:0.5:0.1; the mass-to-volume ratio of polyacrylonitrile and poly-4-styrene sulfonic acid is 1:0.3 g / mL.

[0018] The first electrode layer is an inert electrode layer, and the second electrode layer is either an inert electrode layer or an active electrode layer.

[0019] Furthermore, the inert metal in the inert electrode layer is any one of gold, silver, and platinum, and the active metal in the active electrode layer is any one of magnesium, zinc, aluminum, and iron.

[0020] Furthermore, the inert metal in the inert electrode layer is silver, and the active metal in the active electrode layer is magnesium.

[0021] Furthermore, the thickness of the first electrode layer is 0.8-1.6 μm, the thickness of the barrier layer is 10-15 μm, the thickness of the moisture-absorbing power generation layer is 15-20 μm, the thickness of the diffusion antibacterial layer is 20-25 μm, the thickness of the evaporation power generation layer is 20-25 μm, and the thickness of the second electrode layer is 0.5-0.7 μm.

[0022] The present invention also provides a method for preparing the aforementioned dual biomimetic wound dressing, comprising the following steps:

[0023] (1) According to the above mass ratio of polylactic acid and polycaprolactone, polylactic acid and polycaprolactone are dissolved in hexafluoroisopropanol and stirred to obtain a barrier layer solution.

[0024] (2) A barrier layer is formed by preparing a polylactic acid / polycaprolactone blend electrospun fiber membrane using a barrier layer solution via electrospinning technology.

[0025] (3) According to the above mass-volume ratio of polyethylene glycol and polydiallyl dimethyl ammonium chloride, polyethylene glycol and polydiallyl dimethyl ammonium chloride are dissolved in tetrahydrofuran and stirred to obtain a core layer solution. Polyacrylonitrile is dissolved in N,N-dimethylformamide and stirred to obtain a shell layer solution.

[0026] (4) Using core layer solution and shell layer solution, a core-shell structured nanofiber membrane is prepared on the surface of the barrier layer by coaxial electrospinning technology to form a moisture-absorbing and power-generating layer;

[0027] (5) According to the above mass ratio of polyvinyl alcohol and chitosan, dissolve polyvinyl alcohol and chitosan in an aqueous acetic acid solution, and stir to obtain a diffusion antibacterial solution;

[0028] (6) Using a diffusion antibacterial solution, a polyvinyl alcohol / chitosan blend electrospun fiber membrane is prepared on the surface of the moisture-absorbing power generation layer by electrospinning technology to form a diffusion antibacterial layer;

[0029] (7) According to the above mass ratio of polyacrylonitrile, polyethylene glycol and acetylacetone iron and the mass-volume ratio of polyacrylonitrile and poly4-styrene sulfonic acid, polyacrylonitrile, polyethylene glycol and acetylacetone iron and poly4-styrene sulfonic acid are dissolved in N,N-dimethylformamide and stirred to obtain an evaporation power generation layer solution.

[0030] (8) Using the evaporation power generation layer solution, a polyacrylonitrile / polyethylene glycol / poly4-styrenesulfonic acid / acetylacetone iron blend electrospun fiber membrane is prepared on the surface of the diffusion antibacterial layer by electrospinning technology to form an evaporation power generation layer;

[0031] (9) An inert metal is deposited on the outside of the barrier layer by magnetron sputtering to form the first electrode layer, and an active metal or inert metal is deposited on the outside of the evaporation power generation layer to form the second electrode layer. After vacuum drying and ultraviolet irradiation sterilization, a dual biomimetic wound dressing with exudate management and self-generating power is obtained.

[0032] Furthermore, the barrier layer has a fiber diameter of 1600-2000 nm, an average fiber pore size of 8-10 μm, and a contact angle of 136.8°;

[0033] The moisture-absorbing and power-generating layer has a fiber diameter of 360-400 nm, an average fiber pore size of 1.2-2 μm, and a contact angle of 54.7°.

[0034] The diffusion antibacterial layer has a fiber diameter of 100-150 nm, an average fiber pore size of 0.7-1.2 μm, and a contact angle of 44.7°.

[0035] The evaporation power generation layer has a fiber diameter of 500-550 nm, an average fiber pore size of 1-2 μm, and a contact angle of 64.6°.

[0036] Furthermore, in step (2), the voltage of the electrospinning technology is 6-8 kV, the injection rate is 0.2-0.25 mm / min, the receiving distance is 10-15 cm, and the receiver rotation speed is 200-300 rpm;

[0037] In step (4), the voltage of the coaxial electrospinning technology is 15-18 kV, the core injection rate is 0.02-0.05 mm / min, the shell injection rate is 0.10-0.15 mm / min, the receiving distance is 10-15 cm, and the receiver rotation speed is 200-300 rpm.

[0038] In step (6), the voltage of the electrospinning technology is 18-20 kV, the injection rate is 0.04-0.08 mm / min, the receiving distance is 10-15 cm, and the receiver rotation speed is 200-300 rpm.

[0039] In step (8), the voltage of the electrospinning technology is 12-15 kV, the injection rate is 0.06-0.08 mm / min, the receiving distance is 10-15 cm, and the receiver rotation speed is 200-300 rpm.

[0040] The present invention also provides an application of the aforementioned dual biomimetic wound dressing in antibacterial activity.

[0041] The present invention also provides the application of the aforementioned dual biomimetic wound dressing in the preparation of products that promote wound healing or prevent wound infection.

[0042] The principle of this invention:

[0043] (1) The dual biomimetic wound dressing prepared in this invention has good antibacterial properties, mainly due to the chitosan component in the diffusion antibacterial layer and the iron ions in the evaporation power generation layer. As a cationic polysaccharide, chitosan, after amino protonation, disrupts the integrity of bacterial cell membranes through electrostatic interactions, leading to leakage of intracellular substances; iron ions generate reactive oxygen species through the Fenton reaction, causing oxidative stress damage in bacteria, resulting in lipid peroxidation, protein denaturation, and DNA breakage. After the two are combined, chitosan can enhance the adsorption of iron ions on the bacterial surface and promote the internalization of iron ions, while iron ions enhance the positive charge effect of chitosan, forming more significant membrane damage, and showing significant inhibitory effects on both Gram-positive and Gram-negative bacteria.

[0044] (2) The exudate management function of the dual biomimetic wound dressing prepared in this invention benefits from the Laplace pressure difference formed between the functional layers (barrier layer, moisture-absorbing power generation layer, diffusion antibacterial layer, and evaporative power generation layer) by the pore size gradient and wettability gradient. When the droplet is located at the interface, the liquid (exudate from the wound) is subjected to two Laplace pressures in opposite directions. The resultant force on the droplet in the vertical direction is always upward, and the water transport is unidirectional and irreversible, which can realize the anti-gravity transport of the droplet.

[0045] (3) The exudate-induced self-generating power function of the dual biomimetic wound dressing prepared in this invention is mainly based on the flow potential effect driven by the ion concentration gradient. When the liquid (wound exudate) is transported unidirectionally in the dressing, the positive and negative charges of the exudate-induced functional layer are separated (the hygroscopic power generation layer ionizes to generate chloride ions, and the evaporative power generation layer ionizes to generate hydrogen ions and iron ions). The asymmetric distribution of ions generates an internal electric field, which drives the free-moving ions to migrate in opposite directions to form a current.

[0046] The beneficial effects of this invention are:

[0047] (1) Functional integration and synergistic treatment

[0048] Based on a dual biomimetic design incorporating plant transpiration and electric ray self-generation, this invention achieves unidirectional active transport of wound exudate by constructing a multilayer fiber structure with gradient pore size (10μm→0.7μm) and wettability (contact angle 136.8°→44.7°). Simultaneously, the exudate induces an ion concentration gradient as it flows through the functional layer, driving the directional migration of charge carriers. This allows for a stable output of 1.68V without an external power source, solving the problems of bulky and inconvenient operation of existing electrostimulation therapy devices. This integrated "exudate management-power generation" design can significantly shorten the healing time of burn wounds.

[0049] (2) Energy supply stability

[0050] By optimizing the composition ratio of the hygroscopic power-generating layer and the evaporative power-generating layer, this invention can maintain a voltage fluctuation of less than 5% for 72 hours in an environment of 25°C and 85%RH, which is significantly better than existing triboelectric dressings. If an inert-active asymmetric metal layer is used, the power generation efficiency can be further improved by utilizing the difference in metal activity. This stable power output ensures continuous electrical stimulation therapy, promoting a 4.2-fold increase in fibroblast migration rate and a 1.8-fold increase in blood vessel density.

[0051] (3) Materials Engineering and Industrialization

[0052] The use of electrospinning and magnetron sputtering processes significantly improves production efficiency. By controlling fiber diameter and porosity, biocompatibility is ensured while achieving a water vapor permeability of 12.99 g / (m²·d), superior to commercially available dressings. The magnetron sputtering electrode design reduces the amount of precious metals used, lowering material costs. After UV sterilization, the dressing exhibits a 98% inhibition rate against Staphylococcus aureus and Escherichia coli, and cytotoxicity tests show a survival rate >95%, fully meeting clinical safety requirements. This invention employs a four-layer integrated design: a barrier layer for permeation control, an antibacterial layer for bacteriostasis, a dual-generation layer for power supply, and an electrode layer for stimulation. Animal experiments show a significant improvement in the healing speed of deep second-degree burns and good recovery of skin function.

[0053] The dual biomimetic wound dressing prepared by this invention consists of an electrospun fiber membrane functional layer (barrier layer, moisture-absorbing and power-generating layer, diffusion antibacterial layer, and evaporation power-generating layer) and a magnetron sputtering electrode layer (first electrode layer and second electrode layer). It has good biocompatibility and ensures biological safety to the greatest extent. Through material system innovation and structural optimization, this invention has achieved a technological leap from "passive absorption" to "active treatment" of wound dressings while maintaining excellent biocompatibility, providing a brand-new solution for burn treatment. Attached Figure Description

[0054] Figure 1 A schematic diagram of a dual biomimetic wound dressing for exudate management and self-generating power;

[0055] In the figure, 1 is the second electrode layer, 2 is the evaporative power generation layer, 3 is the diffusion antibacterial layer, 4 is the hygroscopic power generation layer, 5 is the barrier layer, and 6 is the first electrode layer.

[0056] Figure 2 Microscopic morphology images of the hygroscopic power generation layer of polydiallyldimethylammonium chloride at different concentrations;

[0057] Figure 3 The graph shows the power generation capacity of the hygroscopic power generation layer with different concentrations of polydiallyldimethylammonium chloride.

[0058] Figure 4 Microscopic morphology images of the evaporation power generation layer of poly-4-styrene sulfonic acid at different concentrations;

[0059] Figure 5 The graph shows the power generation capacity of the evaporation power generation layer with different concentrations of poly4-styrene sulfonic acid.

[0060] Figure 6 A diagram illustrating the power generation effect of a dual-bionic wound dressing that manages exudate from different inert metals and generates its own electricity.

[0061] Figure 7 A diagram illustrating the power generation effect of a dual biomimetic wound dressing that manages exudate from different active metals and generates its own electricity.

[0062] Figure 8 Figures showing the power generation effect of a dual-bionic wound dressing for exudate management and self-generating electricity under different relative humidity environments.

[0063] Figure 9 Figure 1: Power generation effect of dual biomimetic wound dressing for exudate management and self-generating power at different ambient temperatures;

[0064] Figure 10 A graph showing the water vapor permeability data of a dual biomimetic wound dressing for exudate management and self-generating power generation;

[0065] Figure 11 Figure 1. Antibacterial test results of a plate colony counting method for a dual biomimetic wound dressing for exudate management and self-generating power generation;

[0066] Figure 12 The image shows the results of wound healing using a dual biomimetic wound dressing for exudate management and self-generating electricity in burn wounds. Detailed Implementation

[0067] The present invention will now be described in further detail with reference to specific embodiments, so that those skilled in the art can understand it.

[0068] Example 1

[0069] This embodiment provides a method 1 for preparing a dual biomimetic wound dressing that manages exudate and generates its own electricity, combined with... Figure 1 As shown, it includes the following steps:

[0070] 1. Preparation of the barrier layer:

[0071] S1: Dissolve 0.1 g of polylactic acid and 0.1 g of polycaprolactone in 1 ml of hexafluoroisopropanol, and stir magnetically at room temperature for 3 h to completely dissolve them, thus preparing a barrier layer solution.

[0072] S2: Polylactic acid / polycaprolactone blend electrospun fiber membranes are prepared by electrospinning using a barrier layer solution under the conditions of voltage 6-8 kV, injection rate 0.2-0.25 mm / min, receiving distance 10-15 cm, and receiver rotation speed 200-300 rpm, forming a barrier layer (thickness 10-15 μm). The fiber diameter of the barrier layer is 1600-2000 nm, the average pore size of the fiber is 8-10 μm, and the contact angle of the barrier layer is 136.8°.

[0073] 2. Preparation of the moisture-absorbing power generation layer:

[0074] S1: Dissolve 0.24 ml of polydiallyldimethylammonium chloride and 0.15 g of polyethylene glycol in 3 ml of tetrahydrofuran, and mix thoroughly with magnetic stirring at room temperature for 1 h to obtain the core layer solution.

[0075] S2: Dissolve 0.8 g of polyacrylonitrile in 8 ml of N,N-dimethylformamide, place in a 60℃ constant temperature water bath and stir for 2 h to completely dissolve it, and use it as the shell solution.

[0076] S3: Using core and shell solutions, coaxial electrospinning is performed at a voltage of 15-18 kV, a core injection rate of 0.02-0.05 mm / min, a shell injection rate of 0.10-0.15 mm / min, a receiving distance of 10-15 cm, and a receiver rotation speed of 200-300 rpm to prepare a core-shell structured nanofiber membrane on the surface of the barrier layer, forming a hygroscopic power generation layer (15-20 μm thick). The hygroscopic power generation layer consists of a core and a shell, with a fiber diameter of 360-400 nm, of which the core diameter accounts for 40-60%, the average fiber pore size is 1.2-2 μm, and the contact angle of the hygroscopic power generation layer is 54.7°. It can ionize to generate chloride ions.

[0077] 3. Preparation of the diffusion antibacterial layer:

[0078] S1: Dissolve 1 g of polyvinyl alcohol (degree of hydrolysis 88-90%) and 0.15 g of chitosan (degree of deacetylation ≥95%) in 10 ml of 90% acetic acid aqueous solution, and stir magnetically at room temperature for 3 h to completely dissolve them, thus obtaining a diffusion antibacterial layer solution.

[0079] S2: A polyvinyl alcohol / chitosan blended electrospun fiber membrane was prepared on the surface of the hygroscopic power generation layer by electrospinning the diffusion antibacterial layer solution under the conditions of 18-20 kV voltage, injection rate 0.04-0.08 mm / min, receiving distance 10-15 cm, and receiver rotation speed 200-300 rpm. This formed a diffusion antibacterial layer (20-25 μm thick). The fiber diameter of the diffusion antibacterial layer was 100-150 nm, the average pore size was 0.7-1.2 μm, and the contact angle was 44.7°, exhibiting good liquid diffusion properties and antibacterial activity.

[0080] 4. Preparation of the evaporative power generation layer:

[0081] S1: Dissolve 0.6 g polyacrylonitrile, 0.3 g polyethylene glycol, 0.18 ml poly-4-styrene sulfonic acid and 0.06 g acetylacetone iron in 6 ml N,N-dimethylformamide, place in a 60℃ constant temperature water bath and stir for 2 h to completely dissolve, to obtain the evaporation power generation layer solution.

[0082] S2: Electrospinning is performed on the diffusion antibacterial layer surface using an evaporative power generation layer solution under the following conditions: voltage 12-15 kV, injection rate 0.06-0.08 mm / min, receiving distance 10-15 cm, and receiver rotation speed 200-300 rpm. This produces a polyacrylonitrile / polyethylene glycol / poly4-styrenesulfonic acid / acetylacetone iron blend electrospun fiber membrane, forming an evaporative power generation layer (20-25 μm thick). The fiber diameter of the evaporative power generation layer is 500-550 nm, the average pore size is 1-2 μm, and the contact angle is 64.6°. This allows for efficient absorption of permeate and ionization to generate hydrogen and iron ions, further enhancing the power generation effect.

[0083] 5. Preparation of the electrode layer:

[0084] S1: Silver metal is deposited on the outside of the barrier layer by magnetron sputtering to form the first electrode layer (i.e., the inert electrode layer with a thickness of 0.8-1.6 μm), and magnesium metal is deposited on the outside of the evaporation power generation layer to form the second electrode layer (i.e., the active electrode layer with a thickness of 0.5-0.7 μm).

[0085] S2: Finally, vacuum dry for 24 hours, then sterilize by ultraviolet irradiation for 30-60 minutes to obtain the dual biomimetic wound dressing 1 with exudate management and self-generating power.

[0086] Example 2

[0087] This embodiment provides a method 2 for preparing a dual biomimetic wound dressing with exudate management and self-generating power. The preparation method is the same as in Example 1, except that in step 2, 0.09 ml of polydiallyldimethylammonium chloride and 0.15 g of polyethylene glycol are dissolved in 3 ml of tetrahydrofuran and mixed evenly with magnetic stirring at room temperature for 1 h to obtain the core layer solution.

[0088] A dual biomimetic wound dressing with exudate management and self-generating power was prepared.

[0089] Example 3

[0090] This embodiment provides a method 3 for preparing a dual biomimetic wound dressing with exudate management and self-generating power. The preparation method is the same as in Example 1, except that in step 2, 0.15 ml of polydiallyldimethylammonium chloride and 0.15 g of polyethylene glycol are dissolved in 3 ml of tetrahydrofuran and mixed evenly with magnetic stirring at room temperature for 1 h to obtain the core layer solution.

[0091] A dual biomimetic wound dressing with exudate management and self-generating power was prepared.

[0092] Example 4

[0093] This embodiment provides a method 4 for preparing a dual biomimetic wound dressing with exudate management and self-generating power. The preparation method is the same as in Example 1, except that in step 2, 0.3 ml of polydiallyldimethylammonium chloride and 0.15 g of polyethylene glycol are dissolved in 3 ml of tetrahydrofuran and mixed evenly with magnetic stirring at room temperature for 1 h to obtain the core layer solution.

[0094] A dual biomimetic wound dressing with exudate management and self-generating power was prepared.

[0095] The microstructure and power generation capacity of the hygroscopic power generation layer of polydiallyl dimethyl ammonium chloride at different concentrations in the dual biomimetic wound dressings prepared in Examples 1-4 were tested. The concentrations of polydiallyl dimethyl ammonium chloride in the hygroscopic power generation layer of Examples 1-4 are shown in Table 1. The results are as follows: Figure 2 and Figure 3 As shown, when the concentration of polydiallyldimethylammonium chloride is 8%, the fibers of the moisture-absorbing power generation layer are smoother, have a more uniform diameter, and exhibit excellent power generation capacity.

[0096] Table 1. Concentrations of polydiallyldimethylammonium chloride in Examples 1-4

[0097]

[0098] Example 5

[0099] This embodiment provides a method 5 for preparing a dual biomimetic wound dressing with exudate management and self-generating power. The preparation method is basically the same as in Example 1, except that in step 4, 0.6 g of polyacrylonitrile, 0.3 g of polyethylene glycol, 0.09 ml of poly(4-styrene sulfonic acid), and 0.06 g of acetylacetone iron are dissolved in 6 ml of N,N-dimethylformamide and stirred in a 60°C constant temperature water bath for 2 hours until completely dissolved.

[0100] A dual biomimetic wound dressing with exudate management and self-generating power was prepared.

[0101] Example 6

[0102] This embodiment provides a method 5 for preparing a dual biomimetic wound dressing with exudate management and self-generating power. The preparation method is basically the same as in Example 1, except that in step 4, 0.6 g of polyacrylonitrile, 0.3 g of polyethylene glycol, 0.45 ml of poly(4-styrene sulfonic acid), and 0.06 g of acetylacetone iron are dissolved in 6 ml of N,N-dimethylformamide and stirred in a 60°C constant temperature water bath for 2 hours until completely dissolved.

[0103] A dual-bionic wound dressing with exudate management and self-generating power was prepared.

[0104] Example 7

[0105] This embodiment provides a method 5 for preparing a dual biomimetic wound dressing with exudate management and self-generating power. The preparation method is basically the same as in Example 1, except that in step 4, 0.6 g of polyacrylonitrile, 0.3 g of polyethylene glycol, 0.9 ml of poly(4-styrene sulfonic acid), and 0.06 g of acetylacetone iron are dissolved in 6 ml of N,N-dimethylformamide and placed in a 60°C constant temperature water bath and stirred for 2 h until completely dissolved.

[0106] A dual biomimetic wound dressing with exudate management and self-generating power was prepared.

[0107] The microstructure and power generation capacity of the evaporation power generation layer of poly-4-styrene sulfonic acid in the dual biomimetic wound dressings 1 and 5-7 prepared in Examples 1 and 5-7, respectively, were tested. The concentration of poly-4-styrene sulfonic acid in the evaporation power generation layer is shown in Table 2. The results are as follows: Figure 4 and Figure 5 As shown, when the concentration of poly4-styrene sulfonic acid is 3%, the fibers of the evaporation power generation layer are smoother and have a more uniform diameter. The poly4-styrene sulfonic acid is evenly distributed in the fibers, exhibiting stable and excellent power generation capabilities.

[0108] Table 2. Poly(4-styrene) sulfonic acid concentrations in Examples 1 and 5-7

[0109]

[0110] Example 8

[0111] This embodiment provides a method 8 for preparing a dual biomimetic wound dressing with exudate management and self-generating power. The preparation method is basically the same as that in Embodiment 1, except that in step 5, gold metal is deposited on the outside of the barrier layer by magnetron sputtering to form a first electrode layer (i.e., an inert electrode layer), and gold metal is deposited on the outside of the evaporation power generation layer to form a second electrode layer (i.e., an inert electrode layer).

[0112] A dual biomimetic wound dressing with exudate management and self-generating power was prepared.

[0113] Example 9

[0114] This embodiment provides a method 9 for preparing a dual biomimetic wound dressing with exudate management and self-generating power. The preparation method is basically the same as that in Embodiment 1, except that in step 5, silver metal is deposited on the outside of the barrier layer by magnetron sputtering to form a first electrode layer (i.e., an inert electrode layer), and silver metal is deposited on the outside of the evaporation power generation layer to form a second electrode layer (i.e., an inert electrode layer).

[0115] A dual biomimetic wound dressing with exudate management and self-generating power was prepared.

[0116] Example 10

[0117] This embodiment provides a method 10 for preparing a dual biomimetic wound dressing that manages exudate and generates electricity. The preparation method is basically the same as that in Embodiment 1, except that in step 5, platinum metal is deposited on the outside of the barrier layer by magnetron sputtering to form a first electrode layer (i.e., an inert electrode layer), and platinum metal is deposited on the outside of the evaporation power generation layer to form a second electrode layer (i.e., an inert electrode layer).

[0118] A dual biomimetic wound dressing 10 with exudate management and self-generating power was prepared.

[0119] The open-circuit voltage and current density of the dual biomimetic wound dressings 8-10 prepared in Examples 8-10 were tested. The selection of inert metals in Examples 8-10 is shown in Table 3. The results are as follows: Figure 6 As shown, using silver as a barrier layer and the outer electrode of the evaporation power generation layer results in better electrical output performance.

[0120] Table 3. Inert metals selected in Examples 8-10

[0121]

[0122] Example 11

[0123] This embodiment provides a method 11 for preparing a dual biomimetic wound dressing that manages exudate and generates electricity. The preparation method is basically the same as that in Embodiment 1, except that in step 5, silver metal is deposited on the outside of the barrier layer by magnetron sputtering to form a first electrode layer (i.e., an inert electrode layer), and aluminum metal is deposited on the outside of the evaporation and power generation layer to form a second electrode layer (i.e., an active electrode layer).

[0124] A dual biomimetic wound dressing 11 with exudate management and self-generating power was prepared.

[0125] Example 12

[0126] This embodiment provides a method 12 for preparing a dual biomimetic wound dressing that manages exudate and generates electricity. The preparation method is basically the same as that in Embodiment 1, except that in step 5, silver metal is deposited on the outside of the barrier layer by magnetron sputtering to form a first electrode layer (i.e., an inert electrode layer), and zinc metal is deposited on the outside of the evaporation and power generation layer to form a second electrode layer (i.e., an active electrode layer).

[0127] A dual biomimetic wound dressing 12 with exudate management and self-generating power was prepared.

[0128] Example 13

[0129] This embodiment provides a method 13 for preparing a dual biomimetic wound dressing that manages exudate and generates electricity. The preparation method is basically the same as that in Embodiment 1, except that in step 5, silver metal is deposited on the outside of the barrier layer by magnetron sputtering to form a first electrode layer (i.e., an inert electrode layer), and iron metal is deposited on the outside of the evaporation and power generation layer to form a second electrode layer (i.e., an active electrode layer).

[0130] A dual biomimetic wound dressing 13 with exudate management and self-generating power was prepared.

[0131] Open-circuit voltage and current density tests were performed on the dual biomimetic wound dressings 1 and 11-13 prepared in Examples 1 and 11-13, respectively. The selection of active metals in Examples 1 and 11-13 is shown in Table 4. The results are as follows: Figure 7 As shown, using magnesium as the outer electrode of the evaporative power generation layer has a better electrical output effect.

[0132] Table 4. Active metals selected in Examples 1 and 11-13

[0133]

[0134] Example 14

[0135] This embodiment provides a method 14 for preparing a dual biomimetic wound dressing that manages exudate and generates its own electricity. The preparation method is the same as in Embodiment 1, except that:

[0136] (1) In step 1, 0.1 g of polylactic acid and 0.05 g of polycaprolactone were dissolved in 1 ml of hexafluoroisopropanol;

[0137] (2) In step 3, 1 g of polyvinyl alcohol and 0.1 g of chitosan are dissolved in 10 ml of 90% acetic acid aqueous solution;

[0138] (3) In step 4, 0.6 g of polyacrylonitrile, 0.3 g of polyethylene glycol, 0.18 ml of poly-4-styrene sulfonic acid and 0.03 g of acetylacetone iron are dissolved in 6 ml of N,N-dimethylformamide.

[0139] A dual biomimetic wound dressing 14 with exudate management and self-generating power was prepared.

[0140] Example 15

[0141] This embodiment provides a method 15 for preparing a dual biomimetic wound dressing that manages exudate and generates its own electricity. The preparation method is the same as in Embodiment 1, except that:

[0142] (1) In step 1, 0.1 g of polylactic acid and 0.25 g of polycaprolactone were dissolved in 1 ml of hexafluoroisopropanol;

[0143] (2) In step 3, 1 g of polyvinyl alcohol and 0.25 g of chitosan are dissolved in 10 ml of 90% acetic acid aqueous solution;

[0144] (3) In step 4, 0.6 g of polyacrylonitrile, 0.3 g of polyethylene glycol, 0.18 ml of poly-4-styrene sulfonic acid and 0.12 g of acetylacetone iron are dissolved in 6 ml of N,N-dimethylformamide.

[0145] A dual biomimetic wound dressing 15 with exudate management and self-generating power was prepared.

[0146] Example 16

[0147] Performance Testing of a Dual Bionic Wound Dressing for Exudate Management and Self-Generating Energy1

[0148] 1. Power generation performance testing under different relative humidity environments

[0149] The exudate management and self-generating biomimetic wound dressing 1 from Example 1 were placed in environments with different relative humidity (temperature maintained at 25°C) to test its power generation performance. The voltage and current densities were as follows: Figure 8As shown, the voltage and current density of the dual-bionic wound dressing exhibit a significant humidity dependence, increasing with rising humidity in a positive correlation, with the highest voltage output reaching 1.68 V. This is because higher ambient humidity is more conducive to the separation of positive and negative charges in the functional layer. Simultaneously, high humidity reduces the resistance of the dual-bionic wound dressing, and driven by the internal ion concentration gradient, ions move towards the opposite charge side, generating a higher electrical output.

[0150] 2. Power generation performance testing under different ambient temperatures

[0151] The exudate management and self-generating biomimetic wound dressing 1 from Example 1 were placed in environments at different temperatures (relative humidity maintained at 85%) to test its power generation performance. The voltage and current density were as follows: Figure 9 As shown, the electrical properties of the biomimetic wound dressing, including voltage and current density, exhibit a significant temperature dependence. As temperature increases, the ionic conductivity also increases, reaching a peak voltage output of 1.8 V at 45°C. With further temperature increases, the output performance shows a decreasing trend, which may be due to the increased movement of some polymer chain segments caused by high temperatures, disrupting the stability of the ion transport channels.

[0152] 3. Water vapor permeability testing

[0153] The exudate management and self-generating biomimetic wound dressing 1 from Example 1 was placed over the opening of a cylindrical test dish containing deionized water, ensuring a good seal. The ambient temperature was 37 ± 0.2℃, and the relative humidity was 50 ± 1%. The water evaporation mass was recorded after 24 hours, and the water vapor permeability was measured as follows: Figure 10 As shown, when the barrier layer of the dual biomimetic wound dressing is close to the liquid surface, the water vapor permeability reaches 12.99 g / (m²·d), which is superior to gauze dressings commonly used in clinical practice. This demonstrates that the unidirectional water transport function based on the Laplace pressure difference is more conducive to exudate management and can provide a favorable environment for wound healing.

[0154] Example 17

[0155] Antibacterial performance testing of dual biomimetic wound dressing 1 with exudate management and self-generating power.

[0156] The antibacterial properties of the exudate management and self-generating dual biomimetic wound dressing 1 prepared in Example 1 were evaluated using the plate count method. Staphylococcus aureus and Escherichia coli with good growth activity were diluted to 1×10⁻⁶ with PBS solution. 6 CFU / mL, after ultraviolet irradiation sterilization, the double biomimetic wound dressing 1 (size 1) 1cm 2Add 1 ml of diluted Staphylococcus aureus and Escherichia coli bacterial suspensions, respectively, and co-incubate at 37°C for 24 h. Inoculate 100 μL of the cultured bacterial suspensions evenly onto agar plates (n=3, 3 plates per experimental group, average colony count of the 3 plates). Photographs are taken after incubation at 37°C for 24 h. A control group was prepared using the bacterial suspension without the added biomimetic wound dressing 1. The number of surviving bacteria on the plates is as follows: Figure 11 As shown, the dual-bionic wound dressing exhibits an antibacterial rate exceeding 98% against both Staphylococcus aureus and Escherichia coli, demonstrating broad-spectrum antibacterial activity at three levels: physical destruction, chemical oxidation, and metabolic interference. It also shows significant inhibitory effects against both Gram-positive and Gram-negative bacteria.

[0157] Example 18

[0158] Application of dual biomimetic wound dressing for exudate management and self-generating power1

[0159] Rats were given subcutaneous injection of carbofen for pain relief. 30 minutes later, the rats were anesthetized by intraperitoneal injection of 5% chloral hydrate. All hair on the back was shaved off, and the remaining hair was completely removed with depilatory cream for 10 minutes. The skin was then cleaned and disinfected with 75% alcohol. A constant-temperature internal heating hot press head (15 mm in diameter, 120°C) was used to press on the skin on the rat's back for 20 seconds to form a deep second-degree burn wound with a diameter of 15 mm. The scab on the surface of the burn wound was removed after 24 hours.

[0160] Take 100 μL of Staphylococcus aureus culture with good growth activity from Example 17 (1×10⁻⁶). 6 CFU / mL was applied to the wound, and the wound was treated by applying a dual-bionic wound dressing with exudate management and self-generating power. Treatment continued for 14 days. A control group using commercially available 3M tegaderm dressing was used. Wounds were photographed at specific time points (0, 1, 3, 5, 7, 10, and 14 days), and the wound area was measured using ImageJ. Wound healing progress was assessed as follows. Figure 12 As shown, the wound contraction rate in the treatment group with the dual bionic wound dressing was significantly faster than that in the control group. The healing rate reached 75% on day 7, higher than the control group. By day 14, the wounds in the treatment group had essentially completed epithelialization, achieving a 100% healing rate and essentially restoring skin function.

[0161] All other parts not described in detail are existing technologies. Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, not all embodiments. People can obtain other embodiments based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A dual biomimetic wound dressing for exudate management and self-generating electricity, characterized in that: The dual bionic wound dressing comprises, from bottom to top, a first electrode layer, a barrier layer, a moisture-absorbing power-generating layer, a diffusion antibacterial layer, an evaporative power-generating layer, and a second electrode layer; The barrier layer, moisture-absorbing power generation layer, diffusion antibacterial layer, and evaporation power generation layer are electrospun fiber membranes; the first electrode layer and the second electrode layer are magnetron sputtering electrode layers. The barrier layer is made of polylactic acid and polycaprolactone, wherein the mass ratio of polylactic acid to polycaprolactone is 1:0.5-2.

5. The hygroscopic power generation layer includes a core layer and a shell layer. The raw materials of the core layer include polyethylene glycol and polydiallyl dimethyl ammonium chloride, and the mass-to-volume ratio of polyethylene glycol and polydiallyl dimethyl ammonium chloride is 1:0.6-2 g / mL. The raw material of the shell layer includes polyacrylonitrile. The raw materials for the diffusion antibacterial layer include polyvinyl alcohol and chitosan, wherein the mass ratio of polyvinyl alcohol to chitosan is 1:0.1-0.25; The raw materials for the evaporation power generation layer include polyacrylonitrile, polyethylene glycol, ferric acetylacetone, and poly-4-styrene sulfonic acid, wherein the mass ratio of polyacrylonitrile, polyethylene glycol, and ferric acetylacetone is 1:0.5:0.05-0.2; and the mass-volume ratio of polyacrylonitrile and poly-4-styrene sulfonic acid is 1:0.15-1.5 g / mL.

2. The dual bionic wound dressing according to claim 1, characterized in that: The mass ratio of polylactic acid to polycaprolactone is 1:1; The mass-to-volume ratio of polyethylene glycol and polydiallyl dimethylammonium chloride is 1:1.6 g / mL; The mass ratio of polyvinyl alcohol to chitosan is 1:0.15; The mass ratio of polyacrylonitrile, polyethylene glycol, and iron acetylacetone is 1:0.5:0.1; the mass-to-volume ratio of polyacrylonitrile and poly-4-styrene sulfonic acid is 1:0.3 g / mL. The first electrode layer is an inert electrode layer, and the second electrode layer is either an inert electrode layer or an active electrode layer.

3. The dual bionic wound dressing according to claim 2, characterized in that: The inert metal in the inert electrode layer is any one of gold, silver, and platinum, and the active metal in the active electrode layer is any one of magnesium, zinc, aluminum, and iron.

4. The dual bionic wound dressing according to claim 3, characterized in that: The inert metal in the inert electrode layer is silver, and the active metal in the active electrode layer is magnesium.

5. The dual bionic wound dressing according to claim 1, characterized in that: The thickness of the first electrode layer is 0.8-1.6 μm, the thickness of the barrier layer is 10-15 μm, the thickness of the moisture-absorbing power generation layer is 15-20 μm, the thickness of the diffusion antibacterial layer is 20-25 μm, the thickness of the evaporation power generation layer is 20-25 μm, and the thickness of the second electrode layer is 0.5-0.7 μm.

6. A method for preparing the dual biomimetic wound dressing according to any one of claims 1 to 5, characterized in that: Includes the following steps: (1) According to the above mass ratio of polylactic acid and polycaprolactone, polylactic acid and polycaprolactone are dissolved in hexafluoroisopropanol and stirred to obtain a barrier layer solution. (2) A barrier layer is formed by preparing a polylactic acid / polycaprolactone blend electrospun fiber membrane using a barrier layer solution via electrospinning technology. (3) According to the above mass-volume ratio of polyethylene glycol and polydiallyl dimethyl ammonium chloride, polyethylene glycol and polydiallyl dimethyl ammonium chloride are dissolved in tetrahydrofuran and stirred to obtain a core layer solution. Polyacrylonitrile is dissolved in N,N-dimethylformamide and stirred to obtain a shell layer solution. (4) Using core layer solution and shell layer solution, a core-shell structured nanofiber membrane is prepared on the surface of the barrier layer by coaxial electrospinning technology to form a moisture-absorbing and power-generating layer; (5) According to the above mass ratio of polyvinyl alcohol and chitosan, dissolve polyvinyl alcohol and chitosan in an aqueous acetic acid solution, and stir to obtain a diffusion antibacterial solution; (6) Using a diffusion antibacterial solution, a polyvinyl alcohol / chitosan blend electrospun fiber membrane is prepared on the surface of the moisture-absorbing power generation layer by electrospinning technology to form a diffusion antibacterial layer; (7) According to the above mass ratio of polyacrylonitrile, polyethylene glycol and acetylacetone iron and the mass-volume ratio of polyacrylonitrile and poly4-styrene sulfonic acid, polyacrylonitrile, polyethylene glycol and acetylacetone iron and poly4-styrene sulfonic acid are dissolved in N,N-dimethylformamide and stirred to obtain an evaporation power generation layer solution. (8) Using the evaporation power generation layer solution, a polyacrylonitrile / polyethylene glycol / poly4-styrenesulfonic acid / acetylacetone iron blend electrospun fiber membrane is prepared on the surface of the diffusion antibacterial layer by electrospinning technology to form an evaporation power generation layer; (9) An inert metal is deposited on the outside of the barrier layer by magnetron sputtering to form the first electrode layer, and an active metal or inert metal is deposited on the outside of the evaporation power generation layer to form the second electrode layer. After vacuum drying and ultraviolet irradiation sterilization, a dual biomimetic wound dressing with exudate management and self-generating power is obtained.

7. The preparation method according to claim 6, characterized in that: The barrier layer has a fiber diameter of 1600-2000 nm, an average fiber pore size of 8-10 μm, and a contact angle of 136.8°. The moisture-absorbing and power-generating layer has a fiber diameter of 360-400 nm, an average fiber pore size of 1.2-2 μm, and a contact angle of 54.7°. The diffusion antibacterial layer has a fiber diameter of 100-150 nm, an average fiber pore size of 0.7-1.2 μm, and a contact angle of 44.7°. The evaporation power generation layer has a fiber diameter of 500-550 nm, an average fiber pore size of 1-2 μm, and a contact angle of 64.6°.

8. The preparation method according to claim 6, characterized in that: In step (2), the voltage of the electrospinning technology is 6-8 kV, the injection rate is 0.2-0.25 mm / min, the receiving distance is 10-15 cm, and the receiver rotation speed is 200-300 rpm. In step (4), the voltage of the coaxial electrospinning technology is 15-18 kV, the core injection rate is 0.02-0.05 mm / min, the shell injection rate is 0.10-0.15 mm / min, the receiving distance is 10-15 cm, and the receiver rotation speed is 200-300 rpm. In step (6), the voltage of the electrospinning technology is 18-20 kV, the injection rate is 0.04-0.08 mm / min, the receiving distance is 10-15 cm, and the receiver rotation speed is 200-300 rpm. In step (8), the voltage of the electrospinning technology is 12-15 kV, the injection rate is 0.06-0.08 mm / min, the receiving distance is 10-15 cm, and the receiver rotation speed is 200-300 rpm.

9. The application of the dual biomimetic wound dressing according to any one of claims 1 to 5 in the preparation of antibacterial materials.

10. The use of the dual biomimetic wound dressing according to any one of claims 1 to 5 in the preparation of products that promote wound healing or prevent wound infection.

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